Joseph Banoub
Memorial University of Newfoundland, Biochemistry, Faculty Member
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Crankcase oils are mineral oils containing hydrocarbons and various additives. In the present case, the oil contained 10% aromatics and 1% PAH if concentration is expressed in terms of chrysene units. Rainbow trout were exposed daily to... more
Crankcase oils are mineral oils containing hydrocarbons and various additives. In the present case, the oil contained 10% aromatics and 1% PAH if concentration is expressed in terms of chrysene units. Rainbow trout were exposed daily to food pellets spiked with crankcase oil and sampled monthly for 4 months. Exposure was to 0, 3.2, 6.4 and 9.6 ug oil/g fish/day and represents a water concentration of nearly 0, 10, 20, and 30 ug oil/L. Muscle tissue was analyzed for total and specific aromatics (PAHs, LABs, PCBs) and various elements. The liver was analyzed for enzymatic activity (EROD and AchE) and the gall bladder, for bile metabolites. A dose and time response was observed for the bioaccumulation of aromatics. In another experiment, crabs were exposed to crankcase oil during 6 months and sampled intermittently. Feeding took place once a week during the first 3 months and biweekly for the last 3 months. Exposure was equivalent to 4--8 ug oil/g crab/day or to 510 ug oil/L. Muscle and hepatopancreas were analyzed for aromatic compounds. Comparison is made between the two experiments and the fate of aromatics discussed in terms of temperature, respiration rates, lipid content of tissues and K{sub ow} of chemicalsmore » known to be present in lubricating oils.« less
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This chapter presents an introduction to infective diseases and potential biological agents that could potentially be used for bioterrorism. Technical brief description of the possible treatments and preventions of these biothreats is... more
This chapter presents an introduction to infective diseases and potential biological agents that could potentially be used for bioterrorism. Technical brief description of the possible treatments and preventions of these biothreats is presented with emphasis placed on the principles of immunological defenses, vaccination, and preparation of vaccines. In principle, various types of vaccines that are commercially used as “antibacterial or anticancer vaccines” can be produced using various types of antigenic carbohydrate haptens containing relevant epitopes. This review highlights the strategies used for the characterization of such synthetic neoglycoconjugate vaccines used as a means of protection against biothreats. A complete mass spectrometry-based strategy for validating the preparations of the neoglycoconjugate vaccine is presented.
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Research Interests: OMEGA and Ionization
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Die 1,2‐trans‐Octaacetate (Ia), (Ib), (VI) von Cellobiose, Lactose bzw. Maltose reagieren mit dem Hydroxyester (II) bei ‐10°C zu den β‐Glycosiden (III) bzw. (V) (Verlauf über 1,2‐Acetoxonium‐Ionen).
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RationaleWe report the top‐down lignomics analysis of the virgin released lignin (VRL) extracted from French pine wood by using atmospheric pressure photoionization quadrupole time‐of‐flight mass spectrometry (APPI‐QqTOF‐MS) and... more
RationaleWe report the top‐down lignomics analysis of the virgin released lignin (VRL) extracted from French pine wood by using atmospheric pressure photoionization quadrupole time‐of‐flight mass spectrometry (APPI‐QqTOF‐MS) and low‐energy collision‐induced dissociation tandem mass spectrometry (CID‐MS/MS).MethodsWe used APPI‐QqTOF‐MS (positive ion mode) for the analysis of the complex mixture of VRL oligomers extracted from French pine wood. Some of the major precursor ions were fished out from the complex VRL oligomeric mixture and subjected to low‐energy CID‐MS/MS analyses.ResultsFourteen novel lignin–carbohydrate complexes (LCCs) were identified using APPI‐QqTOF‐MS/MS of the very complex mixture of virgin released lignins (VRLs), directly extracted from French pine wood without any kind of purification. The low‐energy CID‐MS/MS analyses allowed us to establish the fragmentation patterns of the precursor ions and to identify the complex structures of the identified LCC molecules. These novel identified series of LCCs were composed of one or two carbohydrate rings to which one, two, or three lignin units were covalently attached. In addition to the fourteen LCCs, acetyl eugenol was identified in the French pine VRL sample. The identification of acetyl eugenol indicates possible lignin degradation and modification (acetylation) during the mild extraction method developed by the Compagnie Industrielle de la Matière Végétale (CIMV).ConclusionsThe top‐down lignomics analysis of the French pine VRLs using APPI‐QqTOF‐MS and low energy CID‐MS/MS allowed us to identify acetylated eugenol and a novel series of fourteen LCCs. These series of LCCs provide evidence that lignins are covalently linked to carbohydrates in the native wood network and act as cross‐linkers between cellulose and hemicellulose components of wood.
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We report herein the top-down lignomic analysis of virgin released lignin (VRL) extracted from the French oak wood using atmospheric pressure photoionization quadrupole orthogonal time-of-flight mass spectrometry (APPI-QqTOF-MS) (+ ion... more
We report herein the top-down lignomic analysis of virgin released lignin (VRL) extracted from the French oak wood using atmospheric pressure photoionization quadrupole orthogonal time-of-flight mass spectrometry (APPI-QqTOF-MS) (+ ion mode). Eight major protonated lignin oligomers were identified using the APPI-QqTOF-MS/MS of this complex VRL mixture without any kind of purification. This series of protonated oligomer ions were identified as neolignan cedrusin (1), five different aryltetralin lignans dimers (2-6), one lignan-dehydroshikimic acid complex (7), and a lignan trimer (8). Similarly, electrospray ionization (ESI)-QqTOF-MS (+ ion mode) allowed us to identify three extra aryltetralin lignan derivatives (9-11). The Kendrick mass defect analysis was used for the simplification of this complex APPI-QqTOF-MS into a compositional map, which displayed clustering points of associated ions possessing analogous elemental composition. This series of novel protonated molecules were selected and subjected to low-energy collision-induced dissociation (CID)-MS/MS analyses. The obtained gas-phase fragmentation patterns helped to tentatively assign their most likely structures. Also, it was found that the use of different APPI and ESI ambient ionization techniques enhances the ionization of different types of lignin oligomers.
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RATIONALE We report the top-down lignomic analysis of the virgin released lignin (VRL) small oligomers, obtained from French Oak wood. METHODS We have used MALDI-TOF-MS in the negative ion mode for the analysis of the complex lignin... more
RATIONALE We report the top-down lignomic analysis of the virgin released lignin (VRL) small oligomers, obtained from French Oak wood. METHODS We have used MALDI-TOF-MS in the negative ion mode for the analysis of the complex lignin oligomers mixture extracted from French Oak wood. High-energy CID-TOF/TOF-MS/MS analyses were used to support the postulated precursor ion structures. RESULTS Twenty compounds were identified using MALDI-TOF-MS/MS of the VRL extracted from French Oak wood: seven tricin derivatives and/or flavonoids, three syringylglycerol derivatives, two syringol derivatives, two flavonolignin derivatives, and six miscellaneous compounds: luteoferol, lariciresinol isomer, 5-hydroxy guaiacyl derivative, syringyl -C10 H10 O2 dimer, trihydroxy benzaldehyde derivative, and aryl tetralin lignan derivative. Most of the identified compounds were in the form of carbohydrate and/or shikimic acid complexes. CONCLUSION The analysis of this complex mixture led to the identification of a series of lignin dimers, novel lignin-carbohydrate complexes (LCC), and unique tricin derivatives linked to different types of carbohydrates and shikimic acid moieties. This finding supports the presence of lignin-carbohydrate complexes in the isolated VRL. These analyses also showed that French Oak lignin is abundant in syringol moieties present in the lignin syringyl-units or tricin derivatives. Moreover, the identification of some lignin-carbohydrate and/or flavonoid-shikimic acid complexes could provide new insight into the relationship between the biosynthesis of lignin and tricin.
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This study examines the electrospray ionization mass spectrometry (ESI-MS), in-source collision-induced dissociation (CID) fragmentation and low-energy collision-induced dissociation tandem mass spectrometry (CID-MS/MS) of a synthetic... more
This study examines the electrospray ionization mass spectrometry (ESI-MS), in-source collision-induced dissociation (CID) fragmentation and low-energy collision-induced dissociation tandem mass spectrometry (CID-MS/MS) of a synthetic pair of β- and α-anomers of the amphiphilic cholesteryl polyethoxy neoglycolipids containing the 2-azido-2-deoxy-D-galactosyl-D-GalN3 moiety. We describe the novel and unique in situ gas-phase formation of a C-glycoside ion formed during all these gas-phase processes and propose a reasonable mechanism for its formation. The synthetic amphiphilic glycolipids were composed of the 2-deoxy-2-azido-D-galactosyl moiety (GalN3 , the hydrophilic part) covalently attached to a polyethoxy spacer which is covalently linked to the cholesteryl moiety (hydrophobic part). The 2-azido-2-deoxy-α- and β-D-galactosyl-containing glycolipids were studied by in-time and in-space ESI-MS and CID-MS/MS in positive ion mode, with quadrupole ion trap (QIT), quadrupole-quadrupole-time-of-flight (QqTOF), and Fourier transform ion cyclotron resonance (FTICR) instruments. Conventional single-stage ESI-MS analysis showed the formation of the protonated molecule. During the single-stage ESI-MS analysis and the CID-MS/MS of the [M+H](+) and [M+NH4 ](+) adducts obtained from both glycolipid anomers, the presence of a series of specific product ions with different intensities was observed, consistent with the [C-glycoside+H-N2 ](+) , [cholestadiene+H](+) , 2-deoxy-2-D-azido-galactosyl [GalN3 ](+) , [GalNH](+) and [sugar-Spacer+H](+) ions. The gas-phase formation of the [C-glycoside+H-N2 ](+) ion isolated from the glycolipid anomers was observed during both the ESI-MS of the glycolipids and the CID-MS/MS analyses of the [M+H](+) ions and it was found to occur by an intramolecular rearrangement involving an ion-molecule complex. CID-QqTOF-MS/MS and CID-FTICR-MS(2) analysis allowed the differentiation of the two glycolipid anomers and showed noticeable variation in the intensities of the product ions. Copyright © 2015 John Wiley & Sons, Ltd.
Research Interests: Earth Sciences, Chemistry, Mass Spectrometry, Medicine, Electrospray, and 9 moreBiological Sciences, Tandem Mass Spectrometry, CHEMICAL SCIENCES, Liquid Chromatography / Electrospray Ionization Mass Spectrometry, Fourier transform ion cyclotron resonance, Glycolipids, Ions, Monosaccharides, and Electrospray Ionization
Research Interests: Biochemistry, Biology, Medicine, Humans, Female, and 15 moreProtein Tyrosine Kinase, Inositol, Clinical Sciences, High Pressure Liquid Chromatography, Epidermal Growth Factor, Phenols, Growth Factor, Hydrolysis, Metabolite, Acids, Biochemistry and cell biology, Inositol Phosphates, metabolite profiling, Electrospray Ionization, and Breast Neoplasms
This chapter surveys the current detection technologies used in commercially available sensor detection equipment currently employed for identifying warfare chemical agents (CAs). Brief technical descriptions of these technologies are... more
This chapter surveys the current detection technologies used in commercially available sensor detection equipment currently employed for identifying warfare chemical agents (CAs). Brief technical descriptions of these technologies are presented with emphasis placed on the principles of detection. Much of the content presented was obtained from the open-source literature and is an introduction to biosensor fundamentals.
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Traumatic brain injury (TBI) is a major neurological disorder without FDA-approved therapies. In this study, we have examined the concept that TBI might trigger global brain proteolysis in the acute post-injury phase. Thus, we conducted a... more
Traumatic brain injury (TBI) is a major neurological disorder without FDA-approved therapies. In this study, we have examined the concept that TBI might trigger global brain proteolysis in the acute post-injury phase. Thus, we conducted a systemic proteolytic peptidomics analysis using acute cerebrospinal fluid (CSF) samples from TBI patients and normal control samples. We employed ultrafiltration-based low molecular weight (LMW; < 10 kDa) peptide enrichment, coupled with nano-reversed-phase liquid chromatography/tandem mass spectrometry analysis, followed with orthogonal quantitative immunoblotting-based protein degradation analysis. We indeed identified novel patterns of injury-dependent proteolytic peptides derived from neuronal components (pre- and post-synaptic terminal, dendrites, axons), extracellular matrix, oligodendrocytes, microglial cells, and astrocytes. Among these, post-synaptic protein neurogranin was identified for the first time converted to neurogranin peptides including neurogranin peptide (aa 16-64) that is phosphorylated at Ser-36/48 (P-NG-fragment) in acute human TBI CSF samples vs. normal control with a receiver operating characteristic area under the curve of 0.957. We also identified detailed processing of astroglia protein (vimentin) and oligodendrocyte protein (MBP and Golli-MBP) to protein breakdown products (BDPs) and/or LMW proteolytic peptides after TBI. In addition, using MS/MS selected reaction monitoring method, two C-terminally released MBP peptides TQDENPVVHFF and TQDENPVVHF were found to be elevated in acute and subacute TBI CSF samples as compared to their normal control counterparts. These findings imply that future therapeutic strategies might be placed on the suppression of brain proteolysis as a target. The endogenous proteolytic peptides discovered in human TBI biofluid could represent useful diagnostic and monitoring tools for TBI.
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Palm date is an important crop in many Middle Eastern countries. In the present study, seedling date palm wood and old date palm wood were evaluated for their phenolics content. It was found that they may serve as rich source of soluble... more
Palm date is an important crop in many Middle Eastern countries. In the present study, seedling date palm wood and old date palm wood were evaluated for their phenolics content. It was found that they may serve as rich source of soluble and insoluble-bound phenolics with promising reducing power and metal chelation. The observed effects were compared with those of oak, quibracho, banana, and pine woods. Syringic acid, (+)-catechin, and (+)-gallocatechin were present in five out of the six tested samples, as evaluated by MALDI-TOF-MS. Therefore, these compounds are good candidates to be monitored by the industry in order to define quality parameters. Additionally, due to their strong ability in counteracting DNA damage caused by peroxyl and hydroxyl radicals (up to 98.42%) and cupric ion-induced human low-density lipoprotein-cholesterol (LDL-c) peroxidation in vitro (up to 95.80%), wood phenolics may render antimutagenic effects and protection against cardiovascular diseases.
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RATIONALE We report for the first time the top-down lignomic analysis of the virgin released lignin (VRL) oligomers obtained from the Saudi date palm wood (SDPW), using a matrix-assisted laser desorption/ionization... more
RATIONALE We report for the first time the top-down lignomic analysis of the virgin released lignin (VRL) oligomers obtained from the Saudi date palm wood (SDPW), using a matrix-assisted laser desorption/ionization time-of-flight/time-of-flight (MALDI-TOF/TOF) instrument. In addition, we are proposing new collision-induced dissociation tandem mass spectrometry (CID-MS/MS) fragmentation routes for this series of unreported VRL oligomers. METHODS We have used direct MALDI-TOF-MS analysis of the mixture of lignin oligomers without any chromatographic pre-separation. High-energy CID-MS/MS analyses were used to confirm the precursor ion structures. RESULTS Six protonated lignin oligomer molecules were identified: [C19 H24 O8 + H]+ as H(8-O-4')G; [C50 H52 O19 + H]+ as H(8-O-4')H(8-O-4'')S(8-O-4''')S(8-O-4'''')G; [C58 H54 O18 + H]+ as H(8-O-4')H(8-O-4'')H(8-O-4''')G(8-O-4'''')S(8-O-4''''')G; [C58 H54 O19 + H]+ as H(8-O-4')H(8-O-4'')H(8-O-4''')S(8-O-4'''')S(8-O-4''''')G; [C61 H68 O25 + H]+ as H(8-O-4')G(8-O-4'')G(8-O-4''')S(8-O-4'''')S(8-O-4''''')G; and [C61 H68 O26 + H]+ as C(8-O-4')G(8-O-4'')G(8-O-4''')S(8-O-4'''')S(8-O-4''''')G units (H = coniferyl, S = sinapyl, and G = p-coumaryl). Two distonic cations were identified as [C39 H43 O15 + H]+• and [C40 H43 O16 + H]+• deriving from two tetrameric lignin oligomers. The high-energy MS/MS analyses allowed the confirmation of the proposed structures of this series of lignin oligomers. CONCLUSIONS To our knowledge, this is the first elucidation of the lignin structure of the Saudi seedling date palm wood that was accomplished using a top-down lignomic strategy that has not previously been published. The complex high-energy CID-MS/MS fragmentations presented herein are novel and have never been described before.
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We report herein the electrospray ionization mass spectrometry (ESI-MS) negative ion mode and low-energy collision-induced dissociation tandem mass spectrometry (CID-MS/MS) analysis of a mixture of lipid A isolated from the... more
We report herein the electrospray ionization mass spectrometry (ESI-MS) negative ion mode and low-energy collision-induced dissociation tandem mass spectrometry (CID-MS/MS) analysis of a mixture of lipid A isolated from the lipopolysaccharide (LPS) of a rough-resistant wild strain of the Gram-negative bacteria Aeromonas hydrophila grown in the presence of phages (SJ-55Ra). This investigation indicates that the presence of a mixture of lipid A acylated disaccharides, whose molecular structures were not relatively conserved, resulted from the incomplete LPS biosynthesis caused by the phage treatment. The heterogeneous lipid A mixture from the LPS-SJ55Ra was obtained following growth of the Gram-negative bacteria Aeromonas hydrophila (SJ-55R) in the presence of phages and isolation by the aqueous phenol method. Following hydrolysis and purification of the lipopolysaccharide, ESI-MS and low-energy CID-MS/MS analyses were performed on a triple-quadrupole (QqQ) and a Fourier transform ion...
Research Interests: Earth Sciences, Chemistry, Chromatography, Mass Spectrometry, Medicine, and 12 moreBiological Sciences, Fourier Analysis, Fatty acids, Tandem Mass Spectrometry, CHEMICAL SCIENCES, Liquid Chromatography / Electrospray Ionization Mass Spectrometry, Lipopolysaccharides, Aeromonas Hydrophila, Disaccharides, Lipid A, Molecular Structure, and Electrospray Ionization
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ABSTRACT Tungsten aryloxo-complex 1 catalyses the intramolecular metathesis reactions of di- and trisubstituted ω-unsaturated glucose, and glucosamine derivatives, yielding bicyclic carbohydrate-based compounds 12, 13, 14, 15, containing... more
ABSTRACT Tungsten aryloxo-complex 1 catalyses the intramolecular metathesis reactions of di- and trisubstituted ω-unsaturated glucose, and glucosamine derivatives, yielding bicyclic carbohydrate-based compounds 12, 13, 14, 15, containing 12-, and 14-atoms rings. Electrospray tandem mass spectrometry was used for the structural characterization of these novel bicyclic carbohydrate compounds.
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Electrospray mass spectrometry has aided the structural characterization of triazine herbicides standards. Possible fragmentation routes were first obtained by controlled collision-activated dissociation (CAD) initiated by cone voltage... more
Electrospray mass spectrometry has aided the structural characterization of triazine herbicides standards. Possible fragmentation routes were first obtained by controlled collision-activated dissociation (CAD) initiated by cone voltage fragmentation. Low energy CAD MS-MS analyses of the protonated molecules [M+H] confirmed the characteristic fingerprint patterns obtained by cone voltage fragmentation for all investigated triazine herbicides and also permitted differentiation of isomeric triazines.
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In principle, various types of vaccines that are commercially used as “antibacterial or anticancer vaccines” can be produced using various types of antigenic carbohydrate haptens containing relevant epitopes.
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This chapter surveys the current detection technologies used in commercially available luminescence biosensor detection equipments currently employed for identifying warfare biological agents (BAs). Brief technical descriptions of these... more
This chapter surveys the current detection technologies used in commercially available luminescence biosensor detection equipments currently employed for identifying warfare biological agents (BAs). Brief technical descriptions of these technologies are presented with emphasis placed on the principles of detection. Much of the content presented was obtained from the open-source literature and is an introduction to biosensor fundamentals