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WO2013163230A2 - Polymères d'origine biologique et leurs procédés de production - Google Patents

Polymères d'origine biologique et leurs procédés de production Download PDF

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Publication number
WO2013163230A2
WO2013163230A2 PCT/US2013/037862 US2013037862W WO2013163230A2 WO 2013163230 A2 WO2013163230 A2 WO 2013163230A2 US 2013037862 W US2013037862 W US 2013037862W WO 2013163230 A2 WO2013163230 A2 WO 2013163230A2
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Prior art keywords
phosphate
acid
cationic group
produce
saccharide composition
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PCT/US2013/037862
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English (en)
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WO2013163230A3 (fr
Inventor
Brian M. Baynes
Sadesh H. SOOKRAJ
John M. GEREMIA
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Midori Renewables, Inc.
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Publication of WO2013163230A2 publication Critical patent/WO2013163230A2/fr
Publication of WO2013163230A3 publication Critical patent/WO2013163230A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06—Ethanol, i.e. non-beverage
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/16—Butanols
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/18—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic polyhydric
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • the present disclosure relates generally to bio-based polymers and methods of producing such polymers, and more specifically to bio-based polymers that contain components that are derived partially or completely from biomass using the polymer catalysts described herein.
  • Biomass is cellulosic material that is not suitable for food production and can contain, for example, a combination of cellulose, hemicellulose, and lignin. Hydrolysis of biomass to constituent sugars can be followed by chemical or fermentation processes to convert the sugars to the monomers from which plastics are derived.
  • Exemplary monomers that are currently converted into plastics include ethylene glycol.
  • ethylene glycol is to produce polyethylene terephthalate by polymerizing ethylene glycol (MEG) with terephthalic acid (PTA).
  • PET polyethylene terephthalate
  • PET is widely used in, for example, bottles and containers for beverages and food.
  • propylene is chemically polymerized into polypropylene.
  • Polypropylene is used, for example, in making films, labels, trays, carpeting, automotive parts, and many other common plastic components.
  • the present disclosure addresses this need by providing methods to produce bio- based polymers, in which at least one component of the polymer is derived from a renewable source, such as biomass.
  • a method of producing an ethylene glycol compound by: a) providing a cellulosic material; b) contacting the cellulosic material with a polymer catalyst, c) degrading at least a portion of the cellulosic material to produce a saccharide composition; and d) combining the saccharide composition with a fermentation host to produce a fermentation product mixture that includes an ethylene glycol compound.
  • the method further includes isolating the ethylene glycol compound from the fermentation product mixture.
  • the method further includes purifying the isolated ethylene glycol compound.
  • a method of producing an ethylene glycol compound comprising: a) providing a cellulosic material;
  • the polymer catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, wherein a plurality of the acidic monomers independently comprise at least one Bronsted-Lowry acid, wherein one or more of the acidic monomers comprises a linker connecting the Bronsted-Lowry acid to the polymeric backbone, wherein a plurality of ionic monomers independently comprise at least one nitrogen-containing cationic group or phosphorous-containing cationic group, and wherein one or more of the ionic monomers comprises a linker connecting the nitrogen-containing cationic group or the phosphorous- containing cationic group to the polymeric backbone;
  • the method can also include isolating the ethylene glycol compound from the fermentation product mixture.
  • the ethylene glycol compound can be selected from monoethylene glycol, diethylene glycol, and polyethylene glycol.
  • a method of producing an ethylene glycol-containing compound comprising: combining a saccharide composition with a fermentation host to produce a fermentation product mixture comprising the ethylene glycol-containing compound, wherein the saccharide composition is produced by contacting a cellulosic material with a polymer catalyst, wherein the polymer catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, wherein a plurality of the acidic monomers independently comprise at least one Bronsted-Lowry acid, wherein one or more of the acidic monomers comprises a linker connecting the Bronsted-Lowry acid to the polymeric backbone, wherein a plurality of ionic monomers independently comprise at least one nitrogen-containing cationic group or phosphorous-containing cationic group, and wherein one or more of the ionic monomers comprises a linker connecting the nitrogen-containing cationic group or the phosphorous- containing cationic group to the polymeric backbone, under conditions such
  • the saccharide composition can include one or more of glucose, galactose, fructose, xylose, and arabinose. In some embodiments, the saccharide composition can include two or more of these sugars. In other embodiments, the saccharide composition can include xylose and the chemical intermediate is selected from xylonate, 2- dehydro-3-deoxy-D-pentonate, and glyco aldehyde. [0013] Provided is also an ethylene glycol compound produced according to any of the methods described above. In some embodiments, the ethylene glycol compound is monoethylene glycol, diethylene glycol, or polyethylene glycol. In one embodiment, the ethylene glycol compound is monoethylene glycol.
  • a method of producing a propylene-containing compound by: a) providing a cellulosic material; b) contacting the cellulosic material with a polymer catalyst, c) degrading at least a portion of the cellulosic material to produce a saccharide composition; and d) combining the saccharide composition with a fermentation host to produce a fermentation product mixture that includes one or more compounds selected from ethanol, lactic acid, 1,2-propanediol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; and e) converting the one or more compounds to the propylene-containing compound.
  • a method of producing a propylene-containing compound by: a) providing a cellulosic material; b) contacting the cellulosic material with a polymer catalyst, wherein the polymer catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, wherein a plurality of the acidic monomers independently comprise at least one Bronsted-Lowry acid, wherein one or more of the acidic monomers comprises a linker connecting the Bronsted-Lowry acid to the polymeric backbone, wherein a plurality of ionic monomers independently comprise at least one nitrogen-containing cationic group or phosphorous-containing cationic group, and wherein one or more of the ionic monomers comprises a linker connecting the nitrogen-containing cationic group or the phosphorous- containing cationic group to the polymeric backbone; c) degrading at least a portion of the cellulosic material to produce a saccharide composition;
  • the method further includes producing polypropylene from propylene.
  • a method of producing a propylene-containing compound comprising: a) combining a saccharide composition with a fermentation host to produce a fermentation product mixture comprising one or more compounds selected from ethanol, lactic acid, 1,2-propanediol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol, or a chemical intermediate between the saccharide composition and the one or more compounds, wherein the saccharide composition is produced by contacting a cellulosic material with a polymer catalyst, wherein the polymer catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, wherein a plurality of the acidic monomers independently comprise at least one Bronsted-Lowry acid, wherein one or more of the acidic monomers comprises a linker connecting the Bronsted-Lowry acid to the polymeric backbone, wherein a plurality of ionic monomers independently comprise at least one nitrogen-containing cationic group
  • a method of producing a bio-based polymer that has a terephthalate component and an ethylene glycol component by: a) providing a terephthalate component; b) providing an ethylene glycol component; and c) reacting the terephthalate component and the ethylene glycol component to produce a bio-based polymer, wherein at least about 1 wt of the ethylene glycol component is bio-derived.
  • the terephthalate component comprises terephthalic acid, dimethylterephthalate, isophthalic acid, or a combination thereof.
  • at least a portion of the ethylene glycol component is produced from cellulosic material.
  • the ethylene glycol component can be selected from monoethylene glycol, diethylene glycol, and polyethylene glycol.
  • a method of producing a bio-based polymer that has a polypropylene component by: a) providing a propylene component, wherein at least 1 wt of the propylene component is bio-derived; and b) reacting the propylene component to produce a bio-based polymer that has a polypropylene component.
  • the propylene reaction to form polypropylene can be, for example, a direct polymerization reaction or an indirect method, such as a process involving one or more intermediates. Such reactions are well known in the art. See, e.g., Moore, E.P. Polypropylene Handbook. Polymerization, Characterization, Properties, Processing, Applications. Hanser Publishers: New York, 1996.
  • At least about 5 wt , at least about 10 wt , at least about 15 wt , at least about 20 wt , at least about 25 wt , at least about 30 wt , at least about 40 wt , at least about 50 wt , at least about 60 wt , at least about 70 wt , at least about 80 wt , at least about 90 wt , or about 100 wt of the ethylene glycol component is bio-derived.
  • At least about 1 wt , at least about 5 wt , at least about 10 wt , at least about 15 wt , at least about 20 wt , at least about 25wt , at least about 30 wt , at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, at least about 90 wt%, or about 100 wt% of the ethylene glycol component is derived from cellulosic material (e.g. , biomass) degraded by a polymer catalyst.
  • At least about 1 wt%, at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25wt , at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, at least about 90 wt%, or about 100 wt% of the propylene component is derived from cellulosic material (e.g. , biomass) degraded by a polymer catalyst.
  • the polymer catalyst is a solid-supported acid catalyst or a polymeric acid catalyst.
  • the solid-supported acid catalyst can include a support and a plurality of acidic groups attached to the support.
  • the support is selected from biochar, carbon, amorphous carbon, activated carbon, silica, silica gel, and alumina, or a combination thereof.
  • the acidic groups at each occurrence are independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid.
  • the polymer catalyst can include a support and a plurality of acidic groups and cationic groups attached to the support.
  • the support is selected from biochar, carbon, amorphous carbon, activated carbon, silica, silica gel, and alumina, or a combination thereof.
  • the acidic groups at each occurence are independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid.
  • the ionic groups at each occurence are independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium, phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, triphenyl phosphonium and trifluoro phosphonium.
  • the polymer catalyst is a polymeric acid catalyst.
  • the polymeric acid catalyst has acidic monomers that are connected to form a polymeric backbone, in which each acidic monomer has at least one Bronsted-Lowry acid.
  • the polymeric acid catalyst has acidic monomers and ionic monomers that are connected to form a polymeric backbone, in which each acidic monomer has at least one Bronsted-Lowry acid, and each ionic monomer independently has at least one nitrogen- containing cationic group or phosphorous-containing cationic group.
  • the Bronsted-Lowry acid at each occurrence is independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid. In certain embodiments, the Bronsted-Lowry acid at each occurrence is independently sulfonic acid or phosphonic acid. In one embodiment, the Bronsted-Lowry acid at each occurrence is sulfonic acid.
  • the nitrogen-containing cationic group at each occurrence is independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
  • the nitrogen-containing cationic group is imidazolium.
  • the phosphorous-containing cationic group at each occurrence is independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
  • the phosphorous-containing cationic group is triphenyl phosphonium.
  • the one or more of the acidic monomers are directly connected to the polymeric backbone.
  • the one or more of the acidic monomers each further include a linker connecting the Bronsted-Lowry acid to the polymeric backbone.
  • some of the Bronsted-Lowry acids are directly connected to the polymeric backbone, while other the Bronsted-Lowry acids are connected to the polymeric backbone by a linker.
  • the one or more of the ionic monomers are directly connected to the polymeric backbone.
  • the one or more of the ionic monomers each further include a linker connecting the nitrogen-containing cationic group or the phosphorous-containing cationic group to the polymeric backbone.
  • some of the cationic groups are directly connected to the polymeric backbone, while other cationic groups are connected to the polymeric backbone by a linker.
  • the ethylene glycol component includes monoethylene glycol, diethylene glycol, or polyethylene glycol.
  • the bio-based polymer is polyethylene terephthalate, or copolyesters thereof.
  • the bio-based polymer is a polypropylene compound.
  • the bio-based polymer is recyclable, at least partially bio-degradable, or a combination thereof.
  • bio-based polymer produced according to any of the methods described herein.
  • the saccharide composition includes at least one C5 saccharide and at least one C6 saccharide. In other embodiments, the at least one C5 saccharide and the at least one C6 saccharide are present in the saccharide composition in a ratio suitable for fermentation to produce the ethylene glycol compound. In yet other embodiments, the ratio of the at least one C5 saccharide and the at least one C6 saccharide is further suitable to feed the fermentation host producing the ethylene glycol compound. In one embodiment, the saccharide composition includes xylose, glucose and arabinose. In another embodiment, the xylose, glucose and arabinose is present in the saccharide composition in a ratio of about 20 to 1 to 1.
  • the fermentation host is genetically modified to convert xylose to the ethylene glycol compound.
  • the fermentation host is genetically modified to convert xylose to ribulose, and ribulose to the ethylene glycol compound.
  • the fermentation host is a genetically modified E. coli strain.
  • the fermentation host is genetically modified to convert the saccharide composition into one or more compounds selected from ethanol, lactic acid, 1,2- propanediol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol. These intermediates can be converted to propylene via methods well known in the art.
  • the fermnentation host is a genetically modified bacterial strain selected from Citrobacter freundii, Clostridium propionicum, Clostribdium butyricum, Escherichia coli, Lactobacillus buchneri, Lactobacillus brevis, Pichia stipites, Saccharomyces cerevisiae, Salmonello entericia, and Carnobacterium maltaromaticurn.
  • the fermentation host is a genetically modified E. coli strain.
  • a method of producing a bio-based polymer that includes a terephthalate component and a diol component by: a) providing a terephthalate component; b) providing a diol component that includes an ethylene glycol compound, wherein at least a portion of the ethylene glycol compound is produced according to any of the methods described above; and c) reacting the terephthalate component and the diol component to produce a bio-based polymer.
  • the terephthalate component includes terephthalic acid, dimethylterephthalate, and isophthalic acid, or a combination thereof. In other embodiments, at least a portion of the terephthalate component is derived from cellulosic material (e.g., biomass).
  • At least about 1 wt , at least about 5 wt , at least about 10 wt , at least about 15 wt , at least about 20 wt , at least about 25 wt , at least about 30 wt , at least about 40 wt , at least about 50 wt , at least about 60 wt , at least about 70 wt , at least about 80 wt , at least about 90 wt , or about 100 wt of the terephthalate component is derived from cellulosic material. In other embodiments, of the terephthalate component is bio-derived.
  • the diol component further includes cyclohexane dimethanol.
  • at least about 1 wt , at least about 5 wt , at least about 10 wt , at least about 15 wt , at least about 20 wt , at least about 25 wt , at least about 30 wt , at least about 40 wt , at least about 50 wt , at least about 60 wt , at least about 70 wt , at least about 80 wt , at least about 90 wt , or about 100 wt of the ethylene glycol component is derived from cellulosic material (e.g., biomass).
  • At least about 1 wt , at least about 5 wt , at least about 10 wt , at least about 15 wt , at least about 20 wt , at least about 25 wt , at least about 30 wt , at least about 40 wt , at least about 50 wt , at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, at least about 90 wt%, or about 100 wt% of the ethylene glycol compound in the diol component is produced according to any of the methods described above.
  • the ethylene glycol component is derived from cellulosic material degraded by a polymer catalyst.
  • a method of producing a bio-based polymer that includes a polypropylene component by: a) providing a propylene component wherein at least a portion of the propylene-containing compound is produced according to any of the methods described above; and b) reacting the propylene component to produce a bio-based polymer that has a polypropylene component.
  • At least a portion of the propylene component is derived from cellulosic material (e.g. , biomass).
  • cellulosic material e.g. , biomass
  • cellulosic material e.g. , biomass
  • the propylene component is derived from cellulosic material degraded by a polymer catalyst.
  • a method of producing a saccharide composition suitable for use in preparing monoethylene glycol by: a) providing a cellulosic material; b) contacting the cellulosic material with a polymer catalyst, wherein the polymeric catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein a plurality of the acidic monomers independently have at least one Bronsted-Lowry acid, wherein one or more of the acidic monomers have a linker connecting the Bronsted-Lowry acid to the polymeric backbone, wherein a plurality of ionic monomers independently have at least one nitrogen-containing cationic group or phosphorous-containing cationic group, and wherein one or more of the ionic monomers have a linker connecting the nitrogen-containing cationic group or the phosphorous-containing cationic group to the polymeric backbone; and c) degrading at least a portion of the cellulosic material to produce
  • the method further includes combining the saccharide composition with a fermentation host to produce a fermentation product mixture that includes monoethylene glycol. In other embodiments, the method further includes reacting the monoethylene glycol with a terephthalate component to produce a bio-based polymer.
  • a method of producing a saccharide composition suitable for use in preparing suitable for use in preparing one or more compounds selected from ethanol, lactic acid, 1,2-propanediol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol by: a) providing a cellulosic material; b) contacting the cellulosic material with a polymer catalyst, wherein the polymer catalyst includes acidic monomers and ionic monomers connected to form a polymeric backbone, wherein a plurality of the acidic monomers independently have at least one Bronsted- Lowry acid, wherein one or more of the acidic monomers have a linker connecting the Bronsted- Lowry acid to the polymeric backbone, wherein a plurality of ionic monomers independently have at least one nitrogen-containing cationic group or phosphorous-containing cationic group, and wherein one or more of the ionic monomers have a linker connecting the
  • the method further includes d) combining the saccharide composition with a fermentation host to produce a fermentation product mixture that includes one or more compounds selected from compounds selected from ethanol, lactic acid, 1,2- propanediol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol.
  • the method further includes e) isolating the one or more compounds from the fermentation mixture.
  • the method further includes converting the one or more compounds selected from ethanol, lactic acid, 1,2-propanediol, 1-propanol, 2-propanol, 1-butanol, and 2- butanol to propylene, and producing a polypropylene-containing compound from said propylene.
  • composition comprising the saccharide composition and a fermentation host under conditions such that one or more compounds selected from ethanol, lactic acid, 1,2-propanediol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol are capable of being produced.
  • the at least one C5 saccharide and the at least one C6 saccharide are present in the saccharide composition in a ratio suitable for fermentation to produce the monoethylene glycol.
  • the at least one C5 saccharide is xylose and arabinose
  • the at least one C6 saccharide is glucose.
  • the xylose, glucose and arabinose is present in the saccharide composition in a ratio of about 20 to 1 to 1.
  • the Bronsted-Lowry acid at each occurrence is independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid. In certain embodiments, the Bronsted-Lowry acid at each occurrence is independently sulfonic acid or phosphonic acid. In one embodiment, the Bronsted-Lowry acid at each occurrence is sulfonic acid.
  • the nitrogen-containing cationic group at each occurrence is independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
  • the nitrogen-containing cationic group is imidazolium.
  • the phosphorous-containing cationic group at each occurrence is independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
  • the phosphorous-containing cationic group is triphenyl phosphonium.
  • the linker at each occurrence is independently selected from unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene, unsubstituted or substituted alkylene ether, unsubstituted or substituted alkylene ester, and unsubstituted or substituted alkylene carbamate.
  • the linker at each occurence is independently unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene.
  • the linker is unsubstituted or substituted arylene.
  • the linker is phenylene.
  • the linker is hydroxyl- substituted phenylene.
  • compositions having a saccharide composition and a fermentation host under conditions suitable to produce ethylene glycol are provided herein.
  • FIG. 1 illustrates a portion of an exemplary polymer that has a polymeric backbone and side chains.
  • FIG. 2 illustrates a portion of an exemplary polymer, in which a side chain with the acidic group is connected to the polymeric backbone by a linker and in which a side chain with the cationic group is connected directly to the polymeric backbone.
  • FIG. 3A illustrates a portion of an exemplary polymer, in which the monomers are randomly arranged in an alternating sequence.
  • FIG. 3B illustrates a portion of an exemplary polymer, in which the monomers are arranged in blocks of monomers, and the block of acidic monomers alternates with the block of ionic monomers.
  • FIGS. 4A and 4B illustrate a portion of exemplary polymers with cross-linking within a given polymeric chain.
  • FIGS. 5A, 5B, 5C and 5D illustrate a portion of exemplary polymers with cross- linking between two polymeric chains.
  • FIG. 6A illustrates a portion of an exemplary polymer with a polyethylene backbone.
  • FIG. 6B illustrates a portion of an exemplary polymer with a polyvinylalcohol backbone.
  • FIG. 6C illustrates a portion of an exemplary polymer with an ionomeric backbone.
  • FIG. 7A illustrates two side chains in an exemplary polymer, in which there are three carbon atoms between the side chain with the Bronsted-Lowry acid and the side chain with the cationic group.
  • FIG. 7B illustrates two side chains in another exemplary polymer, in which there are zero carbons between the side chain with the Bronsted-Lowry acid and the side chain with the cationic group.
  • FIG. 8 illustrates several non-limiting exemplary series of transformations of biomass to produce propylene.
  • FIG. 9 illustrates metabolic pathways from several sugars that can be produced by the methods described herein through one or more intermediates to reach 2-dihydroxyacetone phosphate (DHAP) and glyco aldehyde.
  • DHAP 2-dihydroxyacetone phosphate
  • FIG. 10 illustrates metabolic pathways from DHAP and glycoaldehyde to precursor compounds of propylene, such as propanol and propanoate.
  • FIG. 11 illustrates metabolic pathways from 1,2-propanediol and DHAP to precursor compounds of propylene, such as 1,3-propanediol and 3-hydroxypropanoate.
  • “Bronsted-Lowry acid” refers to a molecule, or substituent thereof, in neutral or ionic form that is capable of donating a proton (hydrogen cation, H + ).
  • Homopolymer refers to a polymer having at least two monomer units, and where all the units contained within the polymer are derived from the same monomer in the same manner.
  • a non-limiting example is polyethylene, where ethylene monomers are linked to form a uniform repeating chain (-CH 2 -CH 2 -CH 2 -).
  • Heteropolymer refers to a polymer having at least two monomer units, and where at least one monomeric unit differs from the other monomeric units in the polymer. Heteropolymer also refers to polymers having difunctionalized, or trifunctionalized, monomer units that can be incorporated in the polymer in different ways. The different monomer units in the polymer can be in a random order, in an alternating sequence of any length of a given monomer, or in blocks of monomers. A non-limiting example is polyethyleneimidazolium, where if in an alternating sequence, would be the polymer depicted in FIG. 6C.
  • polystyrene-co-divinylbenzene where if in an alternating sequence, could be (-CH 2 -CH(phenyl)-CH 2 -CH(4-ethylenephenyl)-CH 2 -CH(phenyl)-CH 2 -CH(4-ethylenephenyl)-).
  • the ethenyl functionality could be at the 2, 3, or 4position on the phenyl ring.
  • plastic refers to any synthetic or semisynthetic organic solid that is moldable.
  • a plastic contains one or more organic polymers, such as a homopolymer or heteropolymer. These polymers can have a backbone chain with repeating monomer units, and optionally, functional groups attached to the backbone as side chains. Attachment can be directly to the backbone or through a linker as described herein.
  • the plastic can contain one or more additives that are separate entities from the polymer content. Such additives include, but are not limited to, antimicrobials, antioxidants, plasticizers, lubricants, fillers, light and heat stabilizers, fragrances, and pigments.
  • Plastics are catergorized as either thermoplastics or thermosetting polymers. Thermoplastics do not ondergo chemical change when heated and can be remolded. Polypropylene is an example of a thermoplastic. Thermosetting polymers melt during an irreversible chemical process to form a plastic shape which can not be remolded. Vulcanization of rubber is an example of a thermosetting polymer. Plastics can also be characterized by their biodegradability, elastomeric capability, electrical conductance, tensile strength, crystallinity and density.
  • ethylene glycol compound As used herein, the terms "ethylene glycol compound”, “ethylene glycol-containing compound” and “ethylene glycol component” refer to any of monoethylene glycol, diethylene glycol, or polyethylene glycol. The term “ethylene glycol” refers specifically to monoethylene glycol.
  • polypropylene or “polypropylene-containing compound” refers to any addition polymer made from the propylene monomer.
  • Polypropylenes can have thermoplastic and/or isotactic properties. Polypropylene can be atactic, syndiotactic, or a mixture thereof. Generally, there are three types of polypropylene, homopolymer, random copolymer and block copolymer.
  • One common method of polymerization of propylene to afford polypropylene uses one or more of the Ziegler-Natta family of catalysts.
  • ⁇ wv denotes a generic polymeric backbone to which one or more substitutents or sidechains can be attached, as denoted by a straight perpendicular line descending from the mark.
  • Alkyl refers to a straight or branched hydrocarbon chain group consisting solely of carbon and hydrogen atoms, containing no unsaturation, having from one to ten carbon atoms (e.g. , C Cio alkyl, 1- lOC, C1-C10 or Cl-10).
  • a numerical range such as “1 to 10” refers to each integer in the given range; e.g., "1 to 10 carbon atoms” means that the alkyl group can consist of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 10 carbon atoms, although the present definition also covers the occurrence of the term "alkyl” where no numerical range is designated.
  • alkyl groups have 1 to 10, 1 to 6, or 1 to 3 carbon atoms.
  • Representative saturated straight chain alkyls include -methyl, -ethyl, -n-propyl, -n-butyl, -n-pentyl, and -n- hexyl; while saturated branched alkyls include -isopropyl, -sec-butyl, -isobutyl, -tert-butyl, - isopentyl, 2-methylbutyl, 3-methylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2- methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 2,3-dimethylbutyl, and the like.
  • the alkyl is attached to the rest of the molecule by a single bond, for example, methyl (Me), ethyl (Et), w-propyl, 1-methylethyl (isopropyl), w-butyl, w-pentyl, 1,1-dimethylethyl (i-butyl), 3-methylhexyl, 2-methylhexyl, and the like.
  • alkylene refers to the same residues as alkyl, but having bivalency. Examples of alkylene include methylene (-CH 2 -), ethylene (-CH 2 CH 2 -), propylene (-CH 2 CH 2 CH 2 -), butylene (-CH 2 CH 2 CH 2 CH 2 -).
  • an alkyl group is optionally substituted by one or more of substituents which independently include: alkyl, alkoxy, alkylaryl, cycloalkyl, aralkyl, aryl, aryloxy, amino, amido, carbamate, carbonyl, heteroalkyl, heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, ether, thio, alkylthio, arylthio, -OR a , -SR a , - N(Ra) 2 , -C(0)R a , -C(0)N(R a ) 2 , -N(R a )C(0)R a , -N(R a )S(0)tR a (where t is 1 or 2), and - S(0)tN(R a ) 2 (where t is 1 or 2), where each R a is independently hydrogen, alkyl, alkoxy,
  • Perhaloalkyl refers to an alkyl group in which all of the hydrogen atoms have been replaced with a halogen selected from fluoro, chloro, bromo, and iodo. In some embodiments, all of the hydrogen atoms are each replaced with fluoro. In some embodiments, all of the hydrogen atoms are each replaced with chloro. Examples of perhaloalkyl groups include -CF 3 , - CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CC1 3 , -CFC1 2 , -CF 2 C1 and the like.
  • Alkylaryl refers to an -(alkyl)aryl group where aryl and alkyl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for aryl and alkyl respectively.
  • the “alkylaryl” is bonded to the parent molecular structure through the alkyl group.
  • alkoxy refers to the group -O-alkyl, including from 1 to 10 carbon atoms of a straight, branched, cyclic configuration and combinations thereof, attached to the parent molecular structure through an oxygen atom. Examples include methoxy, ethoxy, propoxy, isopropoxy, cyclopropyloxy, cyclohexyloxy and the like.
  • Lower alkoxy refers to alkoxy groups containing one to six carbons.
  • Q-C4 alkoxy is an alkoxy group which encompasses both straight and branched chain alkyls of from 1 to 4 carbon atoms.
  • an alkoxy group is optionally substituted by one or more substituents which independently include: alkyl, alkoxy, alkylaryl, cycloalkyl, aralkyl, aryl, aryloxy, amino, amido, carbamate, carbonyl, heteroalkyl, heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, ether, thio, alkylthio, arylthio, -OR a , -SR a , -N(R a ) 2 , -C(0)R a , - C(0)N(R a ) 2 , -N(R a )C(0)R a , -N(R a )S(0)tR a (where t is 1 or 2), and -S(0)tN(R a ) 2 (where t is 1 or 2), where each R a is independently hydrogen,
  • alkenyl refers to a straight or branched hydrocarbon chain group consisting solely of carbon and hydrogen atoms, containing at least one double bond, and having from two to ten carbon atoms (i.e., C2-C10 alkenyl). Whenever it appears herein, a numerical range such as “2 to 10" refers to each integer in the given range; e.g., "2 to 10 carbon atoms” means that the alkenyl group can consist of 2 carbon atoms, 3 carbon atoms, etc., up to and including 10 carbon atoms. In certain embodiments, an alkenyl comprises two to eight carbon atoms.
  • an alkenyl comprises two to five carbon atoms (e.g., C2-C5 alkenyl).
  • alkenyl residue having a specific number of carbons all geometric isomers having that number of carbons are intended to be encompassed and described; thus, for example, "butenyl” is meant to include w-butenyl, sec-butenyl, and isobutenyl.
  • the alkenyl is attached to the parent molecular structure by a single bond, for example, ethenyl (i.e., vinyl), prop 1 enyl (i.e., allyl), but 1 enyl, pent 1 enyl, penta 1,4 dienyl, and the like.
  • the one or more carbon-carbon double bonds can be internal (such as in 2-butenyl) or terminal (such as in 1-butenyl).
  • Examples of C2-4 alkenyl groups include ethenyl (C2), 1-propenyl (C3), 2-propenyl (C3), 1-butenyl (C4), 2-butenyl (C4), butadienyl (C4) and the like.
  • Examples of C2-6 alkenyl groups include the aforementioned C2- 4 alkenyl groups as well as pentenyl (C5), pentadienyl (C5), hexenyl (C6) and the like. Additional examples of alkenyl include heptenyl (C7), octenyl (C8), octatrienyl (C8) and the like.
  • Alkenyl contains only C and H when unsubstituted. Unless stated otherwise in the specification, an alkenyl group is optionally substituted by one or more substituents which independently include: alkyl, alkoxy, alkylaryl, cycloalkyl, aralkyl, aryl, aryloxy, amino, amido, carbamate, carbonyl, heteroalkyl, heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, ether, thio, alkylthio, arylthio, -OR a , -SR a , -N(R a ) 2 , -C(0)R a , - C(0)N(R a ) 2 , -N(Ra)C(0)Ra, -N(R a )S(0)tR a (where t is 1 or 2), and -S(0)tN(R a ) 2 (where
  • Amino refers to a -N(R b ) 2 , -N(R b ) R b -, or -R b N(R b )R b - group, where each R b is independently selected from hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (bonded through a chain carbon), cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocycloalkyl (bonded through a ring carbon), heterocycloalkylalkyl, heteroaryl (bonded through a ring carbon) or heteroarylalkyl, unless stated otherwise in the specification, each of which moiety can itself be optionally substituted as described herein.
  • a -N(R b ) 2 group When a -N(R b ) 2 group has two R b other than hydrogen, they can be combined with the nitrogen atom to form a 3-, 4-, 5-, 6-, or 7-membered ring.
  • -N(R b ) 2 is meant to include, but not be limited to, 1-pyrrolidinyl and 4- morpholinyl.
  • an amino group is optionally substituted by one or more substituents which independently include: alkyl, alkoxy, alkylaryl, cycloalkyl, aralkyl, aryl, aryloxy, amino, amido, carbamate, carbonyl, heteroalkyl, heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, ether, thio, alkylthio, arylthio, -OR a , -SR a , - N(R a ) 2 , -C(0)R a , -C(0)N(R a ) 2 , -N(R a )C(0)R a , -N(R a )S(0)tR a (where t is 1 or 2), and - S(0)tN(R a ) 2 (where t is 1 or 2), where each R a is independently hydrogen, alkyl, alkoxy, al
  • amino also refers to N-oxides of the groups -N + (H)(R a )0 ⁇ , and - N + (R a )(R a) 0-, R a as described above, where the N-oxide is bonded to the parent molecular structure through the N atom.
  • N-oxides can be prepared by treatment of the corresponding amino group with, for example, hydrogen peroxide or m-chloroperoxybenzoic acid. The person skilled in the art is familiar with reaction conditions for carrying out the N-oxidation.
  • Amide refers to a chemical moiety with formula -C(0)N(R b ) 2 or - NR b C(0)R b , where R b is independently selected from hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (bonded through a chain carbon), cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocycloalkyl (bonded through a ring carbon), heterocycloalkylalkyl, heteroaryl (bonded through a ring carbon) or heteroarylalkyl, unless stated otherwise in the specification, each of which moiety can itself be optionally substituted as described herein.
  • this group is a Ci-C4 amido or amide group, which includes the amide carbonyl in the total number of carbons in the group.
  • a -C(0)N(R b ) 2 has two R b other than hydrogen, they can be combined with the nitrogen atom to form a 3-, 4-, 5-, 6-, or 7-membered ring.
  • N(R b ) 2 portion of a -C(0)N(R b ) 2 group is meant to include, but not be limited to, 1-pyrrolidinyl and 4-morpholinyl.
  • an amido R b group is optionally substituted by one or more substituents which independently include: alkyl, alkoxy, alkylaryl, cycloalkyl, aralkyl, aryl, aryloxy, amino, amido, carbamate, carbonyl, heteroalkyl, heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, ether, thio, alkylthio, arylthio, -OR a , -SR a , - N(R a ) 2 , -C(0)R a , -C(0)N(R a ) 2 , -N(R a )C(0)R a , -N(R a )S(0)tR a (where t is 1 or 2), and - S(0)tN(R a ) 2 (where t is 1 or 2), where each R a is independently
  • Aromatic or “aryl” refers to a group with six to ten ring atoms (e.g., C 6 -Q 0 aromatic or C 6 -Q 0 aryl) which has at least one ring having a conjugated pi electron system which is carbocyclic (e.g., phenyl, fluorenyl, and naphthyl).
  • the aromatic carbocyclic group can have a single ring (e.g. , phenyl) or multiple condensed rings (e.g., naphthyl or anthryl), which condensed rings may or may not be aromatic.
  • bivalent radicals formed from substituted benzene derivatives and having the free valences at ring atoms are named as substituted phenylene radicals.
  • bivalent radicals derived from univalent polycyclic hydrocarbon radicals whose names end in "-yl” by removal of one hydrogen atom from the carbon atom with the free valence are named by adding "-idene" to the name of the corresponding univalent radical, e.g., a naphthyl group with two points of attachment is termed naphthylidene.
  • aryl group having more than one ring where at least one ring is non-aromatic can be connected to the parent structure at either an aromatic ring position or at a non-aromatic ring position.
  • a numerical range such as "6 to 10 aryl” refers to each integer in the given range; e.g., "6 to 10 ring atoms” means that the aryl group can consist of 6 ring atoms, 7 ring atoms, etc., up to and including 10 ring atoms.
  • the term includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of ring atoms) groups. Examples of aryl can include phenyl, phenol, and benzyl.
  • an aryl moiety can be optionally substituted by one or more substituents which independently include: alkyl, alkoxy, alkylaryl, cycloalkyl, aralkyl, aryl, aryloxy, amino, amido, carbamate, carbonyl, heteroalkyl, heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, ether, thio, alkylthio, arylthio, -OR a , -SR a , -N(R a ) 2 , -C(0)R a , -C(0)N(R a ) 2 , -N(R a )C(0)R a , - N(R a )S(0)tR a (where t is 1 or 2), and -S(0)tN(R a ) 2 (where t is 1 or 2), where each R a is independently
  • Aralkyl or “arylalkyl” refers to an (aryl)alkyl— group where aryl and alkyl are as disclosed herein and which are optionally substituted by one or more of the substituents described as suitable substituents for aryl and alkyl respectively.
  • the “aralkyl/arylalkyl” is bonded to the parent molecular structure through the alkyl group.
  • aralkenyl/arylalkenyl and “aralkynyl/arylalkynyl” mirror the above description of “aralkyl/arylalkyl” wherein the “alkyl” is replaced with “alkenyl” or “alkynyl” respectively, and the “alkenyl” or “alkynyl” terms are as described herein.
  • Azide refers to a -N 3 radical.
  • Cyano refers to a -CN group.
  • Cycloalkyl refers to a monocyclic or polycyclic group that contains only carbon and hydrogen, and can be saturated, or partially unsaturated. Partially unsaturated cycloalkyl groups can be termed “cycloalkenyl” if the carbocycle contains at least one double bond, or "cycloalkynyl” if the carbocycle contains at least one triple bond.
  • the cycloalkyl can consist of one ring, such as cyclohexyl, or multiple rings, such as adamantyl.
  • a cycloalkyl with more than one ring can be fused, spiro or bridged, or combinations thereof.
  • Cycloalkyl groups include groups having from 3 to 10 ring atoms (i.e., C 3 -Q0 cycloalkyl). Whenever it appears herein, a numerical range such as “3 to 10" refers to each integer in the given range; e.g., "3 to 10 carbon atoms” means that the cycloalkyl group can consist of 3 carbon atoms, 4 carbon atoms, 5 carbon atoms, etc., up to and including 10 carbon atoms.
  • the term "cycloalkyl” also includes bridged and spiro-fused cyclic structures containing no heteroatoms. The term also includes monocyclic or fused-ring polycyclic (i.e., rings which share adjacent pairs of ring atoms) groups.
  • C 3 _6 carbocyclyl groups include, without limitation, cyclopropyl (C 3 ), cyclobutyl (C 4 ), cyclopentyl (C 5 ), cyclopentenyl (C 5 ), cyclohexyl (C 6 ), cyclohexenyl (C 6 ), cyclohexadienyl (C 6 ) and the like.
  • C 3 _ 8 carbocyclyl groups include the aforementioned C 3 _ 6 carbocyclyl groups as well as cycloheptyl (C 7 ), cycloheptadienyl (C 7 ), cycloheptatrienyl (C 7 ), cyclooctyl (C 8 ), bicyclo[2.2.1]heptanyl, bicyclo[2.2.2]octanyl, and the like.
  • Examples of C 3 _ 10 carbocyclyl groups include the aforementioned C 3 _ 8 carbocyclyl groups as well as octahydro-lH-indenyl, decahydronaphthalenyl, spiro[4.5]decanyl and the like.
  • cycloalkylene refers to the same residues as cycloalkyl, but having bivalency. Unless stated otherwise in the specification, a cycloalkyl group is optionally substituted by one or more substituents which independently include: alkyl, alkoxy, alkylaryl, cycloalkyl, aralkyl, aryl, aryloxy, amino, amido, carbamate, carbonyl, heteroalkyl, heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, ether, thio, alkylthio, arylthio, -OR a , -SR a , -N(R a ) 2 , -C(0)R a , -C(0)N(R a ) 2 , - N(R a )C(0)R a , -N(R a )S(0)tR a (where t
  • Ether refers to a -R b -0-R b - group where each R b is independently selected from hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (bonded through a chain carbon), cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocycloalkyl (bonded through a ring carbon), heterocycloalkylalkyl, heteroaryl (bonded through a ring carbon) or heteroarylalkyl, unless stated otherwise in the specification, each of which moiety can itself be optionally substituted as described herein.
  • Halo means fluoro, chloro, bromo or iodo.
  • haloalkyl means alkyl, alkenyl, alkynyl and alkoxy structures that are substituted with one or more halo groups or with combinations thereof.
  • fluoroalkyl and fluoro alkoxy include haloalkyl and haloalkoxy groups, respectively, in which the halo is fluorine, such as, but not limited to, trifluoromethyl, difluoro methyl, 2,2,2-trifluoroethyl, l-fluoromethyl-2-fluoroethyl, and the like.
  • halo is fluorine, such as, but not limited to, trifluoromethyl, difluoro methyl, 2,2,2-trifluoroethyl, l-fluoromethyl-2-fluoroethyl, and the like.
  • alkyl, alkenyl, alkynyl and alkoxy groups can be optionally substituted as defined herein.
  • Heteroalkyl includes optionally substituted alkyl, alkenyl and alkynyl groups, respectively, and which have one or more skeletal chain atoms selected from an atom other than carbon, e.g., oxygen, nitrogen, sulfur, phosphorus or combinations thereof.
  • a numerical range can be given, e.g., CrC 4 heteroalkyl which refers to the chain length in total, which in this example is 4 atoms long.
  • a -CH 2 OCH 2 CH 3 group is referred to as a "C 4 " heteroalkyl, which includes the heteroatom center in the atom chain length description.
  • heteroalkyl groups include, without limitation, ethers such as methoxyethanyl (-CH 2 CH 2 OCH 3 ), ethoxymethanyl (-CH 2 OCH 2 CH 3 ), (methoxymethoxy)ethanyl (-CH 2 CH 2 OCH 2 OCH ), (methoxymethoxy)methanyl (-CH 2 CH 2 OCH ), (methoxymethoxy)methanyl (-
  • a heteroalkyl group can be optionally substituted by one or more substituents which independently include: alkyl, alkoxy, alkylaryl, cycloalkyl, aralkyl, aryl, aryloxy, amino, amido, carbamate, carbonyl, heteroalkyl, heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, ether, thio, alkylthio, arylthio, -OR a , -SR a , -N(R a ) 2 , -C(0)R a , -C(0)N(R a ) 2 , - N(R a )C(0)R a , -N(R a )S(0)tR a (where t is 1 or 2), and -S(0)tN(R a ) 2 (where t is 1 or 2), where each R a is independently hydrogen, alkyl,
  • Heteroaryl or, alternatively, “heteroaromatic” refers to a refers to a group of a 5- 18 membered monocyclic or polycyclic (e.g., bicyclic or tricyclic) aromatic ring system (e.g., having 6, 10 or 14 ⁇ electrons shared in a cyclic array) having ring carbon atoms and 1-6 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen ,phosphorous and sulfur ("5-18 membered heteroaryl").
  • a heteroaryl group may have a single ring (e.g.
  • heteroaryl group having more than one ring where at least one ring is non-aromatic can be connected to the parent structure at either an aromatic ring position or at a non-aromatic ring position.
  • a heteroaryl group having more than one ring where at least one ring is non-aromatic is connected to the parent structure at an aromatic ring position.
  • Heteroaryl polycyclic ring systems can include one or more heteroatoms in one or both rings.
  • a numerical range such as “5 to 18” refers to each integer in the given range; e.g., "5 to 18 ring atoms” means that the heteroaryl group can consist of 5 ring atoms, 6 ring atoms, etc., up to and including 18 ring atoms.
  • bivalent radicals derived from univalent heteroaryl radicals whose names end in "-yl” by removal of one hydrogen atom from the atom with the free valence are named by adding "-idene" to the name of the corresponding univalent radical, e.g., a pyridyl group with two points of attachment is a pyridylidene.
  • an N-containing “heteroaromatic” or “heteroaryl” moiety refers to an aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom.
  • One or more heteroatom(s) in the heteroaryl group can be optionally oxidized.
  • One or more nitrogen atoms, if present, are optionally quaternized.
  • Heteroaryl also includes ring systems substituted with one or more oxide (-0-) substituents, such as pyridinyl N-oxides. The heteroaryl is attached to the parent molecular structure through any atom of the ring(s).
  • Heteroaryl also includes ring systems wherein the heteroaryl ring, as defined above, is fused with one or more aryl groups wherein the point of attachment is either on the aryl or on the heteroaryl ring, or wherein the heteroaryl ring, as defined above, is fused with one or more carbocycyl or heterocycyl groups wherein the point of attachment is on the heteroaryl ring.
  • a heteroaryl group is a 5-10 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous, and sulfur ("5-10 membered heteroaryl").
  • a heteroaryl group is a 5-8 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous, and sulfur ("5-8 membered heteroaryl").
  • a heteroaryl group is a 5-6 membered aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms provided in the aromatic ring system, wherein each heteroatom is independently selected from nitrogen, oxygen, phosphorous, and sulfur ("5-6 membered heteroaryl”).
  • the 5-6 membered heteroaryl has 1-3 ring heteroatoms selected from nitrogen, oxygen, phosphorous, and sulfur.
  • the 5-6 membered heteroaryl has 1-2 ring heteroatoms selected from nitrogen, oxygen, phosphorous, and sulfur. In some embodiments, the 5-6 membered heteroaryl has 1 ring heteroatom selected from nitrogen, oxygen, phosphorous, and sulfur.
  • heteroaryls include, but are not limited to, azepinyl, acridinyl, benzimidazolyl, benzindolyl, 1,3-benzodioxolyl, benzofuranyl, benzooxazolyl, benzo[d]thiazolyl, benzothiadiazolyl, benzo[b][l,4]dioxepinyl, benzo[b] [l,4]oxazinyl, 1,4-benzodioxanyl, benzonaphthofuranyl, benzoxazolyl, benzodioxolyl, benzodioxinyl, benzoxazolyl, benzopyranyl, benzopyranonyl, benzofuranyl, benzofuranonyl, benzofurazanyl, benzothiazolyl, benzothienyl (benzothiophenyl), benzothieno[3,2-d]pyr
  • a heteroaryl moiety is optionally substituted by one or more substituents which independently include: alkyl, alkoxy, alkylaryl, cycloalkyl, aralkyl, aryl, aryloxy, amino, amido, carbamate, carbonyl, heteroalkyl, heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, ether, thio, alkylthio, arylthio, - OR a , -SR a , -N(Ra) 2 , -C(0)Ra, -C(0)N(R a ) 2 , -N(R a )C(0)R a , -N(R a )S(0)tR a (where t is 1 or 2), and -S(0)tN(R a ) 2 (where t is 1 or 2), where each R a is independently hydrogen, alkyl, alkoxy, al
  • Heterocyclyl refers to any 3- to 18-membered non-aromatic monocyclic or polycyclic moiety comprising at least one heteroatom selected from nitrogen, oxygen, phosphorous and sulfur.
  • a heterocyclyl group can be a monocyclic, bicyclic, tricyclic or tetracyclic ring system, wherein the polycyclic ring systems can be a fused, bridged or spiro ring system.
  • Heterocyclyl polycyclic ring systems can include one or more heteroatoms in one or both rings.
  • a heterocyclyl group can be saturated or partially unsaturated.
  • heterocycloalkenyl if the heterocyclyl contains at least one double bond
  • heterocycloalkynyl if the heterocyclyl contains at least one triple bond.
  • a numerical range such as “3 to 18” refers to each integer in the given range; e.g., "5 to 18 ring atoms” means that the heterocyclyl group can consist of 5 ring atoms, 6 ring atoms, etc., up to and including 18 ring atoms.
  • bivalent radicals derived from univalent heterocyclyl radicals whose names end in "-yl” by removal of one hydrogen atom from the atom with the free valence are named by adding "-idene" to the name of the corresponding univalent radical, e.g., a piperidine group with two points of attachment is a piperidylidene.
  • An N-containing heterocyclyl moiety refers to an non-aromatic group in which at least one of the skeletal atoms of the ring is a nitrogen atom.
  • the heteroatom(s) in the heterocyclyl group is optionally oxidized.
  • One or more nitrogen atoms, if present, are optionally quaternized.
  • Heterocyclyl also includes ring systems substituted with one or more oxide (-0-) substituents, such as piperidinyl N-oxides. The heterocyclyl is attached to the parent molecular structure through any atom of the ring(s).
  • Heterocyclyl also includes ring systems wherein the heterocycyl ring, as defined above, is fused with one or more carbocycyl groups wherein the point of attachment is either on the carbocycyl or heterocyclyl ring, or ring systems wherein the heterocyclyl ring, as defined above, is fused with one or more aryl or heteroaryl groups, wherein the point of attachment is on the heterocyclyl ring.
  • a heterocyclyl group is a 5-10 membered non- aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur (“5-10 membered heterocyclyl").
  • a heterocyclyl group is a 5-8 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur ("5-8 membered heterocyclyl").
  • a heterocyclyl group is a 5-6 membered non-aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen and sulfur ("5-6 membered heterocyclyl").
  • the 5- 6 membered heterocyclyl has 1-3 ring heteroatoms selected from nitrogen, oxygen and sulfur.
  • the 5-6 membered heterocyclyl has 1-2 ring heteroatoms selected from nitrogen, oxygen and sulfur.
  • the 5-6 membered heterocyclyl has 1 ring heteroatom selected from nitrogen, oxygen and sulfur.
  • Exemplary 3-membered heterocyclyls containing 1 heteroatom include, without limitation, azirdinyl, oxiranyl, thiorenyl.
  • Exemplary 4-membered heterocyclyls containing 1 heteroatom include, without limitation, azetidinyl, oxetanyl and thietanyl.
  • Exemplary 5- membered heterocyclyls containing 1 heteroatom include, without limitation, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, dihydrothiophenyl, pyrrolidinyl, dihydropyrrolyl and pyrrolyl-2,5-dione.
  • Exemplary 5-membered heterocyclyls containing 2 heteroatoms include, without limitation, dioxolanyl, oxathiolanyl and dithiolanyl.
  • Exemplary 5-membered heterocyclyls containing 3 heteroatoms include, without limitation, triazolinyl, oxadiazolinyl, and thiadiazolinyl.
  • Exemplary 6-membered heterocyclyl groups containing 1 heteroatom include, without limitation, piperidinyl, tetrahydropyranyl, dihydropyridinyl, and thianyl.
  • Exemplary 6-membered heterocyclyl groups containing 2 heteroatoms include, without limitation, piperazinyl, morpholinyl, dithianyl, dioxanyl.
  • Exemplary 6-membered heterocyclyl groups containing 2 heteroatoms include, without limitation, triazinanyl.
  • Exemplary 7- membered heterocyclyl groups containing 1 heteroatom include, without limitation, azepanyl, oxepanyl and thiepanyl.
  • Exemplary 8-membered heterocyclyl groups containing 1 heteroatom include, without limitation, azocanyl, oxecanyl and thiocanyl.
  • bicyclic heterocyclyl groups include, without limitation, indolinyl, isoindolinyl, dihydrobenzofuranyl, dihydrobenzothienyl, tetrahydrobenzothienyl, tetrahydrobenzofuranyl, tetrahydroindolyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, decahydroquinolinyl, decahydroisoquinolinyl, octahydrochromenyl, octahydroisochromenyl, decahydronaphthyridinyl, decahydro-1,8- naphthyridinyl, octahydropyrrolo[3,2-b]pyrrole, indolinyl, phthalimidyl, naphthalimidyl, chromanyl, chromenyl, lH-benzo[e][l,4-
  • heterocyclyl moieties are optionally substituted by one or more substituents which independently include: alkyl, alkoxy, alkylaryl, cycloalkyl, aralkyl, aryl, aryloxy, amino, amido, carbamate, carbonyl, heteroalkyl, heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, ether, thio, alkylthio, arylthio, -OR a , -SR a , -S(0) t R a , -N(R a ) 2 , - C(0)R a , -C(0)N(R a ) 2 , -N(R a )C(0)R a , -N(R a )S(0)tR a (where t is 1 or 2), and -S(0) t N(R a ) 2 (where t is 1 or 2), and
  • Moiety refers to a specific segment or functional group of a molecule. Chemical moieties are often recognized chemical entities embedded in or appended to a molecule.
  • Niro refers to the -N0 2 group.
  • the term "unsubstituted" means that for carbon atoms, only hydrogen atoms are present besides those valencies linking the atom to the parent molecular group.
  • a non- limiting example is propyl (-CH 2 -CH 2 -CH 3 ).
  • valencies not linking the atom to the parent molecular group are either hydrogen or an electron pair.
  • sulfur atoms valencies not linking the atom to the parent molecular group are either hydrogen, oxygen or electron pair(s).
  • substituted or “substitution” means that at least one hydrogen present on a group (e.g. , a carbon or nitrogen atom) is replaced with a permissible substituent, e.g. , a substituent which upon substitution for the hydrogen results in a stable compound, e.g., a compound which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, or other reaction.
  • a "substituted” group can have a substituent at one or more substitutable positions of the group, and when more than one position in any given structure is substituted, the substituent is either the same or different at each position.
  • Substituents include one or more group(s) individually and independently selected from alkyl, alkoxy, alkylaryl, cycloalkyl, aralkyl, aryl, aryloxy, amino, amido, carbamate, carbonyl, heteroalkyl, heteroaryl, heterocycloalkyl, cyano, halo, haloalkoxy, haloalkyl, ether, thio, alkylthio, arylthio, -OR a , -SR a , -N(R a ) 2 , -C(0)R a , -C(0)N(R a ) 2 , - N(R a )C(0)R a , -N(Ra)S(0)tRa (where t is 1 or 2), and -S(0)tN(R a ) 2 (where t is 1 or 2), where each R a is independently hydrogen, alkyl, haloalkyl,
  • Sulfanyl each refer to the groups: -S-R b , wherein R b is selected from alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (bonded through a chain carbon), cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocycloalkyl (bonded through a ring carbon), heterocycloalkylalkyl, heteroaryl (bonded through a ring carbon) or heteroarylalkyl, unless stated otherwise in the specification, each of which moiety can itself be optionally substituted as described herein.
  • an 'alkylthio refers to the "alkyl-S-” group
  • arylthio refers to the "aryl-S-” group, each of which are bound to the parent molecular group through the S atom.
  • thiol refers to the group -R C SH.
  • Sulfinyl refers to the -S(0)-R b group, wherein R b is selected from hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (bonded through a chain carbon), cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocycloalkyl (bonded through a ring carbon), heterocycloalkylalkyl, heteroaryl (bonded through a ring carbon) or heteroarylalkyl, unless stated otherwise in the specification, each of which moiety can itself be optionally substituted as described herein.
  • Sulfonyl refers to the -S(0 2 )-R b group, wherein R b is selected from hydrogen, alkyl, alkenyl, alkynyl, haloalkyl, heteroalkyl (bonded through a chain carbon), cycloalkyl, cycloalkylalkyl, aryl, aralkyl, heterocycloalkyl (bonded through a ring carbon), heterocycloalkylalkyl, heteroaryl (bonded through a ring carbon) or heteroarylalkyl, unless stated otherwise in the specification, each of which moiety can itself be optionally substituted as described herein.
  • the term designates a Q-C4 sulfonamido, wherein each R in sulfonamido contains 1 carbon, 2 carbons, 3 carbons, or 4 carbons total.
  • substituent groups are specified by their conventional chemical formulae, written from left to right, they equally encompass the chemically identical substituents that would result from writing the structure from right to left, e.g., -CH 2 0- is equivalent to -OCH 2 -.
  • the cellulosic material can be at least partially degraded using a polymer catalyst to produce a saccharide composition, which can undergo fermentation to produce bio-based polymers or one or more precursors suitable for use in producing the bio-based polymers.
  • precursors can include, for example, alcohols (e.g. , ethylene glycol, 1,3-propanediol, 1,4-butanediol), carboxylic acids (e.g., succinic acid, adipic acid, pimelic acid), hydroxyacids (e.g.
  • the precursor produced from fermentation of sugars liberated from cellulosic material is ethylene glycol, which can be used as a building block for the production of polyethylene terephthalate, or copolyesters thereof.
  • the precursors produced from fermentation of sugars liberated from cellulosic material can be used as a building block for the production of propylene and polypropylene.
  • Cellulosic materials can be contacted with the polymer catalysts described herein to render the cellulosic material more susceptible to hydrolysis. In some instances, the cellulosic material can also be hydrolyzed into sugars suitable for use in producing bio-based polymers. a) Cellulosic Materials
  • Cellulosic materials can include any material containing cellulose and/or hemicellulose.
  • cellulosic materials can be lignocellulosic materials that contain lignin in addition to cellulose and/or hemicellulose.
  • Cellulose is a polysaccharide that includes a linear chain of beta-(l-4)-D-glucose units.
  • Hemicellulose is also a polysaccharide; however, unlike cellulose, hemicellulose is a branched polymer that typically includes shorter chains of sugar units.
  • Hemicellulose can include a diverse number of sugar monomers including, for example, xylans, xyloglucans, arabinoxylans, and mannans.
  • Cellulosic materials can typically be found in biomass.
  • the cellulosic materials used with the polymer catalysts described herein contains a substantial proportion of cellulosic material, such as about 5%, about 10%, about 15%, about 20%, about 25%, about 50%, about 75%, about 90% or greater than about 90% cellulose.
  • the cellulosic material can include herbaceous materials, agricultural residues, forestry residues, municipal solid waste, waste paper, and pulp and paper mill residues.
  • the cellulosic material includes corns, natural fibers, sugarcanes, beets, citrus fruits, woody plants, potatoes, plant oils, other polysaccharides such as pectin, chitin, levan, or pullulan, or a combination thereof.
  • the cellulosic material is corn stover, corn fiber, or corn cob.
  • the cellulosic material is bagasse, rice straw, wheat straw, switch grass or miscanthus.
  • the cellulosic material can also include chemical cellulose (e.g., Avicel®), industrial cellulose (e.g., paper or paper pulp), bacterial cellulose, or algal cellulose.
  • the cellulosic materials can be used as obtained from the source, or can be subjected to one or pretreatments.
  • pretreated corn stover (“PCS”) is a cellulosic material derived from corn stover by treatment with heat and/or dilute sulfuric acid, and is suitable for use with the polymer catalysts described herein.
  • crystalline cellulose are forms of cellulose where the linear beta-(l-4)-glucan chains can be packed into a three-dimensional superstructure.
  • the aggregated beta-(l-4)-glucan chains are typically held together via inter- and intra- molecular hydrogen bonds.
  • Steric hindrance resulting from the structure of crystalline cellulose can impede access of the reactive species, such as enzymes or chemical catalysts, to the beta-glycosidic bonds in the glucan chains.
  • non-crystalline cellulose and amorphous cellulose are forms of cellulose in which individual beta-(l-4)-glucan chains are not appreciably packed into a hydrogen-bonded superstructure, where access of reactive species to the beta-glycosidic bonds in the cellulose is hindered.
  • beta-(l-4)-glucan chains present in natural cellulose exhibit a number average degree of polymerization between about 1,000 and about 4,000 anhydroglucose (“AHG") units (i.e., about 1,000-4,000 glucose molecules linked via beta- glycosidic bonds), while the number average degree of polymerization for the crystalline domains is typically between about 200 and about 300 AHG units. See e.g., R.
  • AHG anhydroglucose
  • cellulose has multiple crystalline domains that are connected by noncrystalline linkers that can include a small number of anhydroglucose units.
  • noncrystalline linkers that can include a small number of anhydroglucose units.
  • Dilute acid treatment does not appreciably disrupt the packing of individual beta-(l-4)-glucan chains into a hydrogen-bonded super-structure, nor does it hydrolyze an appreciable number of glycosidic bonds in the packed beta-(l-4)-glucan chains.
  • treatment of natural cellulosic materials with dilute acid reduces the number average degree of polymerization of the input cellulose to approximately 200-300 anhydroglucose units, but does not further reduce the degree of polymerization of the cellulose to below about 150-200 anhydroglucose units (which is the typical size of the crystalline domains).
  • the polymer catalysts described herein can be used to digest natural cellulosic materials.
  • the polymer catalysts can be used to digest crystalline cellulose by a chemical transformation in which the average degree of polymerization of cellulose is reduced to a value less than the average degree of polymerization of the crystalline domains. Digestion of crystalline cellulose can be detected by observing reduction of the average degree of polymerization of cellulose.
  • the polymer catalysts can reduce the average degree of polymerization of cellulose from at least about 300 AGH units to less than about 200 AHG units.
  • the polymer catalysts described herein can be used to digest crystalline cellulose, as well as microcrystalline cellulose.
  • crystalline cellulose typically has a mixture of crystalline and amorphous or noncrystalline domains
  • microcrystalline cellulose typically refers to a form of cellulose where the amorphous or non-crystalline domains have been removed by chemical processing such that the residual cellulose substantially has only crystalline domains.
  • the polymer catalysts described herein can be used with cellulosic material that has been pretreated. In other embodiments, the polymer catalysts described herein can be used with cellulosic material before pretreatment.
  • Any pretreatment process known in the art can be used to disrupt plant cell wall components of cellulosic materials, including, for example, chemical or physical pretreatment processes. See, e.g., Chandra et al., Substrate pretreatment: The key to effective enzymatic hydrolysis of lignocellulosics?, Adv. Biochem. Engin./Biotechnol., 108: 67-93 (2007); Galbe and Zacchi, Pretreatment of lignocellulosic materials for efficient bioethanol production, Adv. Biochem.
  • Suitable pretreatments can include, for example, washing, solvent-extraction, solvent- swelling, comminution, milling, steam pretreatment, explosive steam pretreatment, dilute acid pretreatment, hot water pretreatment, alkaline pretreatment, lime pretreatment, wet oxidation, wet explosion, ammonia fiber explosion, organosolvent pretreatment, biological pretreatment, ammonia percolation, ultrasound, electroporation, microwave, supercritical C02, supercritical H20, ozone, and gamma irradiation, or a combination thereof.
  • One of skill in the art would recognize the conditions suitable to pretreat biomass. See e.g., U.S. Patent Application No. 2002/0164730; Schell et al., Appl. Biochem.
  • the polymer catalysts described herein can be used with cellulosic material that has not been pretreated.
  • the cellulosic material can also be subjected to other processes instead of or in addition to pretreatment including, for example, particle size reduction, pre-soaking, wetting, washing, or conditioning.
  • the use of the term "pretreatment” does not imply or require any specific timing of the steps of the methods described herein.
  • the cellulosic material can be pretreated before hydrolysis.
  • the pretreatment can be carried out simultaneously with hydrolysis.
  • the pretreatment step itself results in some conversion of cellulosic material to sugars (for example, even in the absence of the polymer catalysts described herein).
  • Several common methods that can be used to pretreat cellulose materials for use with the polymer catalysts are described below.
  • Cellulosic material can be heated to disrupt the plant cell wall components ⁇ e.g., lignin, hemicellulose, cellulose) to make the cellulose and/or hemicellulose more accessible to enzymes.
  • Cellulosic material is typically passed to or through a reaction vessel, where steam is injected to increase the temperature to the required temperature and pressure is retained therein for the desired reaction time.
  • the pretreatment can be performed at a temperature between about 140°C and about 230°C, between about 160°C and about 200°C, or between about 170°C and about 190°C. It should be understood, however, that the optimal temperature range for steam pretreatment can vary depending on the polymer catalyst used.
  • the residence time for the steam pretreatment is about 1 to about 15 minutes, about 3 to about 12 minutes, or about 4 to about 10 minutes. It should be understood, however, that the optimal residence time for steam pretreatment can vary depending on the temperature range and the polymer catalyst used.
  • steam pretreatment can be combined with an explosive discharge of the material after the pretreatment, which is known as steam explosion—a rapid flashing to atmospheric pressure and turbulent flow of the material to increase the accessible surface area by fragmentation.
  • steam explosion a rapid flashing to atmospheric pressure and turbulent flow of the material to increase the accessible surface area by fragmentation.
  • acetyl groups in hemicellulose can be cleaved, and the resulting acid can autocatalyze the partial hydrolysis of the hemicellulose to monosaccharides and/or oligosaccharides.
  • a catalyst such as sulfuric acid (typically about 0.3% to about 3% w/w) can be added prior to steam pretreatment, to decrease the time and temperature, increase the recovery, and improve enzymatic hydrolysis. See, e.g., Ballesteros et ah, Appl. Biochem.
  • Chemical pretreatment of cellulosic materials can promote the separation and/or release of cellulose, hemicellulose, and/or lignin by chemical processes.
  • suitable chemical pretreatment processes include, for example, dilute acid pretreatment, lime pretreatment, wet oxidation, ammonia fiber/freeze explosion (AFEX), ammonia percolation (APR), and organosolvent pretreatments.
  • dilute or mild acid pretreatment can be employed.
  • Cellulosic material can be mixed with a dilute acid and water to form a slurry, heated by steam to a certain temperature, and after a residence time flashed to atmospheric pressure.
  • Suitable acids for this pretreatment method can include, for example, sulfuric acid, acetic acid, citric acid, nitric acid, phosphoric acid, tartaric acid, succinic acid, hydrogen chloride, or mixtures thereof.
  • sulfuric acid is used.
  • the dilute acid treatment can be conducted in a pH range of about 1-5, a pH range of about 1-4, or a pH range of about 1-3.
  • the acid concentration can be in the range from about 0.01 to about 20 wt % acid, about 0.05 to about 10 wt % acid, about 0.1 to about 5 wt % acid, or about 0.2 to about 2.0 wt % acid.
  • the acid is contacted with cellulosic material, and can be held at a temperature in the range of about 160-220°C, or about 165-195°C, for a period of time ranging from seconds to minutes (e.g., about 1 second to about 60 minutes).
  • the dilute acid pretreatment can be performed with a number of reactor designs, including for example plug-flow reactors, counter-current reactors, and continuous counter-current shrinking bed reactors.
  • an alkaline pretreatment can be employed.
  • suitable alkaline pretreatments include, for example, lime pretreatment, wet oxidation, ammonia percolation (APR), and ammonia fiber/freeze explosion (AFEX).
  • Lime pretreatment can be performed with calcium carbonate, sodium hydroxide, or ammonia at temperatures of about 85°C to about 150°C, and at residence times from 1 hour to several days. See, e.g., Wyman et al, Bioresource Technol., 96: 1959-1966 (2005); Mosier et al, Bioresource Technol, 96: 673- 686 (2005).
  • wet oxidation can be employed.
  • Wet oxidation is a thermal pretreatment that can be performed, for example, at about 180°C to about 200°C for about 5-15 minutes with addition of an oxidative agent such as hydrogen peroxide or overpressure of oxygen.
  • an oxidative agent such as hydrogen peroxide or overpressure of oxygen.
  • wet oxidation can be performed, for example, at about 1-40% dry matter, about 2-30% dry matter, or about 5-20% dry matter, and the initial pH can also be increased by the addition of alkali (e.g., sodium carbonate).
  • alkali e.g., sodium carbonate
  • wet explosion a combination of wet oxidation and steam explosion, can handle dry matter up to about 30%.
  • the oxidizing agent can be introduced during pretreatment after a certain residence time, and the pretreatment can end by flashing to atmospheric pressure. See, e.g., WO 2006/032282.
  • pretreatment methods using ammonia can be employed. See, e.g., WO 2006/110891; WO 2006/11899; WO 2006/11900; and WO 2006/110901.
  • AFEX ammonia fiber explosion
  • pretreatment methods using ammonia involves treating cellulosic material with liquid or gaseous ammonia at moderate temperatures (e.g., about 90-100°C) and at high pressure (e.g., about 17-20 bar) for a given duration (e.g., about 5-10 minutes), where the dry matter content can be in some instances as high as about 60%. See, e.g., Gollapalli et al., Appl. Biochem.
  • AFEX pretreatment can depolymerize cellulose, partial hydrolyze hemicellulose, and, in some instances, cleave some lignin-carbohydrate complexes.
  • an organosolvent solution can be used to delignify cellulosic material.
  • an organosolvent pretreatment involves extraction using aqueous ethanol (e.g., about 40-60% ethanol) at an elevated temperature (e.g., about 160-200°C) for a period of time (e.g., about 30-60 minutes). See, e.g., Pan et al., Biotechnol. Bioeng., 90: 473-481 (2005); Pan et al., Biotechnol. Bioeng., 94: 851-861 (2006); Kurabi et al., Appl. Biochem. Biotechnol., 121: 219-230 (2005).
  • sulfuric acid is added to the organosolvent solution as a catalyst to delignify the cellulosic material.
  • an organosolvent pretreatment can typically breakdown the majority of hemicellulose
  • Physical pretreatment of cellulosic materials can promote the separation and/or release of cellulose, hemicellulose, and/or lignin by physical processes.
  • suitable physical pretreatment processes can involve irradiation (e.g., microwave irradiation), steaming/steam explosion, hydrothermolysis, and combinations thereof.
  • Physical pretreatment can involve high pressure and/or high temperature.
  • the physical pretreatment is steam explosion.
  • high pressure refers to a pressure in the range of about 300-600 psi, about 350-550 psi, or about 400-500 psi, or about 450 psi.
  • high temperature refers to temperatures in the range of about 100-300°C, or about 140- 235°C.
  • the physical pretreatment is a mechanical pretreatment.
  • mechanical pretreatment can include various types of grinding or milling (e.g., dry milling, wet milling, or vibratory ball milling).
  • mechanical pretreatment is performed in a batch-process, such as in a steam gun hydrolyzer system that uses high pressure and high temperature (e.g., a Sunds Hydrolyzer available from Sunds Defibrator AB, Sweden).
  • cellulosic material can be pretreated both physically and chemically.
  • the pretreatment step can involve dilute or mild acid treatment and high temperature and/or pressure treatment. It should be understood that the physical and chemical pretreatments can be carried out sequentially or simultaneously.
  • the pretreatment can also include a mechanical pretreatment, in addition to chemical pretreatment.
  • Bio pretreatment techniques can involve applying lignin-solubilizing microorganisms. See, e.g., Hsu, T.-A., Pretreatment of Biomass, in Handbook on Bioethanol: Production and Utilization, Wyman, C. E., ed., Taylor & Francis, Washington, D.C., 179-212 (1996); Ghosh and Singh, Physicochemical and biological treatments for enzymatic/microbial conversion of cellulosic biomass, Adv. Appl. Microbiol., 39: 295-333 (1993); McMillan, J. D., Pretreating lignocellulosic biomass: a review, in Enzymatic Conversion of Biomass for Fuels Production, Himmel, M.
  • pretreatment can be performed in an aqueous slurry.
  • the cellulosic material is present during pretreatment in amounts between about 10-80 wt , between about 20-70 wt , or between about 30-60 wt , or about 50 wt %.
  • the pretreated cellulosic material can be unwashed or washed using any method known in the art (e.g., washed with water) before hydrolysis to produce one or more sugars or use with the polymer catalyst.
  • any method known in the art e.g., washed with water
  • the polymer catalyst is capable of degrading at least a portion of the cellulosic material into a saccharide composition, which can include monosaccharides, disaccharides and other oligosaccharides.
  • the polymer catalyst is capable of reducing the degree of crystallization of the cellulosic material.
  • the polymer catalyst is capable of break down at least a portion of the crystalline domains of the cellulose in the cellulosic material.
  • the polymer catalyst used in the methods described herein is a solid-supported acid catalyst that includes a support and a plurality of acidic groups attached to the support.
  • the solid-supported acid catalyst can also include a plurality of cationic groups attached to the support, in addition to the plurality of acidic groups attached to the support.
  • Any suitable supports can be used for the polymer catalyst, including for example biochar, carbon, amorphous carbon, activated carbon, silica, silica gel, and alumina, or a combination thereof.
  • Any suitable acidic groups can be attached to the support in the polymer catalyst, including for example sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid.
  • Any suitable cationic groups can be attached to the support in the polymer catalyst, including for example pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium, phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, triphenyl phosphonium and trifluoro phosphonium.
  • pyrrolium imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, and
  • the polymer catalyst is a polymeric acid catalyst.
  • the polymeric acid catalyst has acidic monomers that are connected to form a polymeric backbone, in which each acidic monomer has at least one Bronsted-Lowry acid.
  • the polymeric acid catalyst has acidic monomers and ionic monomers (which are also known as "ionomers") that are connected to form a polymeric backbone, in which each acidic monomer has at least one Bronsted-Lowry acid, and each ionic monomer independently has at least one nitrogen-containing cationic group or phosphorous- containing cationic group.
  • Some of the acidic and ionic monomers can also include a linker that connects the Bronsted-Lowry acid and cationic group, respectively, to the polymeric backbone.
  • the Bronsted-Lowry acid and the linker together form a side chain.
  • the cationic group and the linker together form a side chain.
  • the side chains are pendant from the polymeric backbone.
  • the catalyst described herein contain monomers that have at least one Bronsted-Lowry acid and at least one cationic group.
  • the Bronsted-Lowry acid and the cationic group can be on different monomers or on the same monomer.
  • the acidic monomers can have one Bronsted-Lowry acid. In other embodiments, the acidic monomers can have two or more Bronsted-Lowry acids, as is chemically feasible. When the acidic monomers have two or more Bronsted-Lowry acids, the acids can be the same or different.
  • Suitable Bronsted-Lowry acids can include any Bronsted-Lowry acid that can form a covalent bond with a carbon.
  • the Bronsted-Lowry acids can have a pK value of less than about 7, less than about 6, less than about 5, less than about 4, less than about 3, less than about 2, less than about 1, or less than zero.
  • the Bronsted-Lowry acid at each occurrence can be independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid.
  • the acidic monomers in the catalyst can either all have the same Bronsted-Lowry acid, or can have different Bronsted-Lowry acids.
  • each Bronsted- Lowry acid in the catalyst is sulfonic acid.
  • each Bronsted- Lowry acid in the catalyst is phosphonic acid.
  • the Bronsted-Lowry acid in some monomers of the catalyst is sulfonic acid, while the Bronsted- Lowry acid in other monomers of the catalyst is phosphonic acid.
  • the ionic monomers can have one cationic group. In other embodiments, the ionic monomers can have two or more cationic groups, as is chemically feasible. When the ionic monomers have two or more cationic groups, the cationic groups can be the same or different.
  • Suitable cationic groups can include any nitrogen-containing cationic group or a phosphorus-containing cationic group.
  • the nitrogen-containing cationic group at each occurrence can be independently selected from ammonium, pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
  • the phosphorous-containing cationic group at each occurrence can be independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
  • each cationic group in the catalyst is a nitrogen-containing cationic group.
  • each cationic group in the catalyst is a phosphorous-containing cationic group.
  • the cationic group in some monomers of the catalyst is a nitrogen-containing cationic group, whereas the cationic group in other monomers of the catalyst is a phosphorous-containing cationic group.
  • each cationic group in the catalyst is imidazolium.
  • the cationic group in some monomers of the catalyst is imidazolium, while the cationic group in other monomers of the catalyst is pyridinium.
  • each cationic group in the catalyst is a substituted phosphonium.
  • the cationic group in some monomers of the catalyst is triphenyl phosphonium, while the cationic group in other monomers of the catalyst is imidazolium.
  • the cationic group can coordinate with a counterion.
  • the counterion can be a halide (e.g., bromide, chloride, iodide, and fluoride), nitrate (N0 3 " ), sulfate (S0 4 2_ ), formate (HCOO ), acetate (H 3 COO ⁇ ), or an organosulfonate (R-SO3 " ; where R is an organic functional group, e.g. , methyl, phenyl).
  • the cationic group can coordinate with a Bronsted-Lowry acid in the catalyst. At least a portion of the Bronsted-Lowry acids and the cationic groups in the catalyst can form inter-monomer ionic associations. Inter-monomeric ionic associations result in salts forming between monomers in the catalyst, rather than with external counterions.
  • the ratio of acidic monomers engaged in inter-monomer ionic associations to the total number of acidic monomers can be at most about 90% internally- coordinated, at most about 80% internally-coordinated, at most about 70% internally- coordinated, at most about 60% internally-coordinated, at most about 50% internally- coordinated, at most about 40% internally-coordinated, at most about 30% internally- coordinated, at most about 20% internally-coordinated, at most about 10% internally- coordinated, at most about 5% internally-coordinated, at most about 1% internally-coordinated, or less than about 1% internally-coordinated. It should be understood that internally-coordinates sites are less likely to exchange with an ionic solution that is brought into contact with the catalyst.
  • Some of the monomers in the catalyst contain both the Bronsted-Lowry acid and the cationic group in the same monomer. Such monomers are referred to as "acidic-ionic monomers".
  • a side chain of an acidic-ionic monomer can contain imidazolium and acetic acid, or pyridinium and boronic acid.
  • the Bronsted-Lowry acid and the cationic group in the side chains of the monomers can be directly connected to the polymeric backbone or connected to the polymeric backbone by a linker.
  • Suitable linkers can include, for example, unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, and unsubstituted or substituted heteroarylene, where the terms unsubstituted and substituted have the meanings as disclosed herein..
  • the linker is an unsubstituted or substituted C5 or C6 arylene.
  • the linker is an unsubstituted or substituted phenylene.
  • the linker is unsubstituted phenylene.
  • the linker is substituted phenylene (e.g., hydroxy- substituted phenylene).
  • some or all of the acidic monomers connected to the polymeric backbone by a linker can have the same linker, or independently have different linkers.
  • some or all of the ionic monomers connected to the polymeric backbone by a linker can have the same linker, or independently have different linkers.
  • some or all of the acidic monomers connected to the polymeric backbone by a linker can have the same or different linkers as some or all of the ionic monomers connected to the polymeric backbone by a linker.
  • a plurality of acidic monomers independently comprises at least one Bronsted- Lowry acid, wherein at least one of the acidic monomers comprises a linker connecting the Bronsted-Lowry acid to the polymeric backbone,
  • each ionic monomer independently comprises at least one nitrogen-containing cationic group or phosphorous-containing cationic group
  • At least one of the ionic monomers comprises a linker connecting the nitrogen- containing cationic group or the phosphorous-containing cationic group to the polymeric backbone.
  • the acidic monomers can be selected from Formulas IA-VIA:
  • each Z is independently selected from C(R 2 )(R 3 ), N(R 4 ), S, S(R 5 )(R 6 ), S(0)(R 5 )(R 6 ), SO 2 , and O, where any two adjacent Z can be joined by a double bond; each m is independently selected from 0, 1, 2, and 3;
  • each n is independently selected from 0, 1, 2, and 3;
  • each R 2 , R 3 , and R 4 is independently selected from hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl;
  • each R 5 and R 6 is independently selected from alkyl, heteroalkyl, cycloalkyl,
  • any two adjacent Z can be taken together to form a group selected from cycloalkyl, heterocycloalkyl, aryl and heteroaryl.
  • the polymer can be selected from Formulas IA, IB, IVA, and IVB. In other embodiments, the polymer can be selected from Formulas IIA, IIB, IIC, IVA, IVB, and IVC. In other embodiments, the polymer can be selected from IIIA, IIIB, and IIIC. In some embodiments, the polymer can be selected from VA, VB, and VC. In some embodiments, the polymer can be selected from IA. In other embodiments, the polymer can be selected from IB.
  • Z can be chosen from C(R 2 )(R3), N R4), S0 2 , and O.
  • any two adjacent Z can be taken together to form a group selected from a heterocycloalkyl, aryl, and heteroaryl.
  • any two adjacent Z can be joined by a double bond. Any combination of these embodiments is also contemplated.
  • m is selected from 2 or 3, such as 3.
  • n is selected from 1, 2, and 3, such as 2 or 3.
  • R 1 can be selected from hydrogen, alkyl and heteroalkyl.
  • R 1 can be selected from hydrogen, methyl, or ethyl.
  • each R 2 , R 3 , and R 4 can be independently selected from hydrogen, alkyl, heterocyclyl, aryl, and heteroaryl.
  • each R 2 , R 3 and R 4 can be independently selected from heteroalkyl, cycloalkyl, heterocyclyl, and heteroaryl.
  • each R 5 and R 6 can be independently selected from alkyl, heterocyclyl, aryl, and heteroaryl. In another embodiment, any two adjacent Z can be taken together to form a group selected from cycloalkyl, heterocycloalkyl, aryl and heteroaryl.
  • the polymer catalyst described herein contains monomers that have at least one Bronsted-Lowry acid and at least one cationic group.
  • the Bronsted-Lowry acid and the cationic group can be on different monomers or on the same monomer.
  • a polymer having acidic monomers and ionic monomers that are connected to form a polymeric backbone in which each acidic monomer has at least one Bronsted-Lowry acid, and each ionic monomer independently has at least one nitrogen- containing cationic group or phosphorous-containing cationic group.
  • each acidic monomer has one Bronsted-Lowry acid.
  • some of the acidic monomers have one Bronsted-Lowry acid, while others have two Bronsted-Lowry acids.
  • each ionic monomer has one nitrogen-containing cationic group or phosphorous-containing cationic group.
  • some of the ionic monomers have one nitrogen-containing cationic group or phosphorous-containing cationic group, while others have two nitrogen-containing cationic groups or phosphorous-containing cationic groups.
  • the acidic monomers can have a side chain with a Bronsted- Lowry acid that is connected to the polymeric backbone by a linker.
  • Side chains with one or more Bronsted-Lowry acids connected by a linker can include, for example,
  • the acidic side chain can be selected from
  • the acidic side chain can be selected from
  • the acidic side chain can be selected from
  • the acidic monomers can have a side chain with a Bronsted- Lowry acid that is directly connected to the polymeric backbone.
  • Side chains with a Bronsted- Lowry acid directly connected to the polymeric backbone can include, for example,
  • the ionic monomers can have one cationic group. In other embodiments, the ionic monomers can have two or more cationic groups, as is chemically feasible. When the ionic monomers have two or more cationic groups, the cationic groups can be the same or different.
  • each cationic group in the polymer catalyst is a nitrogen- containing cationic group. In other embodiments, each cationic group in the polymer catalyst is a phosphorous-containing cationic group. In yet other embodiments, the cationic group in some monomers of the polymer catalyst is a nitrogen-containing cationic group, whereas the cationic group in other monomers of the polymer catalyst is a phosphorous-containing cationic group. In an exemplary embodiment, each cationic group in the polymer catalyst is imidazolium. In another exemplary embodiment, the cationic group in some monomers of the polymer catalyst is imidazolium, while the cationic group in other monomers of the polymer catalyst is pyridinium.
  • each cationic group in the polymer catalyst is a substituted phosphonium.
  • the cationic group in some monomers of the polymer catalyst is triphenyl phosphonium, while the cationic group in other monomers of the polymer catalyst is imidazolium.
  • the nitrogen-containing cationic group at each occurrence can be independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
  • the nitrogen-containing cationic group at each occurrence can be independently selected from imidazolium, pyridinium, pyrimidinium, morpholinium, piperidinium, and piperizinium.
  • the nitrogen-containing cationic group can be imidazolium.
  • the phosphorous-containing cationic group at each occurrence can be independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
  • the phosphorous-containing cationic group at each occurrence can be independently selected from triphenyl phosphonium, trimethyl phosphonium, and triethyl phosphonium.
  • the phosphorous-containing cationic group can be triphenyl phosphonium.
  • each ionic monomer is independently selected from Formulas VIIA-XIB:
  • each Z is independently selected from C(R 2 )(R 3 ), N(R 4 ), S, S(R 5 )(R 6 ),
  • each X is independently selected from F “ , CI “ , Br “ , ⁇ , N0 2 “ , N0 3 , S0 4 2” , R 7 S0 4 “ , R 7 C0 2 “ ,
  • each m is independently selected from 0, 1, 2, and 3;
  • each n is independently selected from 0, 1, 2, and 3;
  • each R 1 , R 2 , R 3 and R 4 is independently selected from hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocyclyl, aryl, and heteroaryl;
  • each R 5 and R 6 is independently selected from alkyl, heteroalkyl, cycloalkyl,
  • heterocyclyl aryl, and heteroaryl; where any two adjacent Z can be taken together to form a group selected from cycloalkyl, heterocycloalkyl, aryl and heteroaryl; and
  • each R is independently selected from hydrogen, C 1-4 alkyl, and C ⁇ heteroalkyl.
  • Z can be chosen from C(R 2 )(R 3 ), N(R 4 ), S0 2 , and O.
  • any two adjacent Z can be taken together to form a group selected from a heterocycloalkyl, aryl and heteroaryl.
  • any two adjacent Z can be joined by a double bond.
  • each X can be selected from CI " , N0 3 , S0 4 2- , R 7 S0 4 " ,
  • each X can be selected from CI “ , Br “ , I “ , HS0 4 " , HC0 2 “ , CH 3 C0 2 " , and N0 3 " .
  • X is acetate.
  • X is bisulfate.
  • X is chloride.
  • X is nitrate.
  • m is selected from 2 or 3, such as 3.
  • n is selected from 1, 2, and 3, such as 2 or 3.
  • R 1 can be selected from hydrogen, alkyl, and heteroalkyl.
  • R 1 can be selected from hydrogen, methyl, or ethyl.
  • each R 2 , R 3 , and R 4 can be independently selected from hydrogen, alkyl, heterocyclyl, aryl, and heteroaryl.
  • each R 2 , R 3 and R 4 can be independently selected from heteroalkyl, cycloalkyl, heterocyclyl, and heteroaryl.
  • each R 5 and R 6 can be independently selected from alkyl, heterocyclyl, aryl, and heteroaryl. In another embodiment, any two adjacent Z can be taken together to form a group selected from cycloalkyl, heterocycloalkyl, aryl and heteroaryl.
  • the ionic monomers can have a side chain with a cationic group that is connected to the polymeric backbone by a linker.
  • Side chains with one or more cationic groups connected by a linker can include, for example,
  • the nitrogen-containing side chain is independently selected from
  • the nitrogen-containing side chain is independently selected from
  • the nitrogen-containing side chain is independently selected from
  • the nitrogen-containing side chain is independently selected from
  • the nitrogen-containing side chain is independently selected from
  • the nitrogen-containing side chain is independently selected from
  • the ionic monomers or moieties can have a side chain with a cationic group that is directly connected to the polymeric backbone or solid support.
  • Side chains with a nitrogen-containing cationic group directly connected to the polymeric backbone or solid support can include, for example,
  • such nitrogen-containing side chains can include
  • the nitrogen-containing cationic group can be an N-oxide, where the negatively charged oxide (0-) is not readily dissociable from the nitrogen cation.
  • Non- limiting examples of such groups include, for example,
  • Side chains with a phosphorous-containing cationic group directly connected to the polymeric backbone can include, for example,
  • the phosphorous-containing side chain is independently selected from
  • the phosphorous-containing side chain is independently selected from
  • the ionic monomers can have a side chain with a cationic group that is directly connected to the polymeric backbone.
  • Side chains with a nitrogen- containing cationic group directly connected to the polymeric backbone can include, for example,
  • each cationic group in the polymer is a nitrogen-containing cationic group.
  • each cationic group in the polymer is a phosphorous-containing cationic group.
  • the cationic group in some monomers of the polymer is a nitrogen-containing cationic group, whereas the cationic group in other monomers of the polymer is a phosphorous-containing cationic group.
  • each cationic group in the polymer is imidazolium.
  • the cationic group in some monomers of the polymer is imidazolium, while the cationic group in other monomers of the polymer is pyridinium.
  • each cationic group in the polymer is a substituted phosphonium.
  • the cationic group in some monomers of the polymer is triphenyl phosphonium, while the cationic group in other monomers of the polymer is imidazolium.
  • the monomers can have a side chain containing both a Bronsted-Lowry acid and a cationic group, where either the Bronsted-Lowry acid is connected to the polymeric backbone by a linker or the cationic group is connected to the polymeric backbone by a linker.
  • the Bronsted-Lowry acid at each occurrence in the acidic- ionic monomer is independently selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid.
  • the Bronsted-Lowry acid at each occurrence is independently sulfonic acid or phosphonic acid.
  • the Bronsted- Lowry acid at each occurrence is sulfonic acid.
  • a side chain of an acidic-ionic monomer can contain imidazolium and acetic acid, or pyridinium and boronic acid.
  • the nitrogen-containing cationic group at each occurrence in the acidic-ionic monomer is independently selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium.
  • the nitrogen- containing cationic group is imidazolium.
  • the phosphorous-containing cationic group at each occurrence in the acidic-ionic monomer is independently selected from triphenyl phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, and trifluoro phosphonium.
  • the phosphorous-containing cationic group is triphenyl phosphonium.
  • the ionic monomers can either all have the same cationic group, or can have different cationic groups.
  • each cationic group in the polymer is a nitrogen-containing cationic group.
  • each cationic group in the polymer is a phosphorous-containing cationic group.
  • the cationic group in some monomers of the polymer is a nitrogen-containing cationic group, whereas the cationic group in other monomers of the polymer is a phosphorous-containing cationic group.
  • each cationic group in the polymer is imidazolium.
  • the cationic group in some monomers of the polymer is imidazolium, while the cationic group in other monomers of the polymer is pyridinium.
  • each cationic group in the polymer is a substituted phosphonium.
  • the cationic group in some monomers of the polymer is triphenyl phosphonium, while the cationic group in other monomers of the polymer is imidazolium.
  • the polymer can include at least one acidic-ionic monomer connected to the polymeric backbone, wherein at least one acidic-ionic monomer comprises at least one Bronsted-Lowry acid, and at least one cationic group, and wherein at least one of the acidic-ionic monomers comprises a linker connecting the acidic-ionic monomer to the polymeric backbone.
  • the cationic group can be a nitrogen-containing cationic group or a phosphorous- containing cationic group as described herein.
  • the linker can be selected from unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, and unsubstituted or substituted heteroarylene, where the terms unsubstituted and substituted have the meanings as disclosed herein.
  • the monomers can have a side chain containing both a Bronsted-Lowry acid and a cationic group, where the Bronsted-Lowry acid is directly connected to the polymeric backbone, the cationic group is directly connected to the polymeric backbone, or both the Bronsted-Lowry acid and the cationic group are directly connected to the polymeric backbone.
  • the linker is unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene. In certain embodiments, the linker is unsubstituted or substituted arylene. In one embodiment, the linker is phenylene. In another embodiment, the linker is hydroxyl- substituted phenylene.
  • the monomers can have a side chain containing both a Bronsted-Lowry acid and a cationic group, where either the Bronsted-Lowry acid is connected to the polymeric backbone by a linker or the cationic group is connected to the polymeric backbone by a linker.
  • Monomers that have side chains containing both a Bronsted-Lowry acid and a cationic group can also be called "acidic ionomers".
  • Such side chains in acidic-ionic monomers that are connected by a linker can include, for example,
  • each X is independently selected from F “ , CI “ , Br “ , ⁇ , ⁇ 2 “ , ⁇ 3 " , S0 4 “ , R S0 4 “ , R 7 C0 2 “ , P0 4 2” , R 7 P0 3 , and R 7 P0 2 “ , where S0 4 2" and P0 4 2" are each independently associated with at least two Bronsted-Lowry acids at any X position on any side chain, and each R is independently selected from hydrogen, C ⁇ alkyl, and C ⁇ heteroalkyl.
  • R 1 can be selected from hydrogen, alkyl, and heteroalkyl. In some embodiments, R 1 can be selected from hydrogen, methyl, or ethyl. In some embodiments, each X can be selected from CI “ , N0 3 " , S0 4 2- " , R 7'S0 4 - “ , and R 7'C0 2 - “ , where R 7' can be selected from hydrogen and C ⁇ alkyl. In another embodiment, each X can be selected from CI " , Br “ , ⁇ , HS0 4 " , HC0 2 " , CH C0 2 " , and N0 3 " . In other embodiments, X is acetate. In other embodiments, X is bisulfate. In other embodiments, X is chloride. In other embodiments, X is nitrate.
  • the acidic-ionic side chain is independently selected from
  • the acidic-ionic side chain is independently selected from
  • the monomers can have a side chain containing both a Bronsted-Lowry acid and a cationic group, where the Bronsted-Lowry acid is directly connected to the polymeric backbone, the cationic group is directly connected to the polymeric backbone, or both the Bronsted-Lowry acid and the cationic group are directly connected to the polymeric backbone.
  • Such side chains in acidic-ionic monomers can include, for example,
  • the counterion is derived from acids selected from hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroioidic acid, nitric acid, nitrous acid, sulfuric acid, carbonic acid, phosphoric acid, phosphorous acid, acetic acid, formic acid, citric acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, dodecylsulfonic acid, and benzene phosphonic acid.
  • the acidic and ionic monomers make up a substantial portion of the catalyst.
  • the acidic and ionic monomers make up at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 90%, at least about 95%, or at least about 99% of the monomers of the polymer, based on the ratio of the number of acidic and ionic monomers to the total number of monomers present in the catalyst.
  • the ratio of the total number of acidic monomers to the total number of ionic monomers can be varied to tune the strength of the acid catalyst.
  • the total number of acidic monomers exceeds the total number of ionic monomers in the catalyst.
  • the total number of acidic monomers is at least about 2, at least about 3, at least about 4, at least about 5, at least about 6, at least about 7, at least about 8, at least about 9 or at least about 10 times the total number of ionic monomers in the catalyst.
  • the ratio of the total number of acidic monomers to the total number of ionic monomers is about 1: 1, about 2: 1, about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1 about, 8: 1, about 9: 1 or about 10: 1.
  • the total number of ionic monomers exceeds the total number of acidic monomers in the catalyst. In other embodiments, the total number of ionic monomers is at least about 2, at least about 3, at least about 4, at least about 5, at least about 6, at least about 7, at least about 8, at least about 9 or at least about 10 times the total number of acidic monomers in the catalyst. In certain embodiments, the ratio of the total number of ionic monomers to the total number of acidic monomers is about 1: 1, about 2: 1, about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1 about, 8: 1, about 9: 1 or about 10: 1.
  • the catalysts described herein can be characterized by the chemical functionalization of the catalyst.
  • the catalyst can have between about 0.1 and about 20 mmol, between about 0.1 and about 15 mmol, between about 0.01 and about 12 mmol, between about 0.01 and about 10 mmol, between about 1 and about 8 mmol, between about 2 and about 7 mmol, between about 3 and about 6 mmol, between about 1 and about 5, or between about 3 and about 5 mmol of the Bronsted-Lowry acid per gram of the catalyst.
  • the catalyst can have between about 0.05 to about 10 mmol of the sulfonic acid per gram of the catalyst. In other embodiments where the catalyst has at least some monomers with side chains having phosphonic acid as the Bronsted-Lowry acid, the catalyst can have between about 0.01 and about 12 mmol of the phosphonic acid per gram of the catalyst. In other embodiments where the catalyst has at least some monomers with side chains having acetic acid as the Bronsted-Lowry acid, the catalyst can have between about 0.01 and about 12 mmol of the acetic acid per gram of the catalyst.
  • the catalyst can have between about 0.01 and about 5 mmol of the isophthalic acid per gram of the catalyst. In other embodiments where the catalyst has at least some monomers with side chains having boronic acid as the Bronsted-Lowry acid, the catalyst can have between about 0.01 and about 20 mmol of the boronic acid per gram of the catalyst.
  • each ionic monomer further includes a counterion for each nitrogen-containing cationic group or phosphorous-containing cationic group.
  • each counterion is independently selected from halide, nitrate, sulfate, formate, acetate, or organosulfonate.
  • the counterion is fluoride, chloride, bromide, or iodide.
  • the counterion is chloride.
  • the counterion is sulfate.
  • the counterion is acetate.
  • the catalyst can have between about 0.01 and about 10 mmol, between about 0.01 and about 8.0 mmol, between about 0.01 and about 4 mmol, between about 1 and about 10 mmol, between about 2 and about 8 mmol, or between about 3 and about 6 mmol of the ionic group.
  • the ionic group includes the cationic group listed, as well as any suitable counterion described herein (e.g. , halide, nitrate, sulfate, formate, acetate, or organosulfonate).
  • the catalyst can have between about 0.01 and about 8 mmol, between about 0.05 and about 8 mmol, between about 1 and about 6 mmol, or between about 2 and about 5 mmol per gram of the ionic group per gram of the catalyst. In other embodiments where the catalyst has at least some monomers with side chains having pyridinium as part of the ionic group, the catalyst can have between between about 0.01 and about 8 mmol, between about 0.05 and about 8 mmol, between about 1 and about 6 mmol, or between about 2 and about 5 mmol per gramof the ionic group per gram of the catalyst.
  • the catalyst can have between about 0.01 and about 5 mmol, between about 0.05 and about 5 mmol, between about 1 and about 4 mmol, or between about 2 and about 3 mmol per gram of the ionic group per gram of the catalyst.
  • the catalyst described herein can further include monomers having a side chain containing a non-functional group, such as a hydrophobic group.
  • the hydrophobic group is connected directly to the polymeric backbone.
  • Suitable hydrophobic groups can include, for example, unsubstituted or substituted alkyl, unsubstituted or substituted cycloalkyl, unsubstituted or substituted aryl, or unsubstituted or substituted heteroaryl.
  • the hydrophobic group is unsubstituted or substituted C5 or C6 aryl.
  • the hydrophobic group is unsubstituted or substituted phenyl.
  • the hydrophobic group is unsubstituted phenyl.
  • the hydrophobic group is unsubstituted phenyl.
  • the hydrophobic monomers can either all have the same hydrophobic group, or can have different hydrophobic groups.
  • the acidic monomers, the ionic monomers, the acidic-ionic monomers and the hydrophobic monomers, where present can be arranged in alternating sequence or in a random order as blocks of monomers. In some embodiments, each block has not more than twenty, fifteen, ten, six, or three monomers.
  • the catalyst is randomly arranged in an alternating sequence.
  • the monomers are randomly arranged in an alternating sequence.
  • the catalyst is randomly arranged as blocks of monomers.
  • the monomers are arranged in blocks of monomers.
  • the catalysts described herein can also be cross-linked.
  • Such cross-linked polymers can be prepared by introducing cross-linking groups.
  • cross-linking can occur within a given polymeric chain, with reference to the portion of the exemplary catalysts depicted in FIGS. 4A and 4B.
  • cross-linking can occur between two or more polymeric chains, with reference to the portion of the exemplary catalysts in FIGS. 5A, 5B, 5C and 5D.
  • the polymer is cross-linked.
  • the polymers described herein are not substantially cross- linked, such as less than about 0.9% cross-linked, less than about 0.5% cross-linked, less than about 0.1% cross-linked, less than about 0.01% cross-linked, or less than 0.001% cross-linked.
  • R 1 , R 2 and R 3 are exemplary cross linking groups.
  • Suitable cross-linking groups that can be used to form a cross-linked polymer with the polymers described herein include, for example, substituted or unsubstituted divinyl alkanes, substituted or unsubstituted divinyl cycloalkanes, substituted or unsubstituted divinyl aryls, substituted or unsubstituted heteroaryls, dihaloalkanes, dihaloalkenes, dihaloalkynes.
  • cross-linking groups can include divinylbenzene, diallylbenzene, dichlorobenzene, divinylmethane, dichloromethane, divinylethane, dichloroethane, divinylpropane, dichloropropane, divinylbutane, dichlorobutane, ethylene glycol, and resorcinol.
  • the polymeric backbone described herein can include, for example, polyalkylenes, polyalkenyl alcohols, polycarbonate, polyarylenes, polyaryletherketones, and polyamide-imides.
  • the polymeric backbone can be selected from polyethylene, polypropylene, polyvinyl alcohol, polystyrene, polyurethane, polyvinyl chloride, polyphenol- aldehyde, polytetrafluoroethylene, polybutylene terephthalate, polycaprolactam, and poly(acrylonitrile butadiene styrene).
  • the polymeric backbone is polyethyelene or polypropylene.
  • the polymeric backbone is polyethylene.
  • the polymeric backbone is polyvinyl alcohol.
  • the polymeric backbone is polystyrene.
  • the polymeric backbone is polyethylene.
  • the polymeric backbone is polyvinyl alcohol.
  • the polymeric backbone described herein can also include an ionic group integrated as part of the polymeric backbone. Such polymeric backbones can also be called "ionomeric backbones". In certain embodiments, the polymeric backbone can be selected
  • polyalkyleneimidazolium polyalkylenepyrazolium, polyalkyleneoxazolium,
  • polyalkylenethiazolium polyalkylenepyridinium, polyalkylenepyrimidinium
  • polyalkylenepyrazinium polyalkylenepyradizimium, polyalkylenethiazinium,
  • polyalkylenemorpholinium polyalkylenepiperidinium, polyalkylenepiperizinium,
  • polyalkylenepyrollizinium polyalkylenetriphenylphosphonium
  • polyalkylenetrimethylphosphonium polyalkylenetriethylphosphonium
  • polyalkylenetripropylphosphonium polyalkylenetributylphosphonium
  • polyalkylenetrichlorophosphonium polyalkylenetrifluorophosphonium
  • polyalkylenediazolium polyarylalkyleneammonium, polyarylalkylenediammonium,
  • polyarylalkylenepyrrolium polyarylalkyleneimidazolium, polyarylalkylenepyrazolium, polyarylalkyleneoxazolium, polyarylalkylenethiazolium, polyarylalkylenepyridinium, polyarylalkylenepyrimidinium, polyarylalkylenepyrazinium, polyarylalkylenepyradizimium, polyarylalkylenethiazinium, polyarylalkylenemorpholinium, polyarylalkylenepiperidinium, polyarylalkylenepiperizinium, polyarylalkylenepyrollizinium,
  • polyarylalkylenetriphenylphosphonium polyarylalkylenetrimethylphosphonium
  • polyarylalkylenetriethylphosphonium polyarylalkylenetripropylphosphonium
  • polyarylalkylenetrifluorophosphonium and polyarylalkylenediazolium.
  • Cationic polymeric backbones can be associated with one or more anions, including but not limited to, F, CI “ , Br “ , I “ , N0 2 ,N0 3 , S0 4 2” , R 7 S0 4 “ , R 7 C0 2 “ , P0 4 2” , R 7 P0 3 " , and R 7 P0 2 " ' where R is selected from hydrogen, C 1 _4alkyl, and C ⁇ heteroalkyl.
  • each X can be selected from CI “ , Br “ , ⁇ , HS0 4 " , HC0 2 " , CH 3 C0 2 " , and N0 3 " .
  • X is acetate.
  • X is bisulfate.
  • X is chloride.
  • X is nitrate.
  • the polymeric backbone is alkyleneimidazolium, which refers to an alkylene moiety, in which one or more of the methylene units of the alkylene moiety has been replaced with imidazolium.
  • the polymeric backbone is selected from polyethyleneimidazolium, polyprolyeneimidazolium, and polybutyleneimidazolium.
  • the number of atoms between side chains in the polymeric backbone can vary. In some embodiments, there are between zero and twenty atoms, zero and ten atoms, zero and six atoms, or zero and three atoms between side chains attached to the polymeric backbone.
  • the polymer can be a homopolymer having at least two monomer units, and where all the units contained within the polymer are derived from the same monomer in the same manner.
  • the polymer can be a heteropolymer having at least two monomer units, and where at least one monomeric unit contained within the polymer that differs from the other monomeric units in the polymer.
  • the different monomer units in the polymer can be in a random order, in an alternating sequence of any length of a given monomer, or in blocks of monomers.
  • exemplary polymers include, but are not limited to, polyalkylene backbones that are substituted with one or more groups selected from hydroxyl, carboxylic acid, unsubstituted and substituted phenyl, halides, unsubstituted and substituted amines, unsubstituted and substituted ammonias, unsubstituted and substituted pyrroles, unsubstituted and substituted imidazoles, unsubstituted and substituted pyrazoles, unsubstituted and substituted oxazoles, unsubstituted and substituted thiazoles, unsubstituted and substituted pyridines, unsubstituted and substituted pyrimidines, unsubstituted and substituted pyrazines, unsubstituted and substituted pyradizines, unsubstituted and substituted thiazines, unsubstituted and substituted morpholines, unsubstit
  • polystyrene a polyethylene backbone with a direct bond to an unsubstituted phenyl group
  • polystyrene a polyethylene backbone with a direct bond to an unsubstituted phenyl group
  • the polymer can be named a polydivinylbenzene (-CH 2 -CH(4-vinylphenyl)-CH 2 -CH(4-vinylphenyl)-).
  • heteropolymers include those that are functionalized after polymerization.
  • a non-limiting example would be polystyrene-co-divinylbenzene: (-CH 2 - CH(phenyl)-CH 2 -CH(4-ethylenephenyl)-CH 2 -CH(phenyl)-CH 2 -CH(4-ethylenephenyl)-).
  • the ethenyl functionality could be at the 2, 3, or 4 position on the phenyl ring.
  • the polymeric backbone is a polyalkyleneimidazolium.
  • the number of atoms between side chains in the polymeric backbone can vary. In some embodiments, there are between zero and twenty atoms, zero and ten atoms, or zero and six atoms, or zero and three atoms between side chains attached to the polymeric backbone. With reference to FIG. 7A, in one exemplary embodiment, there are three carbon atoms between the side chain with the Bronsted-Lowry acid and the side chain with the cationic group. In another example, with reference to FIG. 7B, there are zero atoms between the side chain with the acidic moiety and the side chain with the ionic moiety.
  • the catalyst can include any of the Bronsted-Lowry acids, cationic groups, counterions, linkers, hydrophobic groups, cross-linking groups, and polymeric backbones described herein, as if each and every combination were listed separately.
  • the catalyst can include benzenesulfonic acid (i.e., a sulfonic acid with a phenyl linker) connected to a polystyrene backbone, and an imidazolium chloride connected directly to the polystyrene backbone.
  • the catalyst can include boronyl-benzyl-pyridinium chloride (i.e., a boronic acid and pyridinium chloride in the same monomer unit with a phenyl linker) connected to a polystyrene backbone.
  • the catalyst can include benzenesulfonic acid and an imidazolium sulfate moiety each individually connected to a polyvinyl alcohol backbone.
  • Exemplary polymeric acid catalysts described herein include: poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium chloride- codivinylbenzene] ; poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl- l-(4-vinylbenzyl)-3H- imidazol- 1-ium bisulfate-codivinylbenzene] ;
  • exemplary polymers can include poly [styrene-co-4- vinylbenzene sulfonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- imidazol- 1-ium nitrate-co-di vinylbenzene] ;
  • poly(styrene-co-4-vinylbenzene sulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) poly(styrene-co-4-vinylbenzene sulfonic acid-co-vinylbenzyltriphenylphosphonium chloride-co-divinylbenzene) .
  • exemplary polymers can include poly[styrene-co-4-vinylbenzene sulfonic acid-co- l-(4-vinylbenzyl)-pyridinium-chloride- co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene];
  • exemplary polymers can include poly [styrene-co-4-vinylbenzene sulfonic acid-co-3-methyl-l-(4-vinylbenzyl)-3H- benzoimidazol- 1 -ium chloride-co-divinylbenzene] ;
  • exemplary polymers can include poly[styrene-co-4-vinylbenzene sulfonic acid-co-4-(4-vinylbenzyl)-morpholine-4-oxide- co-divinyl benzene] ;
  • the polymeric backbone is formed from one or more substituted or unsubstituted monomers.
  • Polymerization processes using a wide variety of monomers are well known in the art ⁇ see, e.g., International Union of Pure and Applied Chemistry, et al., IUPAC Gold Book, Polymerization. (2000)).
  • One such process involves monomer(s) with unsaturated substitution, such as vinyl, propenyl, butenyl, or other such substitutent(s). These types of monomers can undergo radical initiation and chain polymerization.
  • monomers having heteroatoms can be combined with one or more difunctionalized compounds, such as, but not limited to, dihaloalkanes, di(alkylsulfonyloxy)alkanes, and di(arylsulfonyloxy)alkanes to form polymers.
  • the monomers have at least two heteroatoms to link with the difunctionalized alkane to create the polymeric chain.
  • difunctionalized compounds can be further substituted as described herein.
  • the difunctionalized compound(s) can be selected from 1,2-dichloroethane,
  • the polymeric backbone is formed from one or more substituted or unsubstituted monomers selected from ethylene, propylene, hydroxyethylene, acetaldehyde, styrene, divinyl benzene, isocyanates, vinyl chloride, vinyl phenols, tetrafluoroethylene, butylene, terephthalic acid, caprolactam, acrylonitrile, butadiene, ammonias, diammonias, pyrrole, imidazole, pyrazole, oxazole, thiazole, pyridine, pyrimidine, pyrazine, pyradizimine, thiazine, morpholine, piperidine, piperizines, pyrollizine, triphenylphosphonate, trimethylphosphonate, triethylphosphonate, tripropylphosphonate, tributylphosphonate, trichlorophosphonate, trifluoro
  • the polymer catalysts described herein can form solid particles.
  • a solid particle can be formed through the procedures of emulsion or dispersion polymerization, which are known to one of skill in the art.
  • the solid particles can be formed by grinding or breaking the polymer into particles, which are also techniques and methods that are known to one of skill in the art. Methods known in the art to prepare solid particles include coating the polymers described herein on the surface of a solid core.
  • Suitable materials for the solid core can include an inert material (e.g., aluminum oxide, corn cob, crushed glass, chipped plastic, pumice, silicon carbide, or walnut shell) or a magnetic material.
  • Polymeric coated core particles can be made by dispersion polymerization to grow a cross-linked polymer shell around the core material, or by spray coating or melting.
  • solid particles include coating the polymers described herein on the surface of a solid core.
  • the solid core can be a non-catalytic support. Suitable materials for the solid core can include an inert material (e.g., aluminum oxide, corn cob, crushed glass, chipped plastic, pumice, silicon carbide, or walnut shell) or a magnetic material.
  • the solid core is made up of iron.
  • Polymeric coated core particles can be made by techniques and methods that are known to one of skill in the art, for example, by dispersion polymerization to grow a cross-linked polymer shell around the core material, or by spray coating or melting.
  • the solid supported polymer catalyst particle can have a solid core where the polymer is coated on the surface of the solid core. In some embodiments, at least about 5%, at least about 10%, at least about 20%, at least about 30%, at least about 40%, or at least about 50% of the catalytic activity of the solid particle can be present on or near the exterior surface of the solid particle.
  • the solid core can have an inert material or a magnetic material. In one embodiment, the solid core is made up of iron.
  • the solid particles coated with the polymer described herein have one or more catalytic properties. In some embodiments, at least about 50%, at least about 60%, at least about 70%, at least about 80% or at least about 90% of the catalytic activity of the solid particle is present on or near the exterior surface of the solid particle.
  • the solid particle is substantially free of pores, for example, having no more than about 50%, no more than about 40%, no more than about 30%, no more than about 20%, no more than about 15%, no more than about 10%, no more than about 5%, or no more than about 1% of pores.
  • Porosity can be measured by methods well known in the art, such as determining the Brunauer-Emmett-Teller (BET) surface area using the absorption of nitrogen gas on the internal and external surfaces of a material (Brunauer, S. et al., J. Am. Chem. Soc. 1938, 60:309).
  • BET Brunauer-Emmett-Teller
  • Other methods include measuring solvent retention by exposing the material to a suitable solvent (such as water), then removing it thermally to measure the volume of interior pores.
  • a suitable solvent such as water
  • Other solvents suitable for porosity measurement of the polymer catalysts include, but are not limited to, polar solvents such as DMF, DMSO, acetone, and alcohols.
  • the solid particles include a microporous gel resin. In yet other embodiments, the solid particles include a macroporous gel resin.
  • the solid particle having the polymer coating has at least one catalytic property selected from:
  • the polymer can include a support and a plurality of acidic moieties and cationic moieties attached to the support.
  • the support is selected from biochar, carbon, amorphous carbon, activated carbon, silica, silica gel, alumina, magnesia, titania, zirconia, clays (e.g., kaolinite), magnesium silicate, silicon carbide, zeolites (e.g., mordenite), ceramics, and any combinations thereof.
  • the material is carbon.
  • the material for carbon support can be biochar, amorphous carbon, or activated carbon. In one embodiment, the material is activated carbon.
  • the acidic groups on the acidic moiety are selected from sulfonic acid, phosphonic acid, acetic acid, isophthalic acid, and boronic acid.
  • the ionic groups on the ionic moiety are selected from pyrrolium, imidazolium, pyrazolium, oxazolium, thiazolium, pyridinium, pyrimidinium, pyrazinium, pyradizimium, thiazinium, morpholinium, piperidinium, piperizinium, and pyrollizinium, phosphonium, trimethyl phosphonium, triethyl phosphonium, tripropyl phosphonium, tributyl phosphonium, trichloro phosphonium, triphenyl phosphonium and trifluoro phosphonium.
  • each linker is independently selected from unsubstituted or substituted alkylene, unsubstituted or substituted cycloalkylene, unsubstituted or substituted alkenylene, unsubstituted or substituted arylene, or unsubstituted or substituted heteroarylene, where the substituents are those as defined herein.
  • the linker is unsubstituted or substituted arylene, unsubstituted or substituted heteroarylene.
  • the linker is unsubstituted or substituted arylene. In one embodiment of the solid-supported catalyst, the linker is phenylene. In another embodiment of the solid-supported catalyst, the linker is hydroxyl- substituted phenylene.
  • each Bronsted-Lowry acid is directly attached to the solid support.
  • the acidic moieties each further include a linker attaching the Bronsted-Lowry acid to the solid support.
  • some of the Bronsted-Lowry acids are directly connected to the solid support, while other Bronsted-Lowry acids are attached to the solid support by a linker.
  • the carbon support can have a surface area from 0.01 to 50 m 2 /g of dry material.
  • the carbon support can have a density from 0.5 to 2.5 kg/L.
  • the support can be characterized using any suitable instrumental analysis methods or techniques known in the art, including for example scanning electron microscopy (SEM), powder X-ray diffraction (XRD), Raman spectroscopy, and Fourier Transform infrared spectroscopy (FTIR).
  • SEM scanning electron microscopy
  • XRD powder X-ray diffraction
  • Raman spectroscopy Raman spectroscopy
  • FTIR Fourier Transform infrared spectroscopy
  • the carbon support can be prepared from carbonaceous materials, including for example, shrimp shell, chitin, coconut shell, wood pulp, paper pulp, cotton, cellulose, hard wood, soft wood, wheat straw, sugarcane bagasse, cassava stem, corn stover, oil palm residue, bitumen, asphaltum, tar, coal, pitch, and any combinations thereof.
  • carbonaceous materials including for example, shrimp shell, chitin, coconut shell, wood pulp, paper pulp, cotton, cellulose, hard wood, soft wood, wheat straw, sugarcane bagasse, cassava stem, corn stover, oil palm residue, bitumen, asphaltum, tar, coal, pitch, and any combinations thereof.
  • suitable methods to prepare the carbon supports used herein See, e.g., M. Inagaki, L.R. Radovic, Carbon, vol. 40, p. 2263 (2002), or A.G. Pandolfo and A.F. Hollenkamp, "Review: Carbon Properties and their role in supercapacitors," Journal of Power Sources, vol.
  • the material is silica, silica gel, alumina, or silica-alumina.
  • silica- or alumina-based solid supports used herein. See, e.g. , Catalyst supports and supported catalysts, by A.B. Stiles, Butterworth Publishers, Stoneham MA, 1987.
  • the material is a combination of a carbon support, with one or more other supports selected from silica, silica gel, alumina, magnesia, titania, zirconia, clays (e.g., kaolinite), magnesium silicate, silicon carbide, zeolites (e.g. , mordenite), and ceramics.
  • a carbon support with one or more other supports selected from silica, silica gel, alumina, magnesia, titania, zirconia, clays (e.g., kaolinite), magnesium silicate, silicon carbide, zeolites (e.g. , mordenite), and ceramics.
  • Polymer catalysts can be advantageous over other catalysts known in the art used for hydrolysis due to, for example, ease of handling.
  • the solid nature of the catalysts can provide for ease of recycling (e.g. , by filtering the catalyst), without requiring distillation or extraction methods.
  • the density and size of the particle can be selected such that the catalyst particles can be separated from the materials used in a process for the break-down of biomaterials.
  • Particles can be selected based on sedimentation rate, e.g., relative to materials used or produced in a reaction mixture, particle density, or particle size.
  • solid particles coated with the catalysts that have a magnetically active core can be recovered by electromagnetic methods known to one of skill in the art.
  • the catalysts described herein have one or more catalytic properties.
  • a "catalytic property" of a material is a physical and/or chemical property that increases the rate and/or extent of a reaction involving the material.
  • the catalytic properties can include at least one of the following properties: a) disruption of a hydrogen bond in cellulosic materials; b) intercalation of the catalyst into crystalline domains of cellulosic materials; and c) cleavage of a glycosidic bond in cellulosic materials.
  • the catalysts that have two or more of the catalytic properties described above, or all three of the catalytic properties described above.
  • the catalysts described herein have the ability to catalyze a chemical reaction by donation of a proton, and can be regenerated during the reaction process. In other embodiments, the catalysts described herein have a greater specificity for cleavage of a glycosidic bond than dehydration of a monosaccharide.
  • compositions involving the catalysts that can be used in a variety of methods described herein, including the break-down of cellulosic material.
  • compositions that include biomass and the catalysts described herein.
  • the composition can include biomass and an effective amount of a catalyst as described herein.
  • the composition further includes a solvent (e.g. , water).
  • the biomass includes cellulose, hemicellulose, or a combination thereof.
  • compositions that include the catalysts described herein, one or more sugars, and residual biomass.
  • the one or more sugars are one or more monosaccharides, one or more oligosaccharides, or a mixture thereof.
  • the one or more sugars are two or more sugars including at least one C4-C6 monosaccharide and at least one oligosaccharide.
  • the one or more sugars are selected from glucose, galactose, fructose, xylose, and arabinose.
  • the one or more sugars are one or more monosaccharides, one or more oligosaccharides, or a mixture thereof.
  • the one or more sugars are two or more sugars that include at least one C4-C6 monosaccharide and at least one oligosaccharide.
  • the one or more sugars are selected from glucose, galactose, fructose, xylose, and arabinose.
  • a saccharification intermediate that includes any of the catalysts described herein hydrogen-bonded to the biomass.
  • the ionic monomer or moiety of the catalyst is hydrogen-bonded to the carbohydrate alcohol groups present in cellulose, hemicellulose, and other oxygen-containing components of feedstock.
  • the acidic monomer or moiety of the catalyst is hydrogen-bonded to the carbohydrate alcohol groups present in cellulose, hemicellulose, and other oxygen-containing components of lignocellulose present in the biomass, including the glycosidic linkages between sugar monomers.
  • the biomass has cellulose, hemicellulose or a combination thereof.
  • the methods provided herein involve contacting the cellulosic material with a polymer catalyst under conditions sufficient to hydrolyze at least a portion of the cellulosic material into sugars.
  • the cellulosic material can be contacted with the polymer catalyst in the presence of a solvent.
  • any method known in the art that includes pretreatment, enzymatic hydrolysis (saccharification), fermentation, or a combination thereof, can be used with the catalysts in the methods described herein.
  • the catalysts can be used before or after pretreatment methods to make the cellulose (and hemicellulose, where present) in the biomass more accessible to hydrolysis
  • the cellulosic material is contacted with the polymer catalyst in an aqueous environment.
  • aqueous solvent is water, which can be obtained from various sources. Generally, water sources with lower concentrations of ionic species are preferable, as such ionic species can reduce effectiveness of the polymer catalyst.
  • the aqueous solvent is water, the water has less than 10% of ionic species (e.g., salts of sodium, phosphorous, ammonium, magnesium, or other species found naturally in lignocellulosic biomass).
  • the methods described herein can further include monitoring the amount of water present in the reaction and/or the ratio of water to cellulosic material over a period of time. In other embodiments, the methods described herein can further include supplying water directly to the reaction, for example, in the form of steam or steam condensate.
  • the hydration conditions in the reactor is such that the water-to-cellulosic material ratio is is about 5: 1, about 4: 1, about 3: 1, about 2: 1, about 1: 1, about 1:2, about 1:3, about 1:4, about 1:5, or less than about 1:5. It should be understood, however, that the ratio of water to cellulosic material can be adjusted based on the specific polymer catalyst used. Processing time, temperature and pH conditions
  • the cellulosic material can be in contact with the polymer catalyst for up to about 200 hours.
  • the feedstock can be in contact with the catalyst from about 1 to about 96 hours, from about 12 to about 72 hours, or from about 12 to about 48 hours.
  • the feedstock can be in contact with the polymer at temperature in the range of about 25°C to about 150°C. In other embodiments, the feedstock can be in contact with the polymer in the range of about 30°C to about 125°C, about 30°C to about 140°C, about 80°C to about 120°C, about 80°C to about 130°C, about 100°C to 110°C, or about 100°C to about 130°C.
  • the pH is generally affected by the intrinsic properties of the polymer catalyst used.
  • the acidic moiety of the polymer catalyst can affect the pH of the reaction to degrade the cellulosic material.
  • the use of sulfuric acid moiety in a polymer catalyst results in a reaction pH of about 3.
  • a pH between about 0 and about 6 is used to degrade the cellulosic material.
  • the reacted effluent typically has a pH of at least about 4, or a pH that is compatible with other processes such as enzymatic treatment. It should be understood, however, that the pH can be modified and controlled by the addition of acids, bases or buffers.
  • the pH can vary within the reactor. For example, high acidity at or near the surface of the catalyst can be observed, whereas regions distal to the catalyst surface can have a substantially neutral pH. Thus, one of skill would recognize that determination of the solution pH should account for such spatial variation.
  • the methods described herein to degrade the cellulosic material can further include monitoring the reaction pH, and optionally adjusting the pH within the reactor.
  • a low pH in solution can indicate an unstable polymer catalyst, in which the catalyst can be losing at least a portion of its acidic groups to the surrounding environment through leaching.
  • the pH near the surface of the polymer catalyst is below about 7, below about 6, or below about 5. Amount and nature of the cellulosic material used
  • the amount of the cellulosic material used in the methods described herein relative to the amount solvent used can affect the rate of reaction and yield.
  • the amount of the cellulosic material used can be characterized by the dry solids content.
  • dry solids content refers to the total solids of a slurry as a percentage on a dry weight basis.
  • the dry solids content of the cellulosic materials is between about 5 wt to about 95 wt , between about 10 wt to about 80 wt , between about 15 wt % to about 75 wt , or between about 15 wt % to about 50 wt %.
  • the amount of the polymer catalysts used in the methods described herein can depend on several factors including, for example, type and composition of the cellulosic material used and the reaction conditions ⁇ e.g., temperature, time, and pH).
  • the weight ratio of the polymer catalyst to the cellulosic material is about O.lg/g to about 50 g/g, about O.lg/g to about 25 g/g, about 0.1 g/g to about 10 g/g, about 0.1 g/g to about 5 g/g, about 0.1 g/g to about 2 g/g, about 0.1 g/g to about 1 g/g, or about 0.1 to about 0.75 g/g.
  • the polymer catalyst and the cellulosic material are introduced into an interior chamber of a reactor, either concurrently or sequentially.
  • the reaction can be performed in a batch process or a continuous process.
  • the reaction is performed in a batch process, where the contents of the reactor are continuously mixed or blended, and all or a substantial amount of the products of the reaction are removed.
  • the reaction is performed in a batch process, where the contents of the reactor are initially intermingled or mixed but no further physical mixing is performed.
  • the reaction is performed in a batch process, wherein once further mixing of the contents, or periodic mixing of the contents of the reactor, is performed ⁇ e.g., at one or more times per hour), all or a substantial amount of the products of the reaction are removed after a certain period of time.
  • the reaction is performed in a continuous process, where the contents flow through the reactor with an average continuous flow rate but with no explicit mixing. After introduction of the polymer catalyst and the cellulosic material into the reactor, the contents of the reactor are continuously or periodically mixed or blended, and after a period of time, less than all of the products of the reaction are removed.
  • the reaction is performed in a continuous process, where the mixture containing the catalyst and cellulosic material is not actively mixed. Additionally, mixing of catalyst and the cellulosic material can occur as a result of the redistribution of polymer catalysts settling by gravity, or the non-active mixing that occurs as the material flows through a continuous reactor.
  • the reactors used for the methods described herein can be open or closed reactors suitable for use in containing the chemical reactions described herein.
  • Suitable reactors can include, for example, a fed-batch stirred reactor, a batch stirred reactor, a continuous flow stirred reactor with ultrafiltration, a continuous plug-flow column reactor, an attrition reactor, or a reactor with intensive stirring induced by an electromagnetic field. See e.g., Fernanda de Castilhos Corazza, Flavio Faria de Moraes, Gisella Maria Zanin and Ivo Neitzel, Optimal control in fed-batch reactor for the cellobiose hydrolysis, Acta Scientiarum. Technology, 25: 33-38 (2003); Gusakov, A.
  • reactor types can include, for example, fluidized bed, upflow blanket, immobilized, and extruder type reactors for hydrolysis and/or fermentation.
  • the reactor can include a continuous mixer, such as a screw mixer.
  • the reactors can be generally fabricated from materials that are capable of withstanding the physical and chemical forces exerted during the processes described herein. In some embodiments, such materials used for the reactor are capable of tolerating high concentrations of strong liquid acids; however, in other embodiments, such materials can not be resistant to strong acids.
  • the reactor can be filled with cellulosic material by a top-load feeder containing a hopper capable of holding cellulosic material.
  • the reactor typically contains an outlet means for removal of contents (e.g., a sugar-containing solution) from the reactor.
  • contents e.g., a sugar-containing solution
  • the outlet means of the reactor is linked to a continuous incubator into which the reacted contents are introduced.
  • the outlet means provides for removal of residual cellulosic material by, e.g., a screw feeder, by gravity, or a low shear screw.
  • the methods described herein further include recovering the sugars that are produced from the hydrolysis of the cellulosic material.
  • the method for degrading cellulosic material using the polymer catalyst described herein further includes recovering the degraded or converted cellulosic material.
  • the sugars which are typically soluble, can be separated from the insoluble residual cellulosic material using technology well known in the art such as, for example, centrifugation, filtration, and gravity settling.
  • Separation of the sugars can be performed in the hydrolysis reactor or in a separator vessel.
  • the method for degrading cellulosic material is performed in a system with a hydrolysis reactor and a separator vessel.
  • Reactor effluent containing the monosaccharides and/or oligosaccharides is transferred into a separator vessel and is washed with a solvent (e.g. , water), by adding the solvent into the separator vessel and then separating the solvent in a continuous centrifuge.
  • a reactor effluent containing residual solids e.g.
  • residual cellulosic materials is removed from the reactor vessel and washed, for example, by conveying the solids on a porous base (e.g. , a mesh belt) through a solvent (e.g., water) wash stream. Following contact of the stream with the reacted solids, a liquid phase containing the monosaccharides and/or oligosaccharides is generated.
  • a cyclone Suitable types of cyclones used for the separation can include, for example, tangential cyclones, spark and rotary separators, and axial and multi-cyclone units.
  • separation of the sugars is performed by batch or continuous differential sedimentation.
  • Reactor effluent is transferred to a separation vessel, optionally combined with water and/or enzymes for further treatment of the effluent.
  • solid biomaterials e.g. , residual treated biomass
  • the solid catalyst, and the sugar-containing aqueous material can be separated by differential sedimentation into a plurality of phases (or layers).
  • the catalyst layer can sediment to the bottom, and depending on the density of the residual biomass, the biomass phase can be on top of, or below, the aqueous phase.
  • the phases are sequentially removed, either from the top of the vessel or an outlet at the bottom of the vessel.
  • the separation vessel When the phase separation is performed in a continuous mode, the separation vessel contains one or more than one outlet means (e.g., two, three, four, or more than four), generally located at different vertical planes on a lateral wall of the separation vessel, such that one, two, or three phases are removed from the vessel.
  • the removed phases are transferred to subsequent vessels or other storage means.
  • one of skill in the art would be able to capture (1) the catalyst layer and the aqueous layer or biomass layer separately, or (2) the catalyst, aqueous, and biomass layers separately, allowing efficient catalyst recycling, retreatment of biomass, and separation of sugars.
  • controlling rate of phase removal and other parameters allows for increased efficiency of catalyst recovery.
  • the catalyst and/or biomass can be separately washed by the aqueous layer to remove adhered sugar molecules.
  • the sugars isolated from the vessel can be subjected to further processing steps (e.g., as drying, fermentation) to produce biofuels and other bio-products.
  • the monosaccharides that are isolated can be at least about 1% pure, at least about 5% pure, at least about 10% pure, at least about 20% pure, at least about 40% pure, at least about 60% pure, at least about 80% pure, at least about 90% pure, at least about 95% pure, at least about 99% pure, or greater than 99% pure, as determined by analytical procedures known in the art, such as determination by high performance liquid chromatography (HPLC), functionalization and analysis by gas chromatography, mass spectrometry, spectrophotometric procedures based on chromophore complexation and/or carbohydrate oxidation-reduction chemistry.
  • HPLC high performance liquid chromatography
  • mass spectrometry mass spectrometry
  • spectrophotometric procedures based on chromophore complexation and/or carbohydrate oxidation-reduction chemistry.
  • the residual biomass isolated from the vessels can be useful as a combustion fuel or as a feed source of non-human animals such as livestock. Rate and Yield
  • the use of the polymer catalysts described herein can increase the rate and/or yield of saccharification.
  • the polymer catalysts described herein are capable of degrading the cellulosic material into one or more sugars at a first-order rate constant of at least about 0.001 per hour, at least about 0.01 per hour, at least about 0.1 per hour, at least about 0.2 per hour, at least about 0.3 per hour, at least about 0.4 per hour, at least about 0.5 per hour, or at least about 0.6 per hour.
  • the hydrolysis yield of the cellulose and hemicellulose components of the cellulosic material to soluble sugars by the polymer catalyst can be measured by determining the degree of polymerization of the residual cellulosic material. The lower the degree of polymerization of the residual cellulosic material, the greater the hydrolysis yield.
  • the polymer catalysts described herein are capable of converting cellulosic material into one or more sugars and residual cellulosic material, wherein the residual cellulosic material has a degree of polymerization of less than about 300, less than about 250, less than about 200, less than about 150, less than about 100, less than about 90, less than about 80, less than about 70, less than about 60, or less than about 50.
  • the catalysts used for saccharification of biomass can be recovered and reused.
  • Sedimentation of the catalyst is used to recover the catalyst following use.
  • the catalyst can sink, while other residuals solids can remain suspended in the saccharification reaction mixture.
  • the sedimentation rate can be measured by the sedimentation coefficient, mv
  • the sedimentation rate of the catalyst can, in some embodiments, be about 10 ⁇ 6 -10 ⁇ 2 , about 10 ⁇ 5 -10 ⁇ 3 , or about lO ⁇ -lO "3 .
  • the density of the catalyst can also have an impact on its ease of recovery from saccharification.
  • the gravimetric density of the catalyst is about 0.5-3.0 kg/L, about 1.0-3.0 kg/L, or about 1.1-3.0 kg/L.
  • One of skill in the art would recognize that various methods and techniques suitable for measuring the density of a catalyst as described herein. d) Saccharide composition
  • the polymer catalysts described above can be used to degrade cellulosic materials into a saccharide composition, or a mixture of two or more saccharide compositions.
  • the saccharide composition can be in the form of a hydrolysate, produced from the hydrolysis of the cellulosic materials.
  • the saccharide compositions can be separated by techniques well known in the art, such as chromatographic methods. Any method of degrading cellulosic material or biomass as disclosed herein should be understood by the skilled artisan to represent a method that can also produce two or more saccharide compositions.
  • Saccharification refers to the hydrolysis of cellulosic materials (e.g., biomass) into one or more saccharides (or sugars), by breaking down the complex carbohydrates of cellulose (and hemicellulose, where present) in the biomass.
  • the one or more sugars can be monosaccharides and/or oligosaccharides.
  • oligosaccharide refers to a compound containing two or more monosaccharide units linked by glycosidic bonds.
  • the one or more sugars are selected from glucose, cellobiose, xylose, xylulose, arabinose, mannose and galactose.
  • the cellulosic material can be subjected to a one-step or a multi-step hydrolysis process.
  • the cellulosic material is first contacted with the polymer catalyst, and then the resulting product is contacted with one or more enzymes in a second hydrolysis reaction (e.g. , using enzymes).
  • the saccharide composition includes at least one C5 saccharide and at least one C6 saccharide.
  • a "C5 saccharide” refers to a five-carbon sugar (or pentose), where as a “C6 saccharide” refers to a six-carbon sugar (or hexose).
  • Examples of C5 saccharides include arabinose, lyxose, ribose, xylose, ribulose, and xylulose.
  • Examples of C6 saccharides include allose, altrose, glucose, mannose, gulose, idose, galactose, talose, psicose, fructose, sorbose and tagatose.
  • the saccharide composition can include C5 saccharides and/or C6 saccharides that can be present as either the D- or L-isomer. In other embodiments, the saccharide composition can include a racemic mixture of the C5 saccharides and/or C6 saccharides.
  • the saccharide composition includes at least one C5 saccharide and the at least one C6 saccharide are present in the saccharide composition in a ratio suitable for fermentation to produce the ethylene glycol compound.
  • the saccharide composition includes at least one C5 saccharide and the at least one C6 saccharide are present in the saccharide composition in a ratio suitable for fermentation to produce one or more precursor compounds of propylene, such as, but not limited to, ethanol, lactic acid, 1,2- propanediol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol.
  • the saccharide composition includes two C5 saccharides and one C6 saccharide present in a ratio suitable for fermentation to produce one or more components suitable for use in a bio-based polymer. The ratio of the C5 and C6
  • saccharides can be further suitable to feed the fermentation host producing the ethylene glycol compound or one or more compounds that can be transformed into propylene.
  • the saccharide composition includes xylose, glucose and arabinose.
  • the xylose, glucose and arabinose can be present in a ratio of at least about 5 to about 1 to about 1, at least about 10 to about 1 to about 1, at least about 15 to about 1 to about 1, at least about 20 to about 1 to about 1.
  • the xylose, glucose and arabinose is present in a ratio of about 20 to about 1 to about 1.
  • the ratio of the sugars present can be optimized for conversion into the component of the bio-based polymer (e.g., ethylene glycol), while the glucose and arabinose present can be consumed by the fermentation host producing the component of the bio-based polymer (e.g. , ethylene glycol).
  • an exogenous source of sugar can not be needed to feed the fermentation host.
  • the ratio of the C5 and C6 saccharides present in saccharide composition can be varied based on the reaction conditions described above in degrading cellulosic materials. Further, it should be understood that the optimal ratio of the saccharides can vary depending the types of saccharides, the component of the bio-based polymer produced by fermentation, and the type of fermentation host used.
  • the saccharide composition has a concentration suitable for fermentation without prior concentration (e.g., by evaporation). It should also be understood that the saccharide composition can vary based on the type of cellulosic material used, as well as the reaction conditions described above in degrading cellulosic material.
  • the one or more sugars obtained from hydrolysis of cellulosic material can be used in a subsequent fermentation process to produce biofuels (e.g. , ethanol) and other bio-based chemicals (e.g. , bio-based polymers).
  • biofuels e.g. , ethanol
  • bio-based chemicals e.g. , bio-based polymers
  • the one or more sugars obtained by the methods described herein can undergo subsequent bacterial or yeast fermentation to produce biofuels and other bio-based chemicals.
  • a given ratio and concentration of sugars present in the saccharide composition can be varied depending on the fermentation host.
  • the saccharide composition obtained from hydrolysis of cellulosic material can be used in downstream processes to produce biofuels and other bio-based chemicals.
  • the saccharide composition obtained from hydrolysis of cellulosic material can be used to produce bio-based polymers, or component(s) thereof.
  • the saccharide composition obtained from hydrolysis of cellulosic material using the polymer catalyst described herein can be fermented to produce one or more downstream products (e.g. , ethanol and other biofuels, vitamins, lipids, proteins).
  • the saccharide composition can undergo fermentation to produce one or more difunctional compounds.
  • difunctional compounds can have an N-carbon chain, with a first functional group and a second functional group.
  • the first and second functional groups can be independent selected from -OH, -NH 2 , -COH, and -COOH.
  • the difunctional compounds can be alcohols, carboxylic acids, hydroxyacids, or amines.
  • Exemplary difunctional alcohols can include ethylene glycol, 1,3-propanediol, and 1,4- butanediol.
  • Exemplary difunctional carboxylic acids can include succinic acid, adipic acid, and pimelic acid.
  • Exemplary difunctional hydroxyacids can include glycolic acid, and 3- hydroxypropanoic acid.
  • Exemplary difunctional amines can include 1,4-diaminobutane, 1,5- diaminopentane, and 1,6-diaminohexane.
  • the methods described herein include combining the saccharide composition with a fermentation host to produce a fermentation product mixture that can have ethylene glycol, succinic acid, adipic acid, or butanediol, or a combination thereof.
  • the methods described herein include combining the saccharide composition with a fermentation host to produce a fermentation product mixture that has ethylene glycol.
  • the ethylene glycol compound can be monoethylene glycol, diethylene glycol, and polyethylene glycol.
  • the ethylene glycol compound is monoethylene glycol.
  • the ethylene glycol compound can be suitable for use in a polymer that is recyclable, at least partially bio-degradable, or a combination thereof.
  • the difunctional compounds can be isolated from the fermentation product mixture, and/or further purified. Any suitable isolation and purification techniques known in the art can be used.
  • the methods described herein include converting saccharide compositions chemically, by fermentation or a combination thereof, into intermediate compounds (e.g., D-xylulose, D-xylulose-5-phosphate, D-ribulose-5-phosphate, D-ribulose, D- ribulose-1 -phosphate, glycolaldehyde, and DHAP) and subsequently converting such intermediate compounds into ethylene glycol, directly or through additional intermediate compounds.
  • intermediate compounds e.g., D-xylulose, D-xylulose-5-phosphate, D-ribulose-5-phosphate, D-ribulose, D- ribulose-1 -phosphate, glycolaldehyde, and DHAP
  • the methods described herein include converting saccharide compositions chemically, by fermentation or a combination thereof, into intermediate compounds (e.g., glyceraldehyde, 2-phosphoglycerate, 3-phosphoglycerate, glycerate, serine, hydroxypyruvate, ethanolamine, or glycolaldehyde), and subsequently converting such intermediate compounds into ethylene glycol, directly or through additional intermediate compounds.
  • intermediate compounds e.g., g., g., US2011/0312049.
  • Glucose directly forms 3-phosphoglycerate, which is coverted by oxidation to 3-phosphohydroxypyruvate.
  • 3-phosphohydroxypyruvate is transaminated with glutamate to form 3-phosphoserine, which is in turn hydrolyzed (e.g., by a serine phosphatase) to serine.
  • the saccharide composition can undergo fermentation to produce one or more compounds selected from ethanol, lactic acid, 1,2-propanediol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol. All of these compounds can be transformed to propylene via chemical or further fermentation.
  • the methods described herein include combining the saccharide composition with a fermentation host to produce a fermentation product mixture that can include ethanol, lactic acid, 1,2-propanediol, 1-propanol, 2-propanol, 1-butanol, and 2- butanol, or a combination thereof.
  • the methods described herein include combining the saccharide composition with a fermentation host to produce a fermentation product mixture that has lactic acid or 1,2-propanediol.
  • the methods described herein include combining the saccharide composition with a fermentation host to produce a fermentation product mixture that has either or both of 1-propanol and 2-propanol.
  • the methods described herein include combining the saccharide composition with a fermentation host to produce a fermentation product mixture that has either or both of 1- butanol and 2-butanol.
  • the one or more compounds selected from ethanol, lactic acid, 1,2- propanediol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol can be suitable for use in a polymer that is recyclable, at least partially bio-degradable, or a combination thereof.
  • the methods described herein include converting saccharide compositions chemically, by fermentation or a combination thereof, into intermediate compounds, including, but not limited to, P-D-glucose-6-phosphate, 2-dihydroxyacetone (DHAP), glycoaldehyde, D-xylose-5-phosphate, D-ribulose-5-phosphate, L-ribulose-5- phosphate, D-ribulose-1 -phosphate, methylglyoxal, acetol, 1,2-propanediol, propanal, 1- propanol, propanoyl-CoA, propanoyl phosphate, propanoate, L-lactaldehyde, L-lactic acid, glycerol- 1 -phosphate, glycerol, dihydroxyacetone, 3-hydroxypropionaldehyde, 3- hydroxypropianate, and 1,3 propanediol.
  • intermediates can be converted directly to propylene or through other intermediate compounds.
  • P-D-glucose-6-phosphate is formed from either ⁇ -D-glucose or ⁇ -D-galactose, then undergoes glycolysis to produce DHAP.
  • D-Xylose can also be be transformed to to DHAP through a pathway that includes D-xylose-5-phosphate and D-ribulose- 1 -phosphate.
  • D- and L-arabinose can lead to DHAP via a route that includes transformation to the corresponding ribulose followed by phosphorylation.
  • DHAP can be converted through a pathway including methylglyoxal, acetol to provide 1,2-propane diol.
  • This diol can be fermented to produce propanal and then 1- propanol.
  • 1-Propanol can be convered into propylene via dehydration techniques well know in the art.
  • 1,2-Propanediol can also be transformed to propanoate using a pathway that includes propanal and propanal-CoA.
  • 1,2-Propane diol can be converted to L-lactaldehyde leading to L- lactic acid.
  • DHAP can be converted to either glycerol- 1 -phosphate or dihydroxyacetone, then to glycerol.
  • Glycerol can be fermented to 3-hydroxypropionaldehyde, which can lead to 3-hydroxypropionate and 1,3-propane diol.
  • the fermentation hosts can include wild type microorganisms or recombinant microorganisms, e.g., biocatalyts.
  • Biocatalysts can be microorganisms selected from bacteria, filamentous fungi and yeast.
  • Biocatalysts can be wild type microorganisms or recombinant microorganisms, and include Escherichia, Zymomonas, Saccharomyces, Candida, Pichia, Streptomyces, Bacillus, Lactobacillus, and Clostridium.
  • biocatalysts can be selected from recombinant Escherichia coli, Zymomonas mobilis, Bacillus stearothermophilus, Saccharomyces cerevisiae, Clostridia thermocellum, Thermoanaerobacterium saccharolyticum, and Pichia stipites.
  • the recombinant biocatalysts can be selected from Escherichia, Homo, Salmonella, Saccharomyces, Clostridium, Citrobacter, Pseudomonas, Bacillus, Caulobacter, Synechocystis, Arabidopsis, Azopirillum, Sulfolobus, Sphingomonas, Corynebacterium, Methanothermobacter, Schizosacchawmyces, and Klebsiella.
  • the wild type microorganisms or recombinant microorganisms can be selected from Escherichia coli, Homo sapiens, Salmonella enterica, Saccharomyces cerevisiae, Clostridium butyricum, Citrobacter freundii Clostridium pasteurianum, Pseudomonas putida, Bacillus coagulans, Caulobacter cescentus, Synechocystis sp. PCC 6803, Mycoplasma pneumoniae, Arabidopsis thaliana col, Azopirillum brasilense, Sulfolobus solfataricus, Sphingomonas sp.
  • XLDN2-5 Corynebacterium sp. SHS0007, Pseudomonas sp. ML2, Salmonella typhimurium LT2, Salmonella entericagene, Methanothermobacter thermautotrophicus Delta H, Schizosaccharomyces pombe, and Klebsiella pnuemoniae.
  • the fermentation host is bacteria.
  • the bacteria are classified in the family of Enterobacteriaceae. Examples of genera in the family include Aranicola, Arsenophonus, Averyella, Biostraticola, Brenneria, Buchnera, Budvicia, Buttiauxella, Candidatus, Curculioniphilus, Cuticobacterium, Candidatus Ishikawaella, Macropleicola, Phlomobacter, Candidatus Riesia, Candidatus Stammerula, Cedecea, Citrobacter, Cronobacter, Dickeya, Edwardsiella, Enterobacter, Erwinia, Escherichia, Ewingella, Grimontella, Hafnia, Klebsiella, Kluyvera, Leclercia, Leminorella, Margalefia, Moellerella, Morganella, Obesumbacterium, Pantoea, Pectobacterium, Photorhabdus, Phytobacter, Plesiomon
  • the fermentation host is genetically modified.
  • the fermentation host is genetically modified E. coli.
  • the fermentation host can be genetically modified to enhance the efficiency of specific pathways encoded by certain genes.
  • the fermentation host can be modified to enhance expression of endogenous genes that can positively regulate specific pathways.
  • the fermentation can be further modified to suppress expression of certain endogenous genes.
  • biocatalysts used in fermentation to produce target chemicals have been described and others can be discovered, produced through mutation, or engineered through recombinant means. Any biocatalyst that uses fermentable sugars produced from saccharification of biomass using the present system can be used to make the target chemical(s) that it is known to produce by fermentation.
  • biocatalysts that produce alcohols or biofuels including ethanol and butanol.
  • Alcohols include, but are not limited to methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propanediol, butanediol, glycerol, erythritol, xylitol, and sorbitol.
  • fermentation of carbohydrates to acetone, butanol, and ethanol (ABE fermentation) by solventogenic Clostridia is well known (Jones and Woods (1986) Microbiol. Rev. 50:484-524).
  • a fermentation process for producing high levels of butanol, also producing acetone and ethanol, using a mutant strain of Clostridium acetobutylicum is described in U.S. Pat. No. 5,192,673.
  • Isobutanol, 1 -butanol or 2-butanol can be produced from fermentation of hydrolysate produced using the present system by a microbial host following the disclosed methods.
  • Genetically modified strains of E. coli have also been used as biocatalysts for ethanol production (Underwood et al., (2002) Appl. Environ. Microbio. 68:6263-6272).
  • US20120122169 discloses the use of two E. coli ethylene glycol producing strains having differential overexpression of the gene coding for yqhD.
  • a genetically modified strain of Zymomonas mobilis that has improved production of ethanol is described in US 2003/0162271 Al.
  • a further engineered ethanol-producing strain of Zymomonas mobilis and its use for ethanol production are described in co-owned and co-pending U.S. patent applications 60/847,813 and 60/847,856, respectively, which are herein incorporated by reference.
  • Ethanol can be produced from fermentation of hydrolysate produced using the present system by Zymomonas mobilis following the disclosed methods.
  • Example 4 Saccharification of pretreated biomass which had pretreatment liquor containing inhibitors removed, to fermentable sugars followed by fermentation of the sugars to a target chemical is exemplified in Example 4 herein for the production of ethanol from pretreated corn cobs using Z. mobilis as the biocatalyst for the fermentation of sugars to ethanol.
  • Lactic acid has been produced in fermentations by recombinant strains of E. coli (Zhou et al., (2003) Appl. Environ. Microbiol. 69:399-407), natural strains of Bacillus (US20050250192), and Rhizopus oryzae (Tay and Yang (2002) Biotechnol. Bioeng. 80: 1-12).
  • Recombinant strains of E. coli have been used as biocatalysts in fermentation to produce 1,3 propanediol (U.S. Pat. No. 6,013,494, U.S. Pat. No. 6,514,733), and adipic acid (Niu et al., (2002) Biotechnol. Prog.
  • Acetic acid has been made by fermentation using recombinant Clostridia (Cheryan et al., (1997) Adv. Appl. Microbiol. 43: 1-33), and newly identified yeast strains (Freer (2002) World J. Microbiol. Biotechnol. 18:271-275).
  • Production of succinic acid by recombinant E. coli and other bacteria is disclosed in U.S. Pat. No. 6,159,738, and by mutant recombinant E. coli in Lin et al., (2005) Metab. Eng. 7: 116-127).
  • Pyruvic acid has been produced by mutant Torulopsis glabrata yeast (Li et al., (2001) Appl. Microbiol. Technol.
  • E. coli Yokota et al., (1994) Biosci. Biotech. Biochem. 58:2164- 2167.
  • Recombinant strains of E. coli have been used as biocatalysts for production of para- hydroxycinnamic acid (US20030170834) and quinic acid (US20060003429).
  • a mutant of Propionibacterium acidipropionici has been used in fermentation to produce propionic acid (Suwannakham and Yang (2005) Biotechnol. Bioeng. 91:325-337), and butyric acid has been made by Clostridium tyrobutyricum (Wu and Yang (2003) Biotechnol. Bioeng.
  • Propionate and propanol have been made by fermentation from threonine by Clostridium sp. strain 17crl (Janssen (2004) Arch. Microbiol. 182:482-486).
  • a yeast-like Aureobasidium pullulans has been used to make gluconic acid (Anantassiadis et al., (2005) Biotechnol. Bioeng. 91:494-501), by a mutant of Aspergillis niger (Singh et al., (2001) Indian J. Exp. Biol. 39: 1136- 43).
  • 5-keto-D-gluconic acid was made by a mutant of Gluconobacter oxydans (Elfari et al., (2005) Appl Microbiol. Biotech. 66:668-674), itaconic acid was produced by mutants of Aspergillus terreus (Reddy and Singh (2002) Bioresour. Technol. 85:69-71), citric acid was produced by a mutant Aspergillus niger strain (Ikram-Ul-Haq et al., (2005) Bioresour. Technol. 96:645-648), and xylitol was produced by Candida guilliermondii FTI 20037 (Mussatto and Roberto (2003) J. Appl. Microbiol.
  • a stable strain of E. coli can be transformed to contain a pathway for converting xylose to D-ribulose by metabolically engineering one or more of the following pathways: a) D-xylose to D-xylulose using an engineered xylose isomerase from, for example, the Escherichia coli gene xylA from Pseudomonas putida or the gene xylA from Bacillus coagulans. b) D-xylulose to D-xylulose- 5 -phosphate using an engineered xylulokinase from, for
  • phosphate 3-epimerase from, for example, the gene rpe from Escherichia coli,
  • the stable strain of E. coli can further be transformed to contain a pathway from D-ribulose to ethylene glycol by metabolically engineering one or more of the following pathways: a) D-ribulose + ATP to D-ribulose- 1 -phosphate + ADP using an engineered D-ribulokinase from, for example, the fuculokinase gene fucK from Escherichia coli; b) D-ribulose- 1 -phosphate to glycolaldehyde + DHAP using an engineered D-ribulose- phosphate aldolase from, for example, the gene fucA from Escherichia coli; and c) Glycolaldehyde + NADH + H + to ethylene glycol + NAD + using an engineered 1,2- propanediol oxidoreductase from, for example, the gene fucO from Escherichia coli.
  • the saccharide composition comprises xylose and the chemical intermediate is selected from one or more of xylulose, D-xylulose-5-phosphate, D- ribulose-5-phosphate, D-ribulose, D-ribulose- 1 -phosphate, glycolaldehyde, and 2- dihydroxyacetone phosphate.
  • the saccharide composition comprises xylose and the chemical intermediate is selected from one or more of D-xylulose-5-phosphate, D-ribulose- 1 -phosphate, and 2-dihydroxyacetone phosphate.
  • the saccharide composition comprises xylose and the chemical intermediate is selected from xylonate, 2-dehydro-3-deoxy-D-pentonate, and glycoaldehyde.
  • the fermentation host is genetically modified to comprise at least one exogenous nucleic acid encoding at least one ethylene glycol pathway enzyme selected from xylose isomerase, xylulokinase, ribulose phosphate 3-epimerase, phosphoribulokinase, D- ribulose-5-phosphate kinase, D-ribulokinase, D-ribulose-phosphate aldolase, and 1,2-propanediol oxidoreductase.
  • the fermentation host is genetically modified to comprise at least one exogenous nucleic acid encoding at least one ethylene glycol pathway enzyme selected from xylose dehydrogenase, xylonate dehydratase, 2-dehydro-3-deoxy-D-pentonate aldolase and glycoaldehyde reductase.
  • the chemical intermediate is selected from glyceraldehyde, 2-phosphoglycerate, 3-phosphoglycerate, glycerate, serine, hydroxypyruvate, ethanolamine, and glycolaldehyde.
  • the fermentation host is genetically modified to convert xylose to ribulose, and ribulose to the ethylene glycol compound or the chemical intermediate.
  • the fermentation host is genetically modified to comprise at least one exogenous nucleic acid encoding at least two ethylene glycol pathway enzymes.
  • the chemical intermediate between the sugar in the saccharide composition and the final product can be selected from D-xylulose, D-xylulose-5-phosphate, D- ribulose-5-phosphate, D-ribulose, D-ribulose-1 -phosphate, glycolaldehyde and DHAP.
  • the chemical intermediate between the sugar in the saccharide composition and the final product can be selected from D-xylulose, D-xylulose-5-phosphate, D-ribulose-5- phosphate.
  • the chemical intermediate between the sugar in the saccharide composition and the final product can be selected from D-ribulose-1 -phosphate, glycolaldehyde and DHAP.
  • DHAP is a gateway intermediate in that multiple pathways can be genetically engineered to create DHAP, such as the path from D-ribulose above, and multiple pathways are already known in the art to convert DHAP to other intermediates or final products.
  • FIGS. 10 and 11 depict pathways from DHAP to 1,2-propane diol, lactic acid, and 1-propanol. Further discussion of these pathways is detailed below.
  • These known pathways beginning with DHAP intersect with routes to compounds that can be chemically converted to propylene.
  • Also contemplated is the development of genetically engineered routes from DHAP, or other key intermediates, to compounds known as precursors of propylene.
  • the fermentation host can be genetically modified to include at least one exogenous nucleic acid encoding at least one ethylene glycol pathway enzyme selected from xylose dehydrogenase, xylonate dehydratase, 2-dehydro-3-deoxy-D-pentonate aldolase and glycoaldehyde reductase.
  • the chemical intermediate can be, for example, selected from glyceraldehyde, 2-phosphoglycerate, 3-phosphoglycerate, glycerate, serine, hydroxypyruvate, ethanolamine, and glycolaldehyde.
  • the fermentation host can be genetically modified to convert xylose to ribulose, and ribulose to the ethylene glycol compound or the chemical intermediate. See, e.g., Liu et al. (2013) Appl. Microbiol. Biotechnol. 97:3409-3417.
  • the fermentation host can be genetically modified to include at least one exogenous nucleic acid encoding at least two ethylene glycol pathway enzymes.
  • the ethylene glycol pathway enzyme can be selected from a serine aminotransferase, a serine decarboxylase, a serine oxidoreductase, a hydroxypyruvate decarboxylase, a glycoaldehyde reductase, an ethanolamine aminotransferase, an ethanolamine oxidoreductase, a hydroxypyruvate reductase, a glycerate decarboxylase, a 3-phosphoglycerate phosphatase, a glycerate kinase, a 2-phosphoglycerate phosphatase, a glycerate-2-kinase, and a glyceraldehyde dehydrogenase.
  • the ethylene glycol pathway enzyme can be selected from a glycerate dehydrogenase, a glycolaldehyde reductase, a hydroxypyruvate decarboxylase, a hydroxypyruvate isomerase, and a glyoxylate carboligase.
  • the ethylene glycol pathway enzyme can be selected from a glycolyl-CoA transferase, a glyoxylate reductase, a glycolyl-CoA synthetase, a glycolyl-CoA reductase, a glycolaldehyde reductase, a glycolate reductase, a glycolate kinase, a phosphotransglycolylase, a glycolylphosphate reductase, and a glycolyl-CoA reductase.
  • a stable strain of E. coli can be transformed to contain a pathway for converting C5 and C6 sugars to DHAP and glycoaldehyde by metabolically engineering one or more of the pathways shown in FIG. 9.
  • ⁇ -D-Glucose and ⁇ -D-galactose can be metabolized using ATP to give P-D-glucose-6-phosphate via the Leloir pathway. See, e.g., Frey (1946)_ FASEB J. 10:461-470).
  • the P-D-glucose-6-phosphate can be transformed into DHAP by glycolysis using ATP.
  • Other routes to propylene pathway intermediates include, but are not limited to: a) converting D-xylose to D-xylulose-5-phosphate as described above, then convert to D- ribulose-1 -phosphate using an engineered L-ribulose 5-phosphate 4-epimerase from, for example, the gene araD from Azopirillum brasilense, Eschericia coli or Sulfolobus solfataricus, or the gene araDh from Sulfolobus solfataricus.
  • D-ribulose-1 -phosphate can be transformed to DHAP as described above.
  • L-arabinose to L-ribulose via an engineered L-arabinose isomerase or L- arabinose 1 -dehydrogenase from, for example, the gene araA in Azospirillum brasilense or Escherichia coli, or the gene carA from Sphingomonas sp. XLDN2-5.
  • D-ribulose-1 -phosphate is transformed to DHAP as described in step a) above.
  • the saccharide composition comprises glucose or galactose and the chemical intermediate is selected from glucose-6-phosphate, 2- dihydroxyacetone phosphate, and glyco aldehyde.
  • the saccharide composition comprises one or more sugars selected from glucose, galactose, arabinose, and xylose, and the chemical intermediate is selected from glucose-6-phosphate, D-ribulose-1 -phosphate, and 2-dihydroxyacetone phosphate.
  • FIGS. 10 and 11 illustrate metabolic pathways from key C3 intermediates, such as DHAP, to propylene precursor compounds: a) converting DHAP to methylglyoxal and phosphate using an engineered methylglyoxal synthase from, for example, the Escherichia coli gene mgsA in Escherichia coli. See, e.g., Cooper (1984) Ann. Rev. Microbiol. 38:49-68.
  • Methylglyoxal can be converted to acetol using NADPH via an engineered L-glyceraldehyde 3-phosphate reductase or methylglyoxal reductase from, for example, the gene yeaE from Escherichia coli or the gene dkgA from Corynebacterium sp. SHS0007 or Escherichia coli. See, e.g., Misra et al. (1996) Mol. Cell Biochem. 156: 117-124.
  • transformation of acetol and NADH to 1,2-propanediol can be achieved with an engineered L- 1,2-propanediol dehydrogenase or glycerol dehydrogenase from, for example, the gene gldA from Escherichia coli, the gene bedD from Pseudomonas sp. ML2, the gene dhaBl from Klebsiella pneumoniae or the gene AKR1B1 from Homo sapien. See, e.g., Gonzalez et al. (2008) Metab. Eng. 105:234-235.
  • 1,2-Propanediol can be converted to propanal with an engineered propanediol dehydratase from, for example, the genes pduC, pduD, and pduE from Salmonella enterica or Salmonella typhimurium LT2, then with NADH producing 1-propanol using an engineered propanol dehydrogenase from, for example, the gene pduQ in Salmonella entericagene. See, e.g., Cheng et al. (2008) Bioessays 30: 1084-1095.
  • Phosphorylation results in forming propanoyl phosphate using an engineered phosphate propanoyltransferase from, for example, the pduL from Salmonella enterica or Salmonella typhimurium LT2 ⁇ see, e.g., Babik (1997) J. Bacteriol. 179:6633-6639), which can be converted into propanoate with an engineered propionate kinase from, for example, the gene pduW from Salmonella enterica or Salmonella typhimurium LT2 (see, e.g., Cheng et al.).
  • L-lactaldehyde converting 1,2-propane diol and NAD + to L-lactaldehyde with an engineered L- 1,2- propanediol oxidoreductase_from, for example, the gene fucO from Escherichia coli. See, e.g., Ting et al. (1964) Biochim. Biophys. Acta 89:217-225.
  • Another route to L-lactaldehyde involves transforming methylglyoxal with NADPH using an engineered methylglyoxal reductase from, for example, the gene GRE2 from Saccharomyces. cerevisiae. See, e.g., Chen (2003) Yeast 20:545-559.
  • L-Lactaldehyde and NAD + can be transformed to L-lactic acid using an engineered aldehyde dehydrogenase from, for example, either the gene ALD2 or the gene ALD3 from Saccharomyces cerevisiae. See, e.g., Navarro-Avino et al. (1999) Yeast 15:829-842.
  • Dephosphorylation provides glycerol using an engineered sugar phosphatase from, for example, the gene yfbT from Escherichia coli. See, e.g., Sussman (1981) Biochim. Biophys. Acta 661: 199-204.
  • DHAP can also be converted to dihydroxyacetone using an engineered dihydroxyacetone kinase from, for example, the gene DAK2 from Saccharomyces cerevisiase (see, e.g., Molin (2003) J. Biol. Chem. 278: 1415-1423), or the gene dak2 from Schizosaccharomyces pombe. See, e.g., Kimura et al. (1998) Biochim. Biophys.
  • Dihydroxyacetone can in turn be converted to glycerol with an engineered glycerol dehydrogenase from, for example, the gene gldA from Escherichia coli, the gene bedD from Pseudomonas sp. ML2, or the gene dhaB 1 from Klebsiella pneumoniae. Transformation of glycerol to 3-hydroxypropionaldehyde can be achieved with an engineered glycerol dehydratase from, for example, the gene dhaB 1 from Clostribium butyricum or Klebsiella pneumoniae, or the genes DhaB, DhaC, and DhE from Citrobacter freundii.
  • Conversion to 3-hydroxypropionate can be performed using an engineered ⁇ - glutamyl-y-aminobutyraldehyde dehydrogenase from, for example, the gene puuC from Escherichia coli. See, e.g., Joje, et al. (2008) Appl. Microbiol. Biotechnol. 81:51-60.
  • 3- Hydroxypropionaldehyde can also be converted to 1,3-propanediol using an engineered 1,3- propanediol dehydrogenase from, for example, the gene dhaT from Clostribium butyricum, Clostridium pasteurium, Citrobacter freundii or Klebsiella pneumoniae. See, e.g., Raynaud, et al., (2003) PNAS 100:5010-5015.
  • the fermentation host is genetically modified to include at least one exogenous nucleic acid encoding at least one propylene pathway enzyme selected from L-ribulose 5-phosphate 4-epimerase, L-arabinose isomerase, L-arabinose 1 -dehydrogenase, L- ribulokinase, L-ribulose 5-phosphate 4-epimerase, L-fucose, L-fuculokinase, methylglyoxal synthase, L-glyceraldehyde 3-phosphate, methylglyoxal reductase, L-l,2-propanediol dehydrogenase, glycerol dehydrogenase, propanediol dehydratase, propanol dehydrogenase, propanediol dehydratase, CoA-dependent propionaldehyde dehydrogenase, phosphate propanoyltransfera
  • propylene pathway enzyme selected from
  • the fermentation host is genetically modified to include at least one exogenous nucleic acid encoding at least one propylene pathway enzyme selected from D-ribulose- phosphate aldolase and L-ribulose 5-phosphate 4-epimerase.
  • the fermentation host is genetically modified to include at least one exogenous nucleic acid encoding at least one propylene pathway enzyme selected from D-ribulose-phosphate aldolase and L-ribulose 5-phosphate 4-epimerase.
  • the saccharide composition includes xylose, and the chemical intermediate is selected from D- xylulose-5-phosphate, D-ribulose-1 -phosphate and 2-dihydroxyacetone phosphate.
  • the fermentation host can be genetically modified to include at least one exogenous nucleic acid encoding at least one propylene pathway enzyme selected from L-arabinose isomerase, L- arabinose 1 -dehydrogenase, L-ribulokinase, L-ribulose 5-phosphate 4-epimerase, and D- ribulose-phosphate aldolase.
  • at least one propylene pathway enzyme selected from L-arabinose isomerase, L- arabinose 1 -dehydrogenase, L-ribulokinase, L-ribulose 5-phosphate 4-epimerase, and D- ribulose-phosphate aldolase.
  • the saccharide composition includes L-arabinose
  • the chemical intermediate is selected from L-ribulose-5 phosphate, D-ribulose-1 -phosphate and 2- dihydroxyacetone phosphate.
  • the fermentation host can be genetically modified to include at least one exogenous nucleic acid encoding at least one propylene pathway enzyme selected from L-fucose, L-fuculokinase, and D-ribulose-phosphate aldolase.
  • the saccharide composition includes D-arabinose and the chemical intermediate is selected from L-ribulose, D-ribulose-1 -phosphate and 2- dihydroxyacetone phosphate.
  • the fermentation host can be genetically modified to include at least one exogenous nucleic acid encoding at least one propylene pathway enzyme selected from methylglyoxal reductase, L-l,2-propanediol dehydrogenase, glycerol dehydrogenase, propanediol dehydratase, and propanol dehydrogenase.
  • the saccharide composition includes glucose or galactose and the chemical intermediate is selected from glucose-6-phosphate, 2-dihydroxyacetone phosphate, and glycoaldehyde.
  • the fermentation host is genetically modified to include at least one exogenous nucleic acid encoding at least one propylene pathway enzyme selected from D- ribulose-phosphate aldolase and L-ribulose 5-phosphate 4-epimerase.
  • the saccharide composition includes xylose
  • the chemical intermediate is selected from D-xylulose-5-phosphate, D-ribulose-1 -phosphate and 2- dihydroxyacetone phosphate.
  • the fermentation host is genetically modified to include at least one exogenous nucleic acid encoding at least one propylene pathway enzyme selected from L- arabinose isomerase, L-arabinose 1 -dehydrogenase, L-ribulokinase, L-ribulose 5-phosphate 4- epimerase, and D-ribulose-phosphate aldolase.
  • the saccharide composition includes L-arabinose
  • the chemical intermediate is selected from L-ribulose-5 phosphate, D-ribulose-1 -phosphate and 2- dihydroxyacetone phosphate.
  • the fermentation host can be genetically modified to include at least one exogenous nucleic acid encoding at least one propylene pathway enzyme selected from L-fucose, L-fuculokinase, and D-ribulose-phosphate aldolase.
  • the saccharide composition includes D-arabinose and the chemical intermediate is selected from L-ribulose, D-ribulose-1 -phosphate and 2- dihydroxyacetone phosphate.
  • the fermentation host can be genetically modified to include at least one exogenous nucleic acid encoding at least one propylene pathway enzyme selected from methylglyoxal reductase, L-l,2-propanediol dehydrogenase, glycerol dehydrogenase, propanediol dehydratase, and propanol dehydrogenase.
  • the chemical intermediate is selected from 1,2-propanediol, methyl glyoxal, L-lactaldehyde, and lactic acid.
  • the fermentation host can be genetically modified to include at least one exogenous nucleic acid encoding at least one propylene pathway enzyme selected from L- 1,2-propanediol oxidoreductase and aldehyde dehydrogenase.
  • the chemical intermediate is selected from 2-dihydroxyacetone phosphate, glycerol, 3-proprionaldehyde, and 1,3-propane diol.
  • the fermentation host can be genetically modified to include at least one exogenous nucleic acid encoding at least one propylene pathway enzyme selected from glycerol- 1 -phosphate dehydrogenase, glycerol-3-phosphate dehydrogenase, sugar phosphatase, dihydroxyacetone kinase, glycerol dehydrogenase, glycerol dehydratase, Y-glutamyl-y-aminobutyraldehyde dehydrogenase, and 1,3-propanediol dehydrogenase.
  • at least one propylene pathway enzyme selected from glycerol- 1 -phosphate dehydrogenase, glycerol-3-phosphate dehydrogenase, sugar phosphatase, dihydroxyacetone kinase, glycerol dehydrogenase, glycerol dehydratase, Y-glutamyl-y-aminobutyral
  • any of the pathways disclosed herein can be utilized to generate a non-naturally occurring microbial organism that produces any pathway intermediate or product, as desired.
  • a microbial organism that produces an intermediate can be used in combination with another microbial organism expressing downstream pathway enzymes to produce a desired product.
  • a non-naturally occurring microbial organism that produces a pathway intermediate can be utilized to produce the intermediate as a desired product.
  • reaction also constitutes reference to the reactants and products of the reaction.
  • reactant or product also references the reaction, and reference to any of these metabolic constituents also references the gene or genes encoding the enzymes that catalyze or proteins involved in the referenced reaction, reactant or product.
  • reference herein to a gene or encoding nucleic acid also constitutes a reference to the corresponding encoded enzyme and the reaction it catalyzes or a protein associated with the reaction as well as the reactants and products of the reaction.
  • any suitable methods known in the art can be employed to metabolically engineer the one or more pathways described above.
  • genetic alterations of microbial organisms include, for example, modifications introducing expressible nucleic acids encoding metabolic polypeptides, other nucleic acid additions, nucleic acid deletions and/or other functional disruption of the microbial organism's genetic material.
  • modifications include, for example, coding regions and functional fragments thereof, for heterologous, homologous or both heterologous and homologous polypeptides for the referenced species.
  • heterologous refers to a molecule or activity derived from a source other than the referenced species whereas “homologous” refers to a molecule or activity derived from the host microbial organism.
  • exogenous nucleic acid can be introduced into the host microbial organism on separate nucleic acid molecules, on polycistronic nucleic acid molecules, or a combination thereof, and still be considered as more than one exogenous nucleic acid.
  • the two exogenous nucleic acids can be introduced as a single nucleic acid, for example, on a single plasmid, on separate plasmids, can be integrated into the host chromosome at a single site or multiple sites, and still be considered as two exogenous nucleic acids.
  • An ortholog is a gene or genes that are related by vertical descent and are responsible for substantially the same or identical functions in different organisms.
  • paralogs are homologs related by, for example, duplication followed by evolutionary divergence and have similar or common, but not identical functions.
  • a nonorthologous gene displacement is a nonorthologous gene from one species that can substitute for a referenced gene function in a different species.
  • Orthologs, paralogs and nonorthologous gene displacements can be determined by methods well known to those skilled in the art. Those skilled in the art will understand that the identification of metabolic modifications can include identification and inclusion or inactivation of orthologs. To the extent that paralogs and/or nonorthologous gene displacements are present in the referenced microorganism that encode an enzyme catalyzing a similar or substantially similar metabolic reaction, those skilled in the art also can utilize these evolutionally related genes.
  • any of the one or more exogenous nucleic acids can be introduced into a microbial organism to produce a non-naturally occurring microbial organism.
  • the non-naturally occurring microbial organisms will include at least one exogenously expressed pathway-encoding nucleic acid and up to all encoding nucleic acids for one or more disclosed biosynthetic pathways.
  • ethylene glycol biosynthesis can be established in a host deficient in a pathway enzyme or protein through exogenous expression of the corresponding encoding nucleic acid.
  • exogenous expression of all enzyme or proteins in the pathway can be included, although it is understood that all enzymes or proteins of a pathway can be expressed even if the host contains at least one of the pathway enzymes or proteins.
  • Methods for constructing and testing the expression levels of a non-naturally occurring host can be performed, for example, by recombinant and detection methods well known in the art. Such methods can be found described in, for example, Sambrook et al., Molecular Cloning: A Laboratory Manual, Third Ed., Cold Spring Harbor Laboratory, New York (2001); and Ausubel et al., Current Protocols in Molecular Biology, John Wiley and Sons, Baltimore, Md. (1999). Exogenous nucleic acid sequences involved in a disclosed pathway can be introduced stably or transiently into a host cell using techniques well known in the art including, but not limited to, conjugation, electroporation, chemical transformation, transduction, transfection, and ultrasound transformation.
  • An expression vector or vectors can be constructed to include one or more bio synthetic pathway elements encoding nucleic acids as exemplified herein operably linked to expression control sequences functional in the host organism.
  • Expression vectors applicable for use in the microbial host organisms of the invention include, for example, plasmids, phage vectors, viral vectors, episomes and artificial chromosomes, including vectors and selection sequences or markers operable for stable integration into a host chromosome.
  • the expression vectors can include one or more selectable marker genes and appropriate expression control sequences. Selectable marker genes also can be included that, for example, provide resistance to antibiotics or toxins, complement auxotrophic deficiencies, or supply critical nutrients not in the culture media.
  • Expression control sequences can include constitutive and inducible promoters, transcription enhancers, transcription terminators, and the like which are well known in the art.
  • both nucleic acids can be inserted, for example, into a single expression vector or in separate expression vectors.
  • exogenous nucleic acid sequences involved in a metabolic or synthetic pathway can be confirmed using methods well known in the art. Such methods include, for example, nucleic acid analysis such as Northern blots or polymerase chain reaction (PCR) amplification of mRNA, or immunoblotting for expression of gene products, or other suitable analytical methods to test the expression of an introduced nucleic acid sequence or its corresponding gene product. It is understood by those skilled in the art that the exogenous nucleic acid is expressed in a sufficient amount to produce the desired product, and it is further understood that expression levels can be optimized to obtain sufficient expression using methods well known in the art and as disclosed herein. c) Fermentation conditions
  • any suitable fermentation conditions in the art can be employed to ferment the saccharide composition described herein to produce bio-based products, and components thereof.
  • a composition including a saccharide composition and a fermentation host under conditions such that ethylene glycol is capable of being produced.
  • a composition comprising a saccharide composition and a fermentation host under conditions such that one or more compounds selected from ethanol, lactic acid, 1,2-propanediol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol are capable of being produced.
  • saccharification described above can be combined with fermentation in a separate or a simultaneous process.
  • the fermentation can use the aqueous sugar phase or, if the sugars are not substantially purified from the reacted biomass, the fermentation can be performed on an impure mixture of sugars and reacted biomass.
  • Such methods include, for example, separate hydrolysis and fermentation (SHF), simultaneous saccharification and fermentation (SSF), simultaneous saccharification and cofermentation (SSCF), hybrid hydrolysis and fermentation (HHF), separate hydrolysis and co-fermentation (SHCF), hybrid hydrolysis and co-fermentation (HHCF), and direct microbial conversion (DMC).
  • SHF separate hydrolysis and fermentation
  • SSF simultaneous saccharification and fermentation
  • SSCF simultaneous saccharification and cofermentation
  • HHF hybrid hydrolysis and fermentation
  • SHCF separate hydrolysis and co-fermentation
  • HHCF hybrid hydrolysis and co-fermentation
  • DMC direct microbial conversion
  • SHF uses separate process steps to first enzymatically hydrolyze cellulosic material to fermentable sugars (e.g. , glucose, cellobiose, cellotriose, and pentose sugars), and then ferment the sugars to ethanol.
  • fermentable sugars e.g. , glucose, cellobiose, cellotriose, and pentose sugars
  • HHF involves a separate hydrolysis step, and in addition a simultaneous saccharification and hydrolysis step, which can be carried out in the same reactor.
  • the steps in an HHF process can be carried out at different temperatures; for example, high temperature enzymatic saccharification followed by SSF at a lower temperature that the fermentation strain can tolerate.
  • DMC combines all three processes (enzyme production, hydrolysis, and fermentation) in one or more steps where the same organism is used to produce the enzymes for conversion of the cellulosic material to fermentable sugars and to convert the fermentable sugars into a final product. See Lynd, L. R., Weimer, P. J., van Zyl, W. H., and Pretorius, I. S., Microbial cellulose utilization: Fundamentals and biotechnology, Microbiol. Mol. Biol. Reviews, 66: 506-577 (2002).
  • bio-based polymers Among the downstream products described herein produced by fermentation of sugars liberated from cellulosic materials are bio-based polymers.
  • the bio-based polymers can be recyclable and/or at least partially bio-degradable. Many bio-based polymers can be incorporated into plastics as described above.
  • the bio-based polymer is polyethylene glycol. In another embodiment, the bio-based polymer is polypropylene.
  • the bio-based polymer is polyethylene terephthalate, or copolyesters thereof.
  • a bio-based polymer can be produced by reacting a terephthalate component and a diol component, as described in U.S. Patent Application Nos. 2009/0246430 and 2010/0028512.
  • the bio-based polymer can include between about 25-75 wt , between about 30-70 wt , or between about 40-65 wt of the terephthalate component.
  • the terephthalate component can include, for example, terephthalic acid, dimethylterephthalate, or isophthalic acid, or a combination thereof.
  • of the terephthalate component is bio-derived, such that at least a portion of the terephthalate component is produced from cellulosic materials.
  • At least about 1 wt%, at least about 5 wt%, at least about 10 wt%, at least about 15 wt%, at least about 20 wt%, at least about 25 wt%, at least about 30 wt%, at least about 40 wt%, at least about 50 wt%, at least about 60 wt%, at least about 70 wt%, at least about 80 wt%, at least about 90 wt%, or about 100 wt% of the terephthalate component is derived from cellulosic material. Any suitable methods currently known in the art can be employed to produce a bio-derived terephthalate component.
  • carene can be derived from cellulosic materials, and converted to cymene and oxidized to form terephthalic acid.
  • limonene can be derived from cellulosic materials, and converted to terpene and then cymene, which can be oxidized to form terephthalic acid. See e.g., U.S. Patent No. 2009/0246430.
  • the bio-based polymer can include between about 25-50 wt%, between about 25-45%, between about 25-40%, or between about 25-35 wt% of the diol component.
  • the diol component can include an ethylene glycol compound, such as monoethylene glycol, wherein at least a portion of the ethylene glycol compound is bio-derived and produced according to the methods described herein.
  • the diol component can further include cyclohexane dimethanol.
  • the bio-based polymer can include between about 30-70 wt% of the terephthalate component and between about 25-45% of the diol component.
  • a product containing an ethylene glycol-containing compound produced by the step of combining a saccharide composition with a fermentation host to produce a fermentation product mixture comprising the ethylene glycol-containing compound, wherein the saccharide composition is produced by contacting a cellulosic material with a polymer catalyst, wherein the polymer catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, wherein a plurality of the acidic monomers independently comprise at least one Bronsted-Lowry acid, wherein one or more of the acidic monomers comprises a linker connecting the Bronsted-Lowry acid to the polymeric backbone, wherein a plurality of ionic monomers independently comprise at least one nitrogen-containing cationic group or phosphorous-containing cationic group, and wherein one or more of the ionic monomers comprises a linker connecting the nitrogen-containing cationic group or the phosphorous-containing cationic group to the polymeric backbone, under conditions such
  • a product containing a propylene-containing compound produced by the step of combining a saccharide composition with a fermentation host to produce a fermentation product mixture comprising one or more second compounds selected from ethanol, lactic acid, 1,2-propanediol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol, or a chemical intermediate between the saccharide composition and the one or more second compounds, wherein the saccharide composition is produced by contacting a cellulosic material with a polymer catalyst, wherein the polymer catalyst comprises acidic monomers and ionic monomers connected to form a polymeric backbone, wherein a plurality of the acidic monomers independently comprise at least one Bronsted-Lowry acid, wherein one or more of the acidic monomers comprises a linker connecting the Bronsted-Lowry acid to the polymeric backbone, wherein a plurality of ionic monomers independently comprise at least one nitrogen-containing cationic group
  • the bio-based polymer can include additional ingredients (e.g. , coloring agent or other additives as described above) to make the polymer suitable for use in various plastics applications.
  • Plastics are used to produce a diverse array of products, including, but not limited to, a) household and kitchenware (e.g., bottles, dishes, utensils, packaging, such as food wrapping and easy seal or reusable bags, non-stick cookware, coffee pots, refridgerator components, microwave casing and components, household implement handles and other components, surface laminates such as countertops, toothbrushes, and hair dryers), toilets, sinks and other bathroom fixtures, plumbing piping and systems, lighting fixtures, flooring (e.g., carpeting, rugs, and laminates), furniture, windows and frames, insulation, textiles (e.g., clothing, shoes and soles, fabrics, upholstery, curtains and window treatments, coverings, rope/string, and high performance fibers), cosmetics, and handbags/tote bags/luggage;
  • textiles e.g., clothing
  • applicances computers, printers, cellular phones and other mobile devices, CDs, cassette tapes, radios, clocks and watches, TVs, VCRs, video games and consoles; vehicle components such as body parts, upholstery, engine components, and cabin parts; and d) laboratory equipment, chemical bottles, drums and carboys, tubing, gaskets, bearings, valves, seals, pumps, knobs, piping, sealants, adhesives, resins, foams, coatings, tapes, packaging such as for commercial products or shipping, pipettes and tips, brushes, and paints, dyes, and pigments.
  • polyethylene terephthalate can be used to produce one or more products selected from vehicle components, electronics, plastic bottles, such as those used for carbonated and non-carbonated beverages, and food packaging, such as egg cartons and plastic films.
  • polyethylene terephthalate can be used to produce a beverage container (e.g. , a bottle).
  • Polypropylene for example, can be used to produce one or more products selected from plastic bottles, food containers, packaging, household and kitchenware, bags, furniture, insulation, toys, vehicle components, chemical drums and totes, and piping.
  • the product is selected from household and kitchenware (e.g., bottles, dishes, utensils, packaging, such as food wrapping and easy seal or reusable bags, nonstick cookware, coffee pots, refridgerator components, microwave casing and components, household implement handles and other components, surface laminates such as countertops, toothbrushes, and hair dryers).
  • the product is selected from bottles, dishes, utensils, and packaging.
  • the product is selected from toilets, sinks and other bathroom fixtures, plumbing piping and systems, lighting fixtures, flooring (e.g., carpeting, rugs, and laminates), furniture, windows and frames, insulation cosmetics, and handbags/tote bags/luggage.
  • the product is a textile, such as clothing, shoes and soles, fabrics, upholstery, curtains and window treatments, coverings, rope/string, and high performance fibers.
  • the product is selected from surgical and medical implements (e.g., syringes, tubing, liquid and solid packaging, prescription bottles, handles for surgical/medical instruments, sterile clothing and masks), medical implants and devices, eyeglass lenses and frames, and contact eye lenses.
  • surgical and medical implements e.g., syringes, tubing, liquid and solid packaging, prescription bottles, handles for surgical/medical instruments, sterile clothing and masks
  • medical implants and devices e.g., eyeglass lenses and frames, and contact eye lenses.
  • eyeglass lenses and frames e.g., contact eye lenses.
  • the product is selected from electronics, including heat resistant components; circuit boards; electrical wire coverings; electrical switches; casings, screens, and components for, e.g., applicances, computers, printers, cellular phones and other mobile devices, CDs, cassette tapes, radios, alarm and other clocks and watches, TVs, VCRs, video games and consoles; and vehicle components such as body parts, upholstery, engine components, and cabin parts.
  • the product is selected from casings, screens and components for applicances, computers, printers, cellular phones and other mobile devices, and TVs.
  • the product is selected from vehicle components such as body parts, upholstery, engine components, and cabin parts.
  • the product is selected from laboratory equipment, chemical bottles, drums and carboys, tubing, gaskets, bearings, valves, seals, pumps, knobs, piping, sealants, adhesives, resins, foams, coatings, tapes, packaging such as for commercial products or shipping, pipettes and tips, brushes, and paints, dyes, and pigments.
  • the product is selected from laboratory equipment, chemical bottles, drums and carboys, and packaging such as for commercial products or shipping.
  • the product is selected from gaskets, bearings, valves, seals, pumps, knobs, piping, sealants, adhesives, resins, foams, coatings, tapes, brushes, and paints, dyes, and pigments.
  • polymers described herein can be made using polymerization techniques known in the art, including for example techniques to initiate polymerization of a plurality of monomer units.
  • the catalysts described herein can be formed by first forming an intermediate polymer functionalized with the ionic group, but is free or substantially free of the acidic group. The intermediate polymer can then be functionalized with the acidic group. In other embodiments, the catalysts described herein can be formed by first forming an intermediate polymer functionalized with the acidic group, but is free or substantially free of the ionic group. The intermediate polymer can then be functionalized with the ionic group. In yet other embodiments, the catalysts described herein can be formed by polymerizing monomers with both acidic and ionic groups.
  • steps a), b), and c) are performed in the order a), b), and c); or in the order a), c), and b); where the polymer is produced in step b) instead of step c).
  • the starting polymer is selected from polyethylene, polypropylene, polyvinyl alcohol, polycarbonate, polystyrene, polyurethane, or a combination thereof.
  • the starting polymer is a polystyrene.
  • the starting polymer is poly(styrene-co-vinylbenzylhalide-co-divinylbenzene).
  • the starting polymer is poly(styrene-co-vinylbenzylchloride-co-divinylbenzene).
  • the nitrogen-containing compound is selected from a pyrrolium compound, an imidazolium compound, a pyrazolium compound, an oxazolium compound, a thiazolium compound, a pyridinium compound, a pyrimidinium compound, a pyrazinium compound, a pyradizimium compound, a thiazinium compound, a morpholinium compound, a piperidinium compound, a piperizinium compound, and a pyrollizinium compound.
  • the nitrogen-containing compound is an imidazolium compound.
  • the phosporus-containing compound is selected from a triphenyl phosphonium compound, a trimethyl phosphonium compound, a triethyl phosphonium compound, a tripropyl phosphonium compound, a tributyl phosphonium compound, a trichloro phosphonium compound, and a trifluoro phosphonium compound.
  • the acid is selected from sulfuric acid, phosphoric acid, hydrochloric acid, acetic acid and boronic acid.
  • the acid is sulfuric acid.
  • polystyrene is poly(styrene-co-vinylbenzylhalide-co-divinylbenzene). In one embodiment, the polystyrene is poly(styrene-co-vinylbenzylchloride-co-divinylbenzene).
  • the polymer has one or more catalytic properties selected from:
  • the polymers described herein can be made, for example, on a scale of at least about 100 g, at least about 1 kg, at least about 20 kg, at least about 100 kg, at least about 500 kg, or at least about 1 ton in a batch or continuous process.
  • chromatographic purification of reactants or products was accomplished using forced-flow chromatography on 60 mesh silica gel according to the method described of Still et al, See Still et al, J. Org. Chem., 43: 2923 (1978).
  • Thin-layer chromatography (TLC) was performed using silica-coated glass plates. Visualization of the developed chromatogram was performed using either Cerium Molybdate (i.e., Hanessian) stain or KMn0 4 stain, with gentle heating, as required.
  • FTIR Fourier- Transform Infrared
  • the reaction flask was transferred to an oil bath to increase the reaction temperature to 75°C, and the mixture was stirred vigorously for 28 hours.
  • the resulting polymer beads were vacuum filtered using a fritted-glass funnel to collect the polymer product.
  • the beads were washed repeatedly with 20% (by volume) methanol in water, THF, and MeOH, and dried overnight at 50°C under reduced pressure to yield 59.84 g of polymer.
  • the polymer beads were separated by size using sieves with mesh sizes 100, 200, and 400.
  • the resulting mixture was titrated against a standardized solution of silver nitrate to the potassium chromate endpoint.
  • the polymer was first treated by stirring the material in aqueous hydrochloric acid, followed by washing repeatedly with water until the effluent was neutral (as determined by pH paper).
  • the chemical functionalization of the polymer resin with methylimidazolium chloride groups was determined to be 2.60 mmol/g via gravimetry and 2.61 mmol/g via titrimetry.
  • Example 7 Preparation of poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4- vinylbenzyl)-3H-imidazol-l-ium bisulfate-co-divinylbenzene]
  • Example 8 Preparation of poly[styrene-co-4-vinylbenzenesulfonic acid-co-3-ethyl-l-(4- vinylbenzyl)-3H-imidazol-l-ium chloride-co-divinylbenzene]
  • Example 10 Preparation of poly [styrene-co-4-vinylbenzenesulfonic acid-co-l-(4- vinylbenzyl)-3H-imidazol-l-ium bisulfate-co -divinylbenzene]
  • Example 12 Preparation of poly [styrene-co-4-vinylbenzenesulfonic acid-co-3-methyl-l-(4- vinylbenzyl)-3H-benzoimidazol-l-ium bisulfate-co -divinylbenzene]
  • Example 15 Preparation of poly [styrene-co-l-(4-vinylbenzyl)-pyridinium chloride-co-3- methyl- 1 - (4- vinylbenzyl) -3H-imidazol- 1 -ium chloride-co -divinylbenzene]
  • Example 16 Preparation of poly[styrene-co-4-vinylbenzenesulfonic acid-co-l-(4- vinylbenzyl)-pyridiniumchloride-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium bisulf ate-co -divinylbenzene]
  • the slurry was heated at 95- 100°C under continuous stirring for 12 h. After completion of reaction, the cooled reaction mixture was filtered using fritted glass funnel under vacuum and then washed repeatedly with de-ionized water until the effluent was neutral, as determined by pH paper. The sulfonated resin beads were finally washed with ethanol and air dried.
  • the chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 1.16 mmol/g, as determined by titrimetry following the procedure of Example 2.
  • Example 20 Preparation of poly[styrene-co-4-vinylbenzenesulfonic acid-co-triphenyl-(4- vinylbenzyl)-phosphonium bisulfate-co-divinylbenzene] [00407] Poly (styrene-co-triphenyl-(4-vinylbenzyl)-phosphonium chloride- co- divinylbenzene) (7 g) was charged into a 100 mL flask equipped with a magnetic stir bar and condenser.
  • Example 22 Preparation of poly[styrene-co-4-vinylbenzenesulfonic acid-co-l-(4- vinylbenzyl)-piperidine-c0-divinyl benzene]
  • Example 23 Preparation of poly[styrene-co-4-vinylbenzenesulfonic acid-co-l-methyl-l-(4- vinylbenzyl)-piperdin-l-ium chloride-co-di vinyl benzene]
  • reaction mixture was filtered using fritted glass funnel under vacuum and then washed multiple times with dilute HC1 solution to ensure complete exchange of ⁇ with CI " .
  • the resin was finally washed with de-ionized water until the effluent was neutral, as determined by pH paper. The resin was finally air-dried.
  • Example 25 Preparation of poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-(4- vinylbenzyl)-morpholine-c0-divinyl benzene]
  • Example 26 Preparation of poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-(4- vinylbenzyl)-morpholine-4-oxide-c0 -divinyl benzene]
  • Example 28 Preparation of poly[styrene-co-4-vinylbenzenesulfonic acid-co-triethyl-(4- vinylbenzyl)-ammonium chloride-co-divinylbenzene]
  • reaction mixture was filtered using fritted glass funnel under vacuum and then washed repeatedly with de-ionized water.
  • the resin beads were finally washed with ethanol and air dried.
  • the chemical functionalization of the polymer with sulfonic acid group and methylimidiazolium chloride groups was determined to be 0.23 mmol/g and 2.63 mmol/g, respectively, as determined by titrimetry following the procedure of Example 2.
  • Example 32 Preparation of poly[styrene-co-3-methyl-l-(4-vinylbenzyl)-3H-imidazol-l-ium chloride-co - 1 - (4- vinylphenyl)methylphosphonic acid-co -divinylbenzene]
  • Example 35 Preparation of poly[styrene-co-4-vinylbenzenesulfonic acid-co-4-(4- vinylbenzyl)-morpholine-4-oxide-c0 -divinyl benzene]
  • Example 36 Preparation of poly [styrene-co-4-vinylphenylphosphonic acid-co-3-methyl-l- (4-vinylbenzyl)-3H-imidazol-l-ium chloride-co -divinylbenzene]
  • the washed resin beads were suspended in the ethanolic sodium hydroxide solution and refluxed overnight.
  • the resin beads were filtered and successively washed with deionized water multiple times and ethanol, and finally air dried.
  • the chemical functionalization of the polymer with carboxylic acid group was determined to be 0.16 mmol/g, as determined by titrimetry following the procedure of Example 2.
  • Example 39 Preparation of poly[styrene-co-(4-vinylbenzylamino)-acetic acid-co-3-methyl- 1 -(4- vinylbenzyl) -3H-imidazol- 1 -ium chloride-co -divinylbenzene]
  • the reaction flask After 2 hours of stirring at 0 °C to homogenize the mixture, the reaction flask is transferred to an oil bath to increase the reaction temperature to 75°C, and the mixture is stirred vigorously for 24 hours.
  • the resulting polymer is vacuum filtered using a fritted-glass funnel, washed repeatedly with 20% (by volume) methanol in water, THF, and MeOH, and then dried overnight at 50°C under reduced pressure.
  • Example 41 Preparation of poly(styrene-co-vinylbenzylmethylimidazolium chloride-co- vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride- co -divinylbenzene)
  • the resulting reaction mixture was refluxed for 24 h. After cooling, the reaction mixture was filtered using a fritted glass funnel under vacuum, washed sequentially with acetone and ethyl acetate, and dried overnight at 70 °C.
  • the chemical functionalization of the polymer resin with chloride groups was determined to be 2.61 mmol / g dry resin via titrimetry.
  • Example 42 Preparation of sulfonated poly(styrene-co-vinylbenzylmethylimidazolium bisulfate-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenyl
  • Example 43 Preparation of poly(styrene-co-vinylbenzylmethylimidazolium chloride-co- vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride- co -divinylbenzene)
  • the resulting reaction mixture was refluxed for 18 h. After cooling, the reaction mixture was filtered using fritted glass funnel under vacuum, washed sequentially with acetone and ethyl acetate, and dried at 70 °C overnight.
  • the chemical functionalization of the polymer resin with chloride groups was determined to be 2.36 mmol / g dry resin dry resin via titrimetry.
  • Example 44 Preparation of sulfonated poly(styrene-co-vinylbenzylmethylimidazolium bisulfate-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenyl
  • Poly(styrene-co-vinylbenzylmethylimidazolium chloride-co vinylbenzylmethylmorpholinium chloride-co-vinylbenzyltriphenylphosphonium chloride-co- divinylbenzene) 35.12 g was charged into a 500 mL flask equipped with a magnetic stir bar and condenser. Fuming sulfuric acid (20% free S0 3 , 175 mL) was gradually added into the flask and stirred to form dark-red colored slurry of resin. The slurry was stirred at 90°C overnight.
  • reaction mixture was filtered using fritted glass funnel under vacuum and then washed repeatedly with de-ionized water until the effluent was neutral, as determined by pH paper.
  • the sulfonated beads were finally air dried.
  • the chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 4.38 mmol / g dry resin.
  • reaction mixture was filtered using fritted glass funnel under vacuum, washed sequentially with acetone and ethyl acetate, and dried at 70 °C overnight.
  • the chemical functionalization of the polymer resin with chloride groups was determined to be 2.22 mmol / g dry resin via titrimetry.
  • Example 46 Preparation of sulfonated poly(styrene-co-vinylbenzylmethylmorpholinium bisulfate-co-vinylbenzyltriphenylphosphonium bisulfate-co -divinylbenzene)
  • reaction mixture was filtered using fritted glass funnel under vacuum and then washed repeatedly with de-ionized water until the effluent was neutral, as determined by pH paper.
  • the sulfonated beads were dried under air to a final moisture content of 52% g H 2 0 / g wet resin.
  • the chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 4.24 mmol / g dry resin.
  • Phenol (12.87 g, 136.8 mmol) was dispensed into a 100 mL round bottom flask (RBF) equipped with a stir bar and condenser.
  • De-ionized water (lOg) was charged into the flask.
  • 37% Formalin solution (9.24g, 110 mmol) and oxalic acid (75mg) were added.
  • the resulting reaction mixture was refluxed for 30 min. Additional oxalic acid (75mg) was then added and refluxing was continued for another 1 hour. Chunk of solid resin was formed, which was ground to a coarse powder using a mortar and pestle. The resin was repeatedly washed with water and methanol and then dried at 70 °C overnight.
  • Phenol-formaldehyde resin (5.23 g, 44 mmol) was dispensed into a 100 mL three neck round bottom flask (RBF) equipped with a stir bar, condenser and nitrogen line. Anhydrous dichloroethane (DCE, 20ml) was then charged into the flask. To ice-cooled suspension of resin in DCE, zinc chloride (6.83g, 50 mmol) was added. Chloromethyl methyl ether (4.0 ml, 51 mmol) was then added dropwise into the reaction. The mixture was warmed to room temperature and stirred at 50°C for 6h. The product resin was recovered by vacuum filtration and washed sequentially with water, acetone and dichloromethane. The washed resin was dried at 40°C overnight.
  • DCE three neck round bottom flask
  • Triphenylphosphine (10.12, 38.61 mmol) were charged into a 100 mL flask equipped with a magnetic stir bar and condenser. Acetone (30 ml) was added into the flask and mixture was stirred at 50°C for 10 min. Chloromethylated phenol-formaldehyde resin (4.61g, 38.03 mmol) was charged into flask while stirring. The resulting reaction mixture was refluxed for 24 h. After cooling, the reaction mixture was filtered using fritted glass funnel under vacuum, washed sequentially with acetone and ethyl acetate, and dried at 70°C overnight.
  • Triphenylphosphine-functionalized phenol-formaldeyde resin (5.12 g, 13.4 mmol) was charged into a 100 mL flask equipped with a magnetic stir bar and condenser. Fuming sulfuric acid (20% free S0 3 , 25 mL) was gradually added into the flask and stirred to form dark- red colored slurry of resin. The slurry was stirred at 90°C overnight. After cooling, the reaction mixture was filtered using fritted glass funnel under vacuum and then washed repeatedly with de-ionized water until the effluent was neutral, as determined by pH paper.
  • the sulfonated resin was dried under air to a final moisture content of 49% g H 2 0 / g wet resin.
  • the chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 3.85 mmol / g dry resin.
  • Benzoyl peroxide (75%, 1.205g) was added, and temperature was raised to 80 °C.
  • the reaction mixture was heated for 8h at 80 °C with stirring rate of 500 rpm.
  • the polymer product was recovered by vacuum filtration and washed with water and acetone multiple times.
  • the isolated polymer was purified by soxhlet extraction with water and acetone. The resin was dried at 40°C overnight.
  • Example 53 Preparation of sulfonated poly(styrene-co-vinylmethylimidazolium bisulfate- co -divinylbenzene)
  • Example 54 Preparation of poly(styrene-co-vinylbenzyltriphenylphosphonium chloride- co -divinylbenzene)
  • reaction mixture was filtered using fritted glass funnel under vacuum, washed sequentially with acetone and ethyl acetate, and dried at 70 °C overnight.
  • the chemical functionalization of the polymer resin with triphenylphosphonium chloride groups was determined to be 1.94 mmol / g dry resin via titrimetry.
  • Example 55 Preparation of sulfonated poly(styrene-co-vinylbenzyltriphenyl phosphonium bisulf ate-co -divinylbenzene)
  • the sulfonated beads were dried under air to a final moisture content of 54% g H 2 0 / g wet resin.
  • the chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 4.39 mmol / g dry resin.
  • reaction mixture was filtered using fritted glass funnel under vacuum, washed sequentially with acetone and ethyl acetate, and dried at 70 °C overnight.
  • the chemical functionalization of the polymer resin with triphenylphosphonium chloride groups was determined to be 2.00 mmol / g dry resin via titrimetry.
  • Example 57 Preparation of sulfonated poly(styrene-co-vinylbenzyltriphenyl phosphonium bisulf ate-co -divinylbenzene)
  • the sulfonated beads were dried under air to a final moisture content of 47% g H 2 0 / g wet resin.
  • the chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 4.36 mmol / g dry resin.
  • reaction mixture was filtered using fritted glass funnel under vacuum, washed sequentially with acetone and ethyl acetate, and dried at 70°C overnight.
  • the chemical functionalization of the polymer resin with methylimidazolium chloride groups was determined to be 3.54 mmol / g dry resin via titrimetry.
  • Example 59 Preparation of sulfonated poly(styrene-co-vinylbenzylmethylimidazolium bisulf ate-co -divinylbenzene)
  • the sulfonated beads were dried under air to a final moisture content of 50% g H 2 0 / g wet resin.
  • the chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 2.87 mmol / g dry resin.
  • Example 60 Preparation of pol (styrene-co -vinylbenzylmethylimidazolium chloride-co- divinylbenzene) [00447] To a 250 mL flask equipped with a magnetic stir bar and condenser was charged 1- methylimidazole (20mL, 248.4 mmol). Acetone (75 mL) was added into the flask and mixture was stirred at 50 °C for 10 min.
  • Example 61 Preparation of sulfonated poly(styrene-co-vinylbenzylmethylimidazolium bisulf ate-co -divinylbenzene)
  • the sulfonated beads were dried under air to a final moisture content of 55% g H 2 0 / g wet resin.
  • the chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 2.78 mmol / g dry resin.
  • Example 63 Preparation of sulfonated poly(styrene-co-vinylbenzyltriphenyl phosphonium bisulf ate-co -divinylbenzene)
  • the sulfonated beads were dried under air to a final moisture content of 46% g H 2 0 / g wet resin.
  • the chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 2.82 mmol / g dry resin.
  • Example 65 Preparation of sulfonated poly(styrene-co-vinylbenzyltriphenyl phosphonium bisulfate-co-divinylbenzene)
  • the sulfonated beads were dried under air to a final moisture content of 49% g H 2 0 / g wet resin.
  • the chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 2.82 mmol / g dry resin.
  • the sulfonated beads were dried under air to a final moisture content of 59% g H 2 0 / g wet resin.
  • the chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 3.03 mmol / g dry resin.
  • Example 69 Preparation of sulfonated poly(styrene-co-vinylbenzyltriphenyl phosphonium bisulf ate-co -divinylbenzene)
  • the sulfonated beads were dried under air to a final moisture content of 57% g H 2 0 / g wet resin.
  • the chemical functionalization of the polymer resin with sulfonic acid groups was determined to be 3.04 mmol / g dry resin.
  • Example 70 Preparation of poly(butyl-vinylimidazolium chloride-co-butylimidazolium chloride-co-styrene)
  • Example 71 Preparation of sulfonated poly(butyl-vinylimidazolium bisulfate-co- butylimidazolium bisulfate-co-styrene)
  • Example Bl Digestion of Sugarcane Bagasse using Catalyst described in Example 3
  • Sugarcane bagasse (50% g H 2 0/g wet bagasse, with a dry-matter composition of: 39.0% g glucan/g dry biomass, 17.3% g xylan / g dry biomass, 5.0% g arabinan / g dry biomass, 1.1% g galactan / g dry biomass, 5.5% g acetate / g dry biomass, 5.0% g soluble extractives / g dry biomass, 24.1% g lignin / g dry biomass, and 3.1% g ash / g dry biomass) was cut such that the maximum particle size was no greater than 1 cm.
  • composition of the lignocellulosic biomass was determined using a method based on the procedures known in the art. See R. Ruiz and T. Ehrman, "Determination of Carbohydrates in Biomass by High Performance Liquid Chromatography," NREL Laboratory Analytical Procedure LAP-002 (1996); D. Tempelton and T. Ehrman, “Determination of Acid-Insoluble Lignin in Biomass," NREL Laboratory Analytical Procedure LAP-003 (1995); T. Erhman, “Determination of Acid-Soluble Lignin in Biomass," NREL Laboratory Analytical Procedure LAP-004 (1996); and T. Ehrman, "Standard Method for Ash in Biomass," NREL Laboratory Analytical Procedure LAP-005 (1994).
  • Example B2 Separation of Catalyst/Product Mixture from the Hydrolysis of Sugarcane Bagasse
  • Example B3 Recovery of Sugars and Soluble Carbohydrates from the Hydrolysis of Sugarcane Bagasse
  • HPLC high performance liquid chromatography
  • RI refractive index
  • the ability of the catalyst to hydrolyze the cellulose and hemicellulose components of the biomass to soluble sugars was measured by determining the effective first-order rate constant.
  • the extent of reaction for a chemical species e.g. , glucan, xylan, arabinan
  • the first-order rate constant for conversion of xylan to xylose was determined to be 0.3/hr.
  • the first- order rate constant for conversion of glucan to soluble monosaccharides and oligosaccharides (including disaccharides) was determined to be 0.08/hr.
  • the number average degree of polymerization of the oligo-glucans was determined to be 19 + 4 anhydroglucose (AHG) units.
  • AHG anhydroglucose
  • the observed reduction of the degree of polymerization of the residual cellulose to a value significantly lower than the degree of polymerization for the crystalline domains of the input cellulose (for which DOP N > 200 AHG units) indicates that the catalyst successfully hydrolyzed crystalline cellulose.
  • the first order rate constant for conversion of ⁇ -glucan to short-chain oligo-glucans was determined to be 0.2/hr.
  • Example B4 An additional lOmL of water was added to the residual solids in Example B4. The mixture was agitated to suspend the residual lignin (and residual unreacted biomass particles) without suspending the catalyst. The recovered catalyst was washed with water and then dried to constant mass at 110°C in a gravity oven to yield 99.6% g/g recovery. The functional density of sulfonic acid groups on the recovered catalyst was determined to be 1.59+0.02mmol/g by titration of the recovered catalyst indicating negligible loss of acid functionalization.
  • Example B7 Hydrolysis of Corn Stover using Catalyst as prepared in Example 34
  • Corn stover (7.2% g H 2 0/g wet biomass, with a dry-matter composition of: 33.9% g glucan/g dry biomass, 24.1% g xylan / g dry biomass, 4.8% g arabinan / g dry biomass, 1.5% g galactan / g dry biomass, 4.0% g acetate / g dry biomass, 16.0% g soluble extractives / g dry biomass, 11.4% g lignin / g dry biomass, and 1.4% g ash / g dry biomass) was cut such that the maximum particle size was no greater than 1 cm.
  • the first-order rate constant for conversion of glucan to soluble monosaccharides and oligosaccharides (including disaccharides) was determined to be 0.04/hr.
  • Example B8 Hydrolysis of Oil Palm Empty Fruit Bunches using Catalyst as prepared in Example 20
  • Shredded oil palm empty fruit bunches (8.7% g H 2 0/g wet biomass, with a dry- matter composition of: 35.0% g glucan/g dry biomass, 21.8% g xylan / g dry biomass, 1.8% g arabinan / g dry biomass, 4.8% g acetate / g dry biomass, 9.4% g soluble extractives / g dry biomass, 24.2% g lignin / g dry biomass, and 1.2% g ash / g dry biomass) was cut such that the maximum particle size was no greater than 1 cm.
  • Example 20 To a 15 mL cylindrical glass reaction vial was added: 0.46 g of the cane bagasse sample, 0.43 g of Catalyst as prepared in Example 20 (initial moisture content: 18.3% g H 2 0 / g dispensed catalyst), and 1.3 mL of deionized H 2 0. The reactants were mixed thoroughly with a glass stir rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compacted to yield a solid reactant cake. The glass reactor was sealed with a phenolic cap and incubated at 110°C for five hours. Following the reaction, the product mixture was separated following the procedure described in Examples B2- B5. The first-order rate constant for conversion of xylan to xylose was determined to be 0.4/hr.
  • the first-order rate constant for conversion of glucan to soluble monosaccharides and oligosaccharides (including disaccharides) was determined to be 0.04/hr.
  • Example B9 Hydrolysis of Sugarcane Bagasse using Catalyst as prepared in Example 32
  • Sugarcane bagasse (12.5% g H 2 0/g wet bagasse, with a dry-matter composition of: 39.0% g glucan/g dry biomass, 17.3% g xylan / g dry biomass, 5.0% g arabinan / g dry biomass, 1.1% g galactan / g dry biomass, 5.5% g acetate / g dry biomass, 5.0% g soluble extractives / g dry biomass, 24.1% g lignin / g dry biomass, and 3.1% g ash / g dry biomass) was cut such that the maximum particle size was no greater than 1 cm.
  • Example 32 To a 15 mL cylindrical glass reaction vial was added: 0.53 g of the cane bagasse sample, 0.52 g of Catalyst as prepared in Example 32 (initial moisture content: 3.29% g H 2 0 / g dispensed catalyst), and 1.4 mL of deionized H 2 0. The reactants were mixed thoroughly with a glass stir rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compacted to yield a solid reactant cake. The glass reactor was sealed with a phenolic cap and incubated at 115°C for four hours. Following the reaction, the product mixture was separated following the procedure described in Examples B2- B5.
  • the first-order rate constant for conversion of xylan to xylose was determined to be 0.59/hr.
  • the first-order rate constant for conversion of glucan to soluble monosaccharides and oligosaccharides (including disaccharides) was determined to be 0.05/hr.
  • Example B10 Hydrolysis of Sugarcane Bagasse using Catalyst as prepared in Example 18
  • Sugarcane bagasse (12.5% g H 2 0/g wet bagasse, with a dry-matter composition of: 39.0% g glucan/g dry biomass, 17.3% g xylan / g dry biomass, 5.0% g arabinan / g dry biomass, 1.1% g galactan / g dry biomass, 5.5% g acetate / g dry biomass, 5.0% g soluble extractives / g dry biomass, 24.1% g lignin / g dry biomass, and 3.1% g ash / g dry biomass) was cut such that the maximum particle size was no greater than 1 cm.
  • Example 18 To a 15 mL cylindrical glass reaction vial was added: 0.51 g of the cane bagasse sample, 0.51 g of Catalyst as prepared in Example 18 (initial moisture content: 7.9% g H 2 0 / g dispensed catalyst), and 1.4 mL of deionized H 2 0. The reactants were mixed thoroughly with a glass stir rod to distribute the catalyst particles evenly throughout the biomass. The resulting mixture was gently compacted to yield a solid reactant cake. The glass reactor was sealed with a phenolic cap and incubated at 115°C for four hours. Following the reaction, the product mixture was separated following the procedure described in Examples B2- B5.
  • the first-order rate constant for conversion of xylan to xylose was determined to be 0.06/hr.
  • the first-order rate constant for conversion of glucan to soluble oligo-, di-, and mono-saccharides was determined to be 0.05/hr.
  • the number average degree of polymerization of residual cellulose was determined to be 20+4AHG units, and the first order rate constant for conversion of ⁇ -glucan to short-chain oligo-glucans was determined to be 0.07/hr.
  • Shredded oil palm empty fruit bunches (8.7% g H 2 0/g wet biomass, with a dry- matter composition of: 35.0% g glucan/g dry biomass, 21.8% g xylan / g dry biomass, 1.8% g arabinan / g dry biomass, 4.8% g acetate / g dry biomass, 9.4% g soluble extractives / g dry biomass, 24.2% g lignin / g dry biomass, and 1.2% g ash / g dry biomass) was cut such that the maximum particle size was no greater than 1 cm.
  • Example B12 Fermentation of Cellulosic Sugars from Sugarcane Bagasse
  • the wet reactant cake was loaded into a syringe equipped with a 0.2 micrometer filter and the hydrolysate was pressed out of the product mixture into a sterile container.
  • To a culture tube was added 2.5mL of culture media (prepared by diluting 10 g of yeast extract and 20 g peptone to 500 mL in distilled water, followed by purification by sterile filtration), 2.5 mL of the hydrolysate, and 100 mL of yeast slurry (prepared by dissolving 500mg of Alcotec 24 hour Turbo Super yeast into 5mL of 30°C of sterile H 2 0.
  • the culture was grown at 30°C in shaking incubator, with 1 mL aliquots removed at 24, 48 and 72 hours.
  • the optical density of the culture was determined by spectrophotometer aliquot.
  • the aliquot was purified by centrifugation and the supernatant was analyzed by HPLC to determine the concentrations of glucose, xylose, galactose, arabinose, ethanol, and glycerol. After 24 hours, ethanol and glycerol were found in the fermentation supernatant, indicating at least 65% fermentation yield on a molar basis relative to the initial glucose in the hydrolysate.
  • Cassava stem (2.0% g H 2 0/g wet cassava stem, with a dry-matter composition of: 53.0% g glucan/g dry biomass, 6.0% g xylan / g dry biomass, 2.5% g arabinan / g dry biomass, 5.5% g acetate / g dry biomass, 5.9% g soluble extractives / g dry biomass, 24.2% g lignin / g dry biomass, and 2.1% g ash / g dry biomass) was shredded in a coffee-grinder such that the maximum particle size was no greater than 2 mm.
  • the wet reactant cake was loaded into a syringe equipped with a 0.2 micrometer filter and the hydrolysate was pressed out of the product mixture into a sterile container.
  • To a culture tube was added 2.5mL of culture media (prepared by diluting 10 g of yeast extract and 20 g peptone to 500 mL in distilled water, followed by purification by sterile filtration), 2.5 mL of the hydrolysate, and 100 mL of yeast slurry (prepared by dissolving 500mg of Alcotec 24 hour Turbo Super yeast into 5mL of 30°C of sterile H 2 0.
  • the culture was grown at 30°C in shaking incubator, with 1 mL aliquots removed at 24, 48 and 72 hours.
  • the optical density of the culture was determined by spectrophotometer aliquot.
  • the aliquot was purified by centrifugation and the supernatant was analyzed by HPLC to determine the concentrations of glucose, xylose, galactose, arabinose, ethanol, and glycerol. After 24 hours, ethanol and glycerol were found in the fermentation supernatant, indicating at least 70% fermentation yield on a molar basis relative to the initial glucose in the hydrolysate.
  • Example B14 Fermentation of Glucose obtained from Insoluble Starch

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Abstract

La présente invention concerne des polymères d'origine biologique dont au moins l'un des composants est partiellement ou intégralement issu de la biomasse, ainsi que des procédés de production desdits polymères d'origine biologique. Lesdits composants d'origine biologique peuvent être obtenus par dégradation de la biomasse en utilisant les catalyseurs décrits ici pour produire un mélange de sucres, lesdits sucres pouvant être convertis en un ou plusieurs composants desdits polymères d'origine biologique.
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