CN102059103A - Hydrophylic phenylboric acid functional porous integral material, preparation method and application thereof - Google Patents
Hydrophylic phenylboric acid functional porous integral material, preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 45
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 230000003993 interaction Effects 0.000 claims abstract description 8
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
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- CSSYQJWUGATIHM-IKGCZBKSSA-N l-phenylalanyl-l-lysyl-l-cysteinyl-l-arginyl-l-arginyl-l-tryptophyl-l-glutaminyl-l-tryptophyl-l-arginyl-l-methionyl-l-lysyl-l-lysyl-l-leucylglycyl-l-alanyl-l-prolyl-l-seryl-l-isoleucyl-l-threonyl-l-cysteinyl-l-valyl-l-arginyl-l-arginyl-l-alanyl-l-phenylal Chemical compound C([C@H](N)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CS)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCC(N)=O)C(=O)N[C@@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCSC)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CCCCN)C(=O)N[C@@H](CC(C)C)C(=O)NCC(=O)N[C@@H](C)C(=O)N1CCC[C@H]1C(=O)N[C@@H](CO)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)O)C(=O)N[C@@H](CS)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](CCCNC(N)=N)C(=O)N[C@@H](C)C(=O)N[C@@H](CC=1C=CC=CC=1)C(O)=O)C1=CC=CC=C1 CSSYQJWUGATIHM-IKGCZBKSSA-N 0.000 description 2
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- DQJCDTNMLBYVAY-ZXXIYAEKSA-N (2S,5R,10R,13R)-16-{[(2R,3S,4R,5R)-3-{[(2S,3R,4R,5S,6R)-3-acetamido-4,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy}-5-(ethylamino)-6-hydroxy-2-(hydroxymethyl)oxan-4-yl]oxy}-5-(4-aminobutyl)-10-carbamoyl-2,13-dimethyl-4,7,12,15-tetraoxo-3,6,11,14-tetraazaheptadecan-1-oic acid Chemical compound NCCCC[C@H](C(=O)N[C@@H](C)C(O)=O)NC(=O)CC[C@H](C(N)=O)NC(=O)[C@@H](C)NC(=O)C(C)O[C@@H]1[C@@H](NCC)C(O)O[C@H](CO)[C@H]1O[C@H]1[C@H](NC(C)=O)[C@@H](O)[C@H](O)[C@@H](CO)O1 DQJCDTNMLBYVAY-ZXXIYAEKSA-N 0.000 description 1
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- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a hydrophilic phenylboric acid functional porous integral material, which is a cross-linked framework structured hydrophilic phenylboric acid functional porous integral material with penetrated transparent ducts, is formed by 4-(-3-butenyl sulfone) phenylboric acid and crosslinker N,N-bisacrylamide under initiation of a free radical reaction initiator, and can perform a covalent interaction with dihydroxyl compound under a neutral pH condition. The hydrophilic phenylboric acid functional porous integral material can be used for specifically identifying, separating, enriching or immobilizing the dihydroxyl compounds. The invention also discloses a method for preparing the hydrophilic phenylboric acid functional porous integral material.
Description
Technical field
The present invention relates to a kind of preparation of phenyl boric acid functionalization porous integral material.This material is the high-molecular porous integral material of sulfuryl substituted benzene boric acid-methylene diacrylamide.It is characterized in that: 1) this material is a function monomer with sulfuryl substituted benzene boric acid; 2) this material is a hydrophilic material, a little less than the non-special interaction; 3) under condition of neutral pH can with o-dihydroxy compound generation covalent interaction.This material can be used for enrichment, separation, the immobilized and sensing of o-dihydroxy compound.
Background technology
In the aqueous solution of alkalescence, hydroxylation can take place in boron, and the structure of self is the boron ion (referring to Liu X. Chin. J. Chromatogr., 2006,24,73) of positive tetrahedron by the coplanar transfer of shapes of triangle thereupon.So boric acid and substituted boracic acid can form the ester of five-membered ring or hexatomic ring with cis o-dihydroxy compound under alkali condition, and the product ester dissociates under acid condition.Whole process is the reversible covalent reaction that is subjected to the pH regulation and control.Because in a lot of important biomolecule, all contain the o-dihydroxy compound as sugar, catechol, nucleosides, RNA, glycoprotein and glycopeptide etc., the esterification affinity interaction of boron has extensive use.Early stage acid esterification affinity interaction mainly is used to the detection (referring to Boeseken J., Adv. Carbohydr. Chem., 1949,4,189) to sugar; Last century 50, the sixties, the separation that is used for zone electrophoresis or ion-exchange chromatography mutually mainly as flowing (referring to: Foster A., Adv. Carbohydr. Chem., 1957,12,81; Mattok G. L., Wilson D. L., Anal. Biochem., 1965,11,575).
1970, and people such as Weith (referring to: Weith H. L, Wiebers J. L., Gilham P. T., Biochemistry, 1970,9,4396) first boric acid class substituent is fixed on the chromatographic isolation matrix, realized separation to nucleosides etc.After this, people such as Monzo (referring to: Monzo A., Bonn G. K, Guttman A., Anal. Bioanal. Chem. 2007,389 2097) aminobenzene boric acid is entrained in the various agglutinins, the glycoprotein in the enrichment blood is to distinguish the difference of healthy people and bladder cancer patients protein glycosylation.People such as Liu Zhen (referring to: Dou P., Liang L., He J. G., Liu Z., Chen H. Y., J. Chromatogr. A, 2009,1216,7558) on magnetic nano-particle bonding the success of aminobenzene boric acid enrichment the riboflavin in people's urine sample.Yet common boric acid compound has higher pKa value (~ 8.8), so will just can form stable circulus with cis o-dihydroxy compound under high pH (ordinary circumstance, pH〉8.0) condition.And under high pH condition, a lot of biomolecule are all unstable, easily oxidation, easily degraded (referring to: Tian R., Ye M., Hu l., Li X., Zou H., J. Sep. Sci., 2007,30,2204).At present, this type of boric acid compound separating filler of the great majority of Chu Shouing all has phenyl ring on the market, as the m-aminophenyl boric acid agarose of Sigma company, and the m-aminophenyl boric acid matrix of Pieice company etc.This makes such chromatographic isolation filler can produce tangible hydrophobic effect in enrichment and the process of separating cis o-dihydroxy compound, thereby can particularly produce nonspecific absorption to the detection of protein-based sample to a lot of samples.Can suppress non-specific adsorption although in flowing mutually, add organic solvent, cause the sex change of sample easily.
Summary of the invention
The invention provides a kind of hydrophilic phenyl boric acid functionalization porous integral material.The penetrating duct that this integral material has the skeleton structure that is cross-linked with each other and runs through mutually, good hydrophilic property, under condition of neutral pH can with o-dihydroxy compound generation covalent interaction.
A kind of hydrophilic phenyl boric acid functionalization porous integral material, it be have the penetrating duct run through mutually, by 4-(-3-alkene butyl sulfone) phenyl boric acid and crosslinking agent N, the reaction under the radical reaction initator causes of N-methylene-bisacrylamide forms the hydrophilic phenyl boric acid functionalization porous integral material of crosslinked skeleton structure.
A kind of method for preparing above-mentioned hydrophilic phenyl boric acid functionalization porous integral material, it is with function monomer 4-(-3-alkene butyl sulfone) phenyl boric acid (SPBA) and crosslinking agent N, N-methylene-bisacrylamide (MBAA) is dissolved in the admixture solvent of good solvent methyl-sulfoxide (DMSO) and poor solvent lauryl alcohol, wherein the mass ratio of function monomer and crosslinking agent is 1:3-4:1, function monomer adds the volume of crosslinking agent and the volume ratio of solvent is 1.5:8.5-5:5, the volume ratio of good solvent and poor solvent is 1:1-1:2, good solvent and poor solvent play pore-foaming agent, through vortex, after ultrasonic the mixing, add an amount of initator, vortex once more, ultrasonic mixing, this homogeneous solution is filled into centrifuge tube, in the conventional post of capillary column or high performance liquid chromatography, mould is sealed, under 50 ℃-90 ℃ temperature, isothermal reaction 6-36 hour, after reaction finishes, the method that product adopts the methyl alcohol Soxhlet to extract is extracted, or capillary column or performance liquid chromatographic column be linked in syringe pump or the high performance liquid chromatography system, with organic solvents such as methyl alcohol flushing integral material, promptly get hydrophilic phenyl boric acid functionalization porous integral material of the present invention.
Above-mentioned hydrophilic phenyl boric acid functionalization material can be applicable to specific recognition, separation, enrichment or immobilized o-dihydroxy compound.
Advantage of the present invention is:
(1) selecting pKa for use is 7.0 4-(-3-alkene butyl sulfone) phenyl boric acid is a function monomer, thereby the pH of acid esterification affinity interaction also has been reduced to condition of neutral pH accordingly; (2) sulfuryl in the function monomer is as a kind of hydrophilic group and hydrophilic crosslinker N, and the N-methylene-bisacrylamide increases the hydrophilic ability of integral material jointly, reduces the hydrophobic effect that phenyl ring produces in the phenyl boric acid; (3) compare with existing boron functionalization integral material, the enrichment that can under the physiological pH condition of whole water phase, carry out to the o-dihydroxy compound with separate; (4) manufacture of materials cost of the present invention is low, and operating process is simple, good reproducibility.
Description of drawings
Fig. 1 is the FFIR figure of hydrophily phenyl boric acid functionalization porous integral material of the present invention.
Fig. 2 is the sem photograph of hydrophily phenyl boric acid functionalization material skeleton of the present invention, and wherein: Fig. 1 (a) is for amplifying 900 times, and Fig. 1 (b) is for amplifying 8,000 times.
Fig. 3 is that hydrophily boron functionalization integral material is to the specific enrichment of glycoprotein and the chromatogram that separates.
The specific embodiment
Further specify the present invention by the following examples.
The preparation of embodiment 1 block hydrophilic phenyl boric acid functionalization porous integral material
(1) get the centrifuge tube of suitable size, 60mg SPBA and 120mg MBAA are dissolved in the DMSO solution of 340uL, add the lauryl alcohol of 250mg again, the AIBN of 4mg, ultrasonic 15 minutes of vortex, sealing is put into thermostat water bath in 75 ℃ of reactions 12 hours;
(2) then integral material is taken out, be cut into small pieces, put into apparatus,Soxhlet's, add methyl alcohol under 110 ℃ of temperature, extracted 24 hours, to remove unreacted monomer, crosslinking agent;
(3) above-mentioned material is placed vacuum drying chamber, drying is 12 hours under 100 ℃, can obtain hydrophily phenyl boric acid functionalization integral material;
(4) be milled into particle with above-mentioned material, after mixing, the KBr crystal is milled into less than 200 purpose powder, characterize with Fourier transform infrared spectrometry behind the compressing tablet, can observe the absworption peak of sulfuryl (1382,1218,1116.0 cm-1), phenyl ring (807,643cm-1) and hydroxyl characteristic groups such as (3307cm-1), infrared spectrogram is seen Fig. 1.
Embodiment 2: the preparation of hydrophilic phenyl boric acid functionalization porous integral material in the capillary
Do not wait at internal diameter (25mm, 75mm, 100mm, 150mm, the phenyl boric acid functionalization porous integral material of synthetic possess hydrophilic property in capillary 250mm):
(1) preliminary treatment capillaceous, at first washed the capillary void column 1 hour with 0.1M NaOH solution, be 7.0 with deionized water rinsing capillary to trickle pH value again, then washed capillary 2 hours with 0.1M HCl solution, again with the deionized water rinsing capillary to trickle pH be 7.0, washed capillary 30 minutes with methanol solution then, and dry up with nitrogen.Inject the mixture of methyl alcohol and methacryloxypropyl-trimethoxy silane in the capillary.Reaction is 5-24 hour under 20 ℃ to 70 ℃ temperature.Use washed with methanol again, dry up stand-by at last with nitrogen.
(2) 15mg SPBA and 30mg MBAA are dissolved in the DMSO solution of 85uL, add the lauryl alcohol of 62.5mg again, the AIBN of 1mg, ultrasonic 15 minutes of vortex makes polymer fluid;
(3) polymer fluid of being prepared is pressed in the capillary that activates after drying up with nitrogen, nitrogen gas pressure is controlled at 0.03-0.1Mpa;
(4) the capillary two ends are sealed with silicon rubber, put into 50-90 ℃ of water-bath then, isothermal reaction 12 hours;
(5) take out capillary, be connected on the high pressure liquid chromatography pump, wash away unreacted polymerization single polymerization monomer and perforating agent etc. completely mutually for flowing, can obtain hydrophily phenyl boric acid functionalization porous integral material with methyl alcohol;
(5) get one section above-mentioned phenyl boric acid functionalization entire capillary post, with the pattern of scanning electron microscopic observation cross section, can observe loose structure, Electronic Speculum figure sees Fig. 2.
Embodiment 3: the preparation of hydrophilic phenyl boric acid functionalization porous integral material in the conventional chromatogram post
The phenyl boric acid functionalization porous integral material of synthetic possess hydrophilic property in conventional post such as the efficient liquid phase that internal diameter does not wait:
(1) cleaning of the conventional post of efficient liquid phase at first is dipped in the conventional post of efficient liquid phase in the dried up water, and ultrasonic cleaning 1 hour changes methyl alcohol ultrasonic cleaning 1 again into, and drying is 2 hours in baking oven;
(2) 150mg SPBA and 300mg MBAA are dissolved in the DMSO solution of 850mL, add the lauryl alcohol of 625 mg again, the AIBN of 10mg, ultrasonic 15 minutes of vortex makes polymer fluid;
(3) prepared polymer fluid is slowly added in the conventional post of efficient liquid phase with liquid-transfering gun is careful;
(4) 50-90 ℃ of water-bath put into, isothermal reaction 12 hours with the sealing of tip head in the conventional post of processing two ends;
(5) take out the conventional post of efficient liquid phase, be connected on the high pressure liquid chromatography pump, wash away unreacted polymerization single polymerization monomer and perforating agent etc. completely mutually for flowing, can obtain hydrophily phenyl boric acid functionalization integral material with methyl alcohol.
Embodiment 4: the application of hydrophilic phenyl boric acid functionalization porous integral material
The prepared boric acid functionalization integral material of the present invention can be applicable to the o-dihydroxy compound is carried out enrichment and separates, as biological micromolecule catechol, nucleosides, glycoprotein etc.Whole enrichment and separating process all are in full aqueous systems, finish under the condition of physiological pH.Concrete operations are as follows:
1) standard protein is respectively: the glycoprotein HRPO (HRP) of suitable concentration, lactoferrin (lactoferrin) and non-glycoprotein bovine serum albumin(BSA) (BSA), myoglobins (myoglobin), cytochrome c (cytochrome c);
2) above-mentioned albumen sample introduction one by one adopts the operation of step gradient, and adopting concentration earlier is 100 mM PBS (pH=7.4) drip washing, and the drip washing duration was greater than 5 minutes;
3) adopt 100 mM HAc solution drip washing, until being eluted by the albumen of specific enrichment.
Adopt above-mentioned steps, can observe, glycoprotein is by specific reservation, but not glycoprotein is by complete wash-out (chromatogram is seen Fig. 3).
Claims (3)
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104056608A (en) * | 2014-06-12 | 2014-09-24 | 北京理工大学 | Boric acid affinity chromatography material for temperature switch, and preparation method and application of boric acid affinity chromatography material |
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| CN105542076A (en) * | 2016-01-28 | 2016-05-04 | 安徽师范大学 | Thiophilic porous material, and preparation method and application thereof |
| CN105749586A (en) * | 2015-07-14 | 2016-07-13 | 大连医科大学 | Preparation method of phenylboronic acid affinity monolithic column |
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| CN108607527A (en) * | 2018-05-16 | 2018-10-02 | 江苏大学 | A kind of preparation method of the high osmosis porous composite film adsorbent of phenyl boric acid type modification |
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| CN112430289A (en) * | 2020-11-09 | 2021-03-02 | 南昌大学 | High-selectivity phenylboronic acid functionalized organic polymer and preparation method and application thereof |
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| CN104072678B (en) * | 2013-03-29 | 2017-02-08 | 中国科学院大连化学物理研究所 | Polymer microsphere, preparation and applications thereof |
| CN104072678A (en) * | 2013-03-29 | 2014-10-01 | 中国科学院大连化学物理研究所 | Polymer microsphere, preparation and applications thereof |
| CN104056608A (en) * | 2014-06-12 | 2014-09-24 | 北京理工大学 | Boric acid affinity chromatography material for temperature switch, and preparation method and application of boric acid affinity chromatography material |
| CN104549182A (en) * | 2014-12-29 | 2015-04-29 | 上海烟草集团有限责任公司 | Branched boric acid functionalized monolithic column and preparation method and application thereof |
| CN104861130A (en) * | 2015-05-07 | 2015-08-26 | 西北大学 | Polymer brush graft boracic acid affinity separation material and preparation method and application |
| CN105749586A (en) * | 2015-07-14 | 2016-07-13 | 大连医科大学 | Preparation method of phenylboronic acid affinity monolithic column |
| CN105542076A (en) * | 2016-01-28 | 2016-05-04 | 安徽师范大学 | Thiophilic porous material, and preparation method and application thereof |
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| CN106076298B (en) * | 2016-06-13 | 2018-11-02 | 哈尔滨工业大学 | A kind of application of phenyl boric acid affinity chromatography stationary phase |
| CN108607527A (en) * | 2018-05-16 | 2018-10-02 | 江苏大学 | A kind of preparation method of the high osmosis porous composite film adsorbent of phenyl boric acid type modification |
| CN108607527B (en) * | 2018-05-16 | 2019-08-27 | 江苏大学 | A kind of preparation method of the highly permeable porous composite membrane adsorbent modified by phenylboronic acid |
| CN111272911A (en) * | 2020-03-19 | 2020-06-12 | 中国烟草总公司郑州烟草研究院 | Sample pretreatment method for determining Amadori compound in food |
| CN112430289A (en) * | 2020-11-09 | 2021-03-02 | 南昌大学 | High-selectivity phenylboronic acid functionalized organic polymer and preparation method and application thereof |
| CN112552395A (en) * | 2020-11-26 | 2021-03-26 | 北京化工大学 | Method for rapidly separating and enriching lactoferrin in dairy product |
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