- Probing low affinity and multivalent interactions with surface plasmon resonance: Ligands for concanavalin A
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The affinities of the carbohydrate-binding protein concanavalin A (Con A) for mono- and multivalent ligands were measured by surface plasmon resonance (SPR) detection. Assessing protein-carbohydrate affinities is typically difficult due to weak affinities observed and the complications that arise from the importance of multivalency in these interactions. We describe a convenient method to rapidly evaluate the inhibitory constants for a panel of different ligands, both monovalent and multivalent, for low- affinity receptors, such as the carbohydrate-binding protein Con A. A nonnatural, mannose-substituted glycolipid was synthesized, and self- assembled monolayers of varying carbohydrate density were generated. The synthetic surfaces bind Con A. Competition experiments that employed monovalent ligands in solution yielded K(i) values similar to equilibrium binding constants obtained in titration microcalorimetry experiments. In addition, this assay could be used to examine various polymeric ligands of defined lengths, generated by ring-opening metathesis polymerization (ROMP). This study demonstrates the utility of this method for rapidly screening ligands that engage in low affinity interactions with their target receptors. Our results emphasize that those molecules that can simultaneously occupy two or more saccharide binding sites within a lectin oligomer are effective inhibitors of protein-carbohydrate interactions.
- Mann, David A.,Kanai, Motomu,Maly, Dustin J.,Kiessling, Laura L.
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Read Online
- Bimodal Targeting Using Sulfonated, Mannosylated PEI for Combined Gene Delivery and Photodynamic Therapy
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Photodynamic therapy (PDT) and gene delivery have both been used to target both cancer cells and tumor-associated macrophages (TAMs). Given the complex nature of tumor tissue, there could be merit in combining these strategies simultaneously. In this study, we developed a bimodal targeting approach to both cancer cells and macrophages, employing materials conducive to both gene delivery and PDT. Polymers libraries were created that consisted of cationic polyethyleneimine (PEI) conjugated to the photosensitizer pyropheophorbide-a, with sulfonation (to target selectin-expressing cells) and mannosylation (to target TAMs). Polyplexes, consisting of these polymers electrostatically bound to DNA, were analyzed for transfection efficacy and cytotoxicity toward epithelial cells and macrophages to assess dual-targeting. This study provides preliminary proof of principle for using modified PEI for targeted gene delivery and PDT.
- Chitgupi, Upendra,Li, Yi,Chen, Mingfu,Shao, Shuai,Beitelshees, Marie,Tan, Myles Joshua,Neelamegham, Sriram,Pfeifer, Blaine A.,Jones, Charles,Lovell, Jonathan F.
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Read Online
- Structure-function assessment of mannosylated poly(β-amino esters) upon targeted antigen presenting cell gene delivery
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Antigen presenting cell (APC) gene delivery is a promising avenue for modulating immunological outcomes toward a desired state. Recently, our group developed a delivery methodology to elicit targeted and elevated levels of APC-mediated gene delivery. During these initial studies, we observed APC-specific structure-function relationships with the vectors used during gene delivery that differ from current non-APC cell lines, thus, emphasizing a need to re-evaluate vector-associated parameters in the context of APC gene transfer. Thus, we describe the synthesis and characterization of a second-generation mannosylated poly(β-amino ester) library stratified by molecular weight. To better understand the APC-specific structure-function relationships governing polymeric gene delivery, the library was systematically characterized by (1) polymer molecular weight, (2) relative mannose content, (3) polyplex biophysical properties, and (4) gene delivery efficacy. In this library, polymers with the lowest molecular weight and highest relative mannose content possessed gene delivery transfection efficiencies as good as or better than commercial controls. Among this group, the most effective polymers formed the smallest polymer-plasmid DNA complexes (~300 nm) with moderate charge densities (10 mV). This convergence in polymer structure and polyplex biophysical properties suggests a unique mode of action and provides a framework within which future APC-targeting polymers can be designed.
- Jones, Charles H.,Chen, Mingfu,Gollakota, Akhila,Ravikrishnan, Anitha,Zhang, Guojian,Lin, Sharon,Tan, Myles,Cheng, Chong,Lin, Haiqing,Pfeifer, Blaine A.
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Read Online
- Synthesis, CI-MS analyses and preliminary biological evaluation of a novel library of hydrophobic persulfide-spacers α-alkyl glycosides
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We report the synthesis of novel polyether-based polyols derived from simple glycosides that bear sulfur spacers in the attempt to potentially provide new antibiotics. The CI-MS demonstrated the stepwise and successive fission of the sulfide-spacer groups; however, it does not distinguish between the alditols having different arrangement of O- (CH2)3-S(CH 2)2OH groups. The investigated compounds exhibited antimicrobial activities against Staphylococcus aureus, Pseudomonas aeruginosa, Escherichia coli and antifungal activities against Candida albicans at a concentration of 1 mg /ml in DMF.
- Hassan, Hammed H.A.M.
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Read Online
- Anomeric alkylations and acylations of unprotected mono- and disaccharides mediated by pyridoneimine in aqueous solutions
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A site-specific deprotonation followed by alkylations and acylations of sugar hemiacetals to the corresponding alkyl glycosides and acylated sugars in aqueous solutions is disclosed herein. Pyridoneimine as a new base is developed to mediate the deprotonation of readily available sugar hemiacetals and further reactions with alkylation and acylation agents.
- Dey, Kalyan,Jayaraman, Narayanaswamy
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supporting information
p. 2224 - 2227
(2022/02/17)
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- Carbon tetrachloride-free allylic halogenation-mediated glycosylations of allyl glycosides
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The allylic bromination of allyl glycosides is conducted using NBS/AIBN reagents in (EtO)2CO and PhCF3 solutions, without using CCl4 as a solvent. The activated mixed halo-allyl glycosides led to glycosylations, mediated by a triflate, in a latent-active
- Das, Anupama,Jayaraman, Narayanaswamy
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p. 9318 - 9325
(2021/11/13)
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- Synthesis of the hyper-branched core tetrasaccharide motif of chloroviruses
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Chemical synthesis of complex oligosaccharides, especially those possessing hyper-branched structures with one or multiple 1,2-cisglycosidic bonds, is a challenging task. Complementary reactivity of glycosyl donors and acceptors and proper tuning of the s
- Mishra, Bijoyananda,Manmode, Sujit,Walke, Gulab,Chakraborty, Saptashwa,Neralkar, Mahesh,Hotha, Srinivas
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p. 1315 - 1328
(2021/02/26)
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- Total Synthesis of 6-Amino-2,6-dideoxy-α-Kdo from d -Mannose
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3-Deoxy-d-manno-oct-2-ulosonic acid (Kdo) biosynthetic pathway is a promising target in antibacterial drug discovery. Herein, we report the total synthesis of 6-amino-2,6-dideoxy-α-Kdo in 15 steps from d-mannose as a potential inhibitor of Kdo-processing
- Ameur, Nassima,Gamboa Marin, Oscar Javier,Gauthier, Charles,Gormand, Paul,Hussain, Nazar,Ravicoularamin, Gokulakrishnan,Sauvageau, Janelle
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supporting information
(2020/07/27)
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- Automated Solution-Phase Synthesis of S-Glycosides for the Production of Oligomannopyranoside Derivatives
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Thioglycosides are more resistant to enzymatic hydrolysis than their O-linked counterparts, thereby becoming attractive targets for carbohydrate-based therapeutic development. We report the first development of methods for the site-selective incorporation
- Kern, Mallory K.,Pohl, Nicola L. B.
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supporting information
(2020/06/08)
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- Chemoenzymatic Synthesis of Campylobacter jejuni Lipo-oligosaccharide Core Domains to Examine Guillain-Barré Syndrome Serum Antibody Specificities
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Guillain-Barré syndrome is often caused by Campylobacter jejuni infection that has induced antibodies to the lipo-oligosaccharide (LOS) that cross-react with gangliosides at peripheral nerves causing polyneuropathy. To examine fine specificities of anti-ganglioside antibodies and develop a more robust platform for diagnosis and disease monitoring, we developed a chemoenzymatic approach that provided an unprecedented panel of oligosaccharides composed of the inner-core of the LOS of C. jejuni extended by various ganglioside mimics. The compounds and corresponding ganglio-oligosaccharides were printed as a microarray to examine binding specificities of lectins, anti-ganglioside antibodies, and serum antibodies of GBS patients. Although lectins and anti-ganglioside antibodies did not differentiate the ganglio-oligosaccharides and mimics, the patient serum samples bound much more strongly to the ganglioside mimics. The data indicate that antibodies have been elicited to a foreign epitope that includes a heptosyl residue unique of bacterial LOS and that these antibodies subsequently cross-react with lower affinity to gangliosides. The microarray detected anti-GM1a antibodies with high sensitivity and will be attractive for diagnosis, disease monitoring, and immunological research.
- Li, Tiehai,Wolfert, Margreet A.,Wei, Na,Huizinga, Ruth,Jacobs, Bart C.,Boons, Geert-Jan
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supporting information
p. 19611 - 19621
(2020/12/21)
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- Synthesis, Conformational Analysis, and Complexation Study of an Iminosugar-Aza-Crown, a Sweet Chiral Cyclam Analog
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A new family of chiral C2 symmetric tetraazamacrocycles, coined ISAC for IminoSugar Aza-Crown, incorporating two iminosugars adopting a 4C1 conformation is disclosed. Multinuclear NMR experiments on the corresponding Cdsu
- Ardá, Ana,Blériot, Yves,Bordes, Alexandra,Désiré, Jér?me,Franconetti, Antonio,Guillard, Jer?me,Jiménez-Barbero, Jesús,Ménand, Micka?l,Perrin, Flavie,Poveda, Ana,Sollogoub, Matthieu,Tripier, Rapha?l,Troadec, Thibault
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supporting information
(2020/03/26)
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- A Synthetic Carbohydrate-Protein Conjugate Vaccine Candidate against Klebsiella pneumoniae Serotype K2
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Klebsiella pneumoniae causes pneumonia and liver abscesses in humans worldwide and contains virulence factor capsular polysaccharides and lipopolysaccharides linked to the cell wall. Although capsular polysaccharides are good antigens for vaccine producti
- Ravinder, Mettu,Liao, Kuo-Shiang,Cheng, Yang-Yu,Pawar, Sujeet,Lin, Tzu-Lung,Wang, Jin-Town,Wu, Chung-Yi
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p. 15964 - 15997
(2020/11/13)
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- Preparation method of fondaparinux sodium disaccharide intermediate
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The invention discloses a preparation method of fondaparinux sodium disaccharide intermediate. 1-O-substituent sulfonyl-2,3-bis-O-benzyl-4,6-O-benzylidene-beta-D-glucopyranose directly reacts with 1,6-dehydrated-2-deoxy-2-azido-3-O-acetyl-beta-D-glucopyranose to prepare the fondaparinux sodium disaccharide intermediate as shown in a formula I; and meanwhile, the fondaparinux sodium intermediate asshown in the formula I can be used as a raw material to synthesize fondaparinux sodium intermediate as shown in a formula IV. The preparation method is simple and small in steps, the yield is high, the atomic utilization rate is high, the three wastes are small, and the preparation method is suitable for industrial large-scale production. Please see the description for the formula.
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Paragraph 0053; 0054; 0055
(2020/02/19)
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- Stereoselective β-Mannosylation with 2,6-Lactone-bridged Thiomannosyl Donor by Remote Acyl Group Participation
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Stereoselective β-mannosylation has been recognized as one of the greatest challenges of carbohydrate chemistry. Herein, we described a practical method for stereoselective construction of β-mannosides by using a 2,6-lactone-bridged thiomannosyl donor through the remote acyl-group participation as well as the steric effect of O-4 substituent. The two effects are enabled through the conversion of a regular mannopyranosyl 4C1 conformation into a 2,6-lactone bridged conformation. The lactone donor could be readily prepared in three steps on a gram scale and the β-mannosylation proceeded smoothly with high stereoselectivity for primary, secondary and tertiary alcohol acceptors. In addition, this strategy was successfully applied to the synthesis of a naturally occurring trisaccharide.
- Xu, Huanfang,Chen, Long,Zhang, Qi,Feng, Yingle,Zu, Yujia,Chai, Yonghai
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supporting information
p. 1424 - 1428
(2019/03/21)
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- Acid-Assisted Direct Olefin Metathesis of Unprotected Carbohydrates in Water
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The ability to use unprotected carbohydrates in olefin metathesis reactions in aqueous media is demonstrated. By using water-soluble, amine-functionalized Hoveyda–Grubbs catalysts under mildly acidic aqueous conditions, the self-metathesis of unprotected alkene-functionalized α-d-manno- and α-d-galactopyranosides could be achieved through minimization of nonproductive chelation and isomerization. Cross-metathesis with allyl alcohol could also be achieved with reasonable selectivity. The presence of small quantities (2.5 vol %) of acetic acid increased the formation of the self-metathesis product while significantly reducing the alkene isomerization process. The catalytic activity was furthermore retained in the presence of large amounts (0.01 mm) of protein, underlining the potential of this carbon–carbon bond-forming reaction under biological conditions. These results demonstrate the potential of directly using unprotected carbohydrate structures in olefin metathesis reactions under mild conditions compatible with biological systems, and thereby enabling their use in, for example, drug discovery and protein derivatization.
- Timmer, Brian J. J.,Ramstr?m, Olof
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p. 14408 - 14413
(2019/11/11)
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- Synthesis, kinetics and inhibition of Escherichia coli Heptosyltransferase I by monosaccharide analogues of Lipid A
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Gram-negative bacteria comprise the majority of microbes that cause infections that are resistant to pre-existing antibiotics. The complex cell wall architecture contributes to their ability to form biofilms, which are often implicated in hospital-acquired infections. Biofilms promote antibiotic resistance by enabling the bacteria to survive hostile environments such as UV radiation, pH shifts, and antibiotics. The outer membrane of Gram-negative bacteria contains lipopolysaccharide (LPS), which plays a role in adhesion to surfaces and formation of biofilms. The main focus of this work was the synthesis of a library of glycolipids designed to be simplified analogues of the Lipid A, the membrane embedded portion component of LPS, to be tested as substrates or inhibitors of Heptosyltransferase I (HepI or WaaC, a glycosyltransferase enzyme involved in the biosynthesis of LPS). Fourteen analogues were synthesized successfully and characterized. While these compounds were designed to function as nucleophilic substrates of HepI, they all demonstrated mild inhibition of HepI. Kinetic characterization of inhibition mechanism identified that the compounds exhibited uncompetitive and mixed inhibition of HepI. Since both uncompetitive and mixed inhibition result in the formation of an Enzyme-Substrate-inhibitor complex, molecular docking studies (using AutoDock Vina) were performed, to identify potential allosteric binding site for these compounds. The inhibitors were shown to bind to a pocket formed after undergoing a conformational change from an open to a closed active site state. Inhibition of HepI via an allosteric site suggest that disruption of protein dynamics might be a viable mechanism for the inhibition of HepI and potentially other enzymes of the GT-B structural class.
- Nkosana, Noreen K.,Czyzyk, Daniel J.,Siegel, Zarek S.,Cote, Joy M.,Taylor, Erika A.
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supporting information
p. 594 - 600
(2018/02/19)
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- Glycosyl Aldehydes: New Scaffolds for the Synthesis of Neoglycoconjugates via Bioorthogonal Oxime Bond Formation
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The straightforward preparation of glycosyl neoconjugates by oxime (or hydrazone) bond formation represents a key bioorthogonal tool in chemical biology. However, when this strategy is employed by reacting the reducing end of the glycan moiety, the configuration and the stereochemical information is lost due to partial (or complete) opening of the glycan cyclic hemiacetal and the formation of the corresponding opened tautomers. We have completed the synthesis of a library of glycosyl aldehydes to be used as scaffold for the synthesis of neoglycoconjugates via oxime bond formation. These glycosyl aldehydes constitute a simple and accessible alternative to avoid loss of chiral information when conjugating, by oxime (or hydrazone) bonds, the aldehyde functionality present at the reducing end of natural carbohydrates.
- Reina, José J.,Rioboo, Alicia,Montenegro, Javier
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p. 831 - 845
(2018/01/11)
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- Chemical Synthesis of Modified Hyaluronic Acid Disaccharides
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Herein we report a chemical synthesis towards new modified hyaluronic acid oligomers by using only commercially available d-glucose and d-glucosamine hydrochloride. The various protected hyaluronic acid disaccharides were synthesized bearing new functional groups at C-6 of the β-d-glucuronic acid moiety with a view to structure-related biological activity tests. The orthogonal protecting group pattern allows ready access to the corresponding higher oligomers. Also, 1H NMR studies of the new derivatives demonstrated the effect of the various functional groups on the intramolecular electronic environment.
- Mende, Marco,Nieger, Martin,Br?se, Stefan
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p. 12283 - 12296
(2017/09/14)
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- β-1,6-GLUCAN CETUXIMAB ANTIBODY CONJUGATES
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The present invention encompasses embodiments in which cetuximab or a related cetuximab antibody is conjugated to β-1,6-glucan oligomers. Thus, the present invention includes, among other things, compositions including cetuximab conjugated to one or more
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Paragraph 0248; 0253; 0254
(2016/12/22)
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- Direct glycosylation of unprotected and unactivated sugars using bismuth nitrate pentahydrate
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Bi(NO3)3, a low-cost, mild, and environmentally green catalyst, has been successfully utilized for Fischer glycosylation for the synthesis of alkyl/aryl glycopyranosides by reacting unprotected sugars, namely, D-glucose, L-rhamnose, D-galactose, D-arabinose, and N-acetyl-D-glucosamine with various alcohols in good to excellent yields. The glycosides were formed with high α-selectivity. Further, an expedient separation of α- and β-glycosides using silver nitrate-impregnated silica gel flash liquid chromatography has been developed.
- Polanki, Innaiah K.,Kurma, Siva H.,Bhattacharya, Asish K.
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p. 196 - 205
(2015/06/08)
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- Synthesis of high-mannose 1-thio glycans and their conjugation to protein
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The oligosaccharides Man4 and Man5, substructures of the high-mannose glycans of HIV glycoprotein gp120, were synthesized with a terminal 1-thiomannopyranose residue. The anomeric thiol can be readily converted to an azidomethyl aglycone through reaction with dichloromethane and displacement with sodium azide. The resulting oligomannans were then conjugated to ubiquitin utilizing thiol alkylation or azide/alkyne reactive tethers of minimal length. By combining high efficiency conjugation reactions and a short tether, we sought to establish conjugation conditions that would permit high density clustering of oligomannans in conjugate vaccines that could produce antibodies able to bind gp120 and potentially neutralize virus. LC-UV-MS was used to separate, identify and quantify the ubiquitin glycoconjugates with differing degrees of oligomannan incorporation. Binding of the HIV protective monoclonal antibody 2G12 and concanavalin A to microtitre plates coated with glycoconjugates was measured by ELISA. This journal is
- Bailey, Justin J.,Bundle, David R.
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p. 2193 - 2213
(2014/04/03)
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- Synthesis of oligosaccharide fragments of the rhamnogalacturonan of Nerium indicum
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Three trisaccharides, one pentasaccharide, and one heptasaccharide, namely α-D-GalA-(1→2)-α-L-Rha-(1→4)-β-D-GalA-OC 3H7 (1), α-L-Rha-(1→4)-α-D-GalA- (1→4)-β-D-GalA-OC3H7 (2), α-D-GalA- (1→4)-α-DGalA-(1→2)-α-L-Rh
- Ma, Yuyong,Cao, Xin,Yu, Biao
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- Regiospecific anomerisation of acylated glycosyl azides and benzoylated disaccharides by using TiCl4
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Chelation induced anomerisation is promoted when Lewis acids, such as TiCl4 or SnCl4, coordinate to the pyranose ring oxygen atom and another site, giving rise to endocyclic cleavage and isomerisation to the more stable anomer. In this research regiospecific site-directed anomerisation is demonstrated. TiCl4 (2.5equiv) was employed to induce anomerisation of 15 glycosyl azide and disaccharide substrates of low reactivity, and high yields (>75 %) and stereoselectivies (α/β>9:1) were achieved. The examples included glucopyranuronate, galactopyranuronate and mannopyranuronate as well as N-acetylated glucopyranuronate and galactopyranuronate derivatives. A disaccharide with the α1→4 linkage found in polygalacturonan was included. The use of benzoylated saccharides was found to be important in disaccharide anomerisation as attempts to isomerise related acetyl protected and 2,3-carbonate protected derivatives were not successful. Copyright
- Farrell, Mark,Zhou, Jian,Murphy, Paul V.
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p. 14836 - 14851
(2013/11/06)
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- An unusual synthesis of 2-pyridone and 3,5-dihydroxypyridine from a carbohydrate
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An unusual aromatization to perbenzylated 3,5-dihydroxy-6-(hydroxymethyl)- 2-pyridone was demonstrated utilizing sugar lactam, under strong basic conditions, derived from d-Galactose. 2-Pyridone was efficiently converted into a pharmaceutically relevant s
- Gorantla, Jaggaiah N.,Kovval, Divya,Lankalapalli, Ravi S.
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supporting information
p. 3230 - 3232
(2013/06/27)
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- OLEFIN METATHESIS REACTIONS OF AMINO ACIDS, PEPTIDES AND PROTEINS CONTAINING ALLYL SULFIDE GROUPS
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A method for the modification of an amino acid, protein or peptide is disclosed. The method comprises reacting a carbon-carbon double bond-containing compound with an amino acid, a protein or a peptide containing an allyl sulfide group in the presence of a catalyst which promotes olefin metathesis, to form a modified amino acid, protein or peptide. Preferred carbon-carbon double bond-containing compounds include carbohydrates.
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Page/Page column 7
(2012/07/27)
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- Stereoselective dihydroxylation reaction of alkenyl β- D -hexopyranosides: A methodology for the synthesis of glycosylglycerol derivatives and 1-O-Acyl-3-O-β- D -glycosyl-sn-glycerol analogues
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A variety of new glycosylglycerol derivatives have been prepared by stereoselective dihydroxylation of a range of alkenyl β-D-hexopyanosides under Donohoe's conditions. We have studied the relationship between the diastereoisomeric excess and the structural features of the precursor (sugar and alkenyl moieties). The stereochemical yields demonstrated that the presence of a hydrogen-bond donor group (OH, NHAc) at the 2-position of the sugar moiety is required to obtain high levels of stereofacial discrimination. New 1-O-acyl-3-O-β-D-glycosyl-sn-glycerol analogues were obtained by functionalisation of the primary hydroxy group with a fatty acid. Preliminary cytotoxic activity assays of both glycosylglycerol and glycoglycerolipid analogues are also presented. An efficient asymmetric dihydroxylation reaction of alkenyl β-D-hexopyranoside derivatives is described. New glycosylglycerol and glycoglycerolipid analogues have been synthesised by this methodology. Preliminary cytotoxic activity assays are presented. Copyright
- Vega-Perez, Jose M.,Palo-Nieto, Carlos,Perinan, Ignacio,Vega-Holm, Margarita,Calderon-Montano, Jose M.,Lopez-Lazaro, Miguel,Iglesias-Guerra, Fernando
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experimental part
p. 1237 - 1252
(2012/04/10)
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- Fluorine-directed β-galactosylation: Chemical glycosylation development by molecular editing
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Validation of the 2-fluoro substituent as an inert steering group to control chemical glycosylation is presented. A molecular editing study has revealed that the exceptional levels of diastereocontrol in glycosylation processes by using 2-fluoro-3,4,6-tri-O-benzyl glucopyranosyl trichloroacetimidate (TCA) scaffolds are a consequence of the 2R,3S,4S stereotriad. This study has also revealed that epimerization at C4, results in a substantial enhancement in β-selectivity (up to β/α 300:1). Copyright
- Durantie, Estelle,Bucher, Christoph,Gilmour, Ryan
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supporting information; experimental part
p. 8208 - 8215
(2012/08/27)
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- Saccharide-modified nanodiamond conjugates for the efficient detection and removal of pathogenic bacteria
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The detection and removal of bacteria, such as E. coli in aqueous environments by using safe and readily available means is of high importance. Here we report on the synthesis of nanodiamonds (ND) covalently modified with specific carbohydrates (glyco-ND) for the precipitation of type 1 fimbriated uropathogenic E. coli in solution by mechanically stable agglutination. The surface of the diamond nanoparticles was modified by using a Diels-Alder reaction followed by the covalent grafting of the respective glycosides. The resulting glyco-ND samples are fully dispersible in aqueous media and show a surface loading of typically 0.1 mmol g-1. To probe the adhesive properties of various ND samples we have developed a new sandwich assay employing layers of two bacterial strains in an array format. Agglutination experiments in solution were used to distinguish unspecific interactions of glyco-ND with bacteria from specific ones. Two types of precipitates in solution were observed and characterized in detail by light and electron microscopy. Only by specific interactions mechanically stable agglutinates were formed. Bacteria could be removed from water by filtration of these stable agglutinates through 10 μm pore-size filters and the ND conjugate could eventually be recovered by addition of the appropriate carbohydrate. The application of glycosylated ND allows versatile and facile detection of bacteria and their efficient removal by using an environmentally and biomedically benign material. Copyright
- Hartmann, Mirja,Betz, Patrick,Sun, Yuchen,Gorb, Stanislav N.,Lindhorst, Thisbe K.,Krueger, Anke
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supporting information; experimental part
p. 6485 - 6492
(2012/06/16)
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- C-C bond formation by sequential intramolecular hydrogen atom transfer/intermolecular radical allylation reaction in carbohydrate systems
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A tandem 1,5-, 1,6- or 1,8-intramolecular hydrogen atom transfer (HAT)/intermolecular radical allylation using mono- or (1→4)-O-disaccharide models is described. It is a simple, sequential, stereocontrolled methodology for C-C bond formation by remote free radical functionalization, giving access to interesting carbohydrate structures carrying differently functionalized tethers. A tandem intramolecular hydrogen atom transfer (HAT)/intermolecular radical allylation is described. This process occurs by a completely regio- and stereoselective route that provides a simple methodology for C-C bond formation on remote positions without modifying the remainder of the carbohydrate. Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
- Leon, Elisa I.,Martin, Angeles,Perez-Martin, Ines,Quintanal, Luis M.,Suarez, Ernesto
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p. 3818 - 3829
(2012/09/21)
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- CELLULOSE SUPPORT CONTAINING D-MANNOSE DERIVATIVES
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Cellulose support containing mannose derivatives able to fix type 1 piliated bacteria, application to disinfecting wipes especially. Support intended to bind type 1 piliated bacteria comprising cellulose fibers and/or regenerated cellulose fibers onto which mannose derivative is fixed characterized in that the mannose derivative is present in the form of copolymer obtained by copolymerization of: —a monomer derivative of alkenyl α-D-mannopyranoside modified with a function capable of reacting with an acrylamid monomer, —a cationic monomer —an acrylamid monomer.
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- Total synthesis of a glycosylphosphatidylinositol anchor of the human lymphocyte CD52 antigen
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The first total synthesis of a glycosylphosphatidylinositol (GPI) anchor bearing a polyunsaturated arachidonoyl fatty acid is reported. This lipid is found in mammalian GPIs that do not undergo lipid remodeling, a process that has important implications in the localization and function of GPI-anchored proteins. Incorporation of the oxidation- and reduction-sensitive arachidonoyl lipid in the target GPI was accomplished by using the para-methoxybenzyl (PMB) group for permanent hydroxyl group protection, which featured a selective, rapid, and efficient global deprotection protocol. The flexibility of this synthetic strategy was further highlighted by the inclusion of two additional GPI core structural modifications present in the GPI anchor of the human lymphocyte CD52 antigen. Lipid diversity in GPI synthesis: The convergent synthesis of an arachidonoyl-containing glycosylphosphatidylinositol (GPI) anchor of the human lymphocyte CD52 antigen is reported. Incorporation of the oxidation- and reduction-sensitive polyunsaturated arachidonoyl lipid, as well as two additional GPI core modifications (see structure), was enabled by using a para-methoxybenzyl (PMB)-based global protection strategy. Copyright
- Burgula, Srinivas,Swarts, Benjamin M.,Guo, Zhongwu
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supporting information; experimental part
p. 1194 - 1201
(2012/03/26)
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- Synthesis of biotinylated multipodal glycoclusters on a solid support
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Trivalent glycoconjugates, each bearing a biotin side arm in addition to three different sugar ligands, have been synthesized on a solid support. The conjugates were assembled on an orthogonally protected pentaerythrityl tetramine core that was anchored to the support through a backbone amide linker. Peptide coupling chemistry was applied to elongate three of the branches with β-alanine and a fully acylated glycosylacetic acid. The fourth branch was levulinoylated and oximated with aminooxy-derivatized D-biotin, followed by acidolytic release into solution. The acyl protecting groups were removed by methoxide-catalyzed transesterification in methanol.
- Karskela, Marika,Von Usedom, Miriam,Virta, Pasi,Loennberg, Harri
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p. 6594 - 6605
(2013/01/15)
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- Green glycosylation promoted by reusable biomass carbonaceous solid acid: An easy access to β-stereoselective terpene galactosides
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An efficient green protocol has been developed for the atom economic glycosylation of unprotected, unactivated glycosyl donors and glycosylation of glycosyl trichloroacetimidates with the aid of reusable eco-friendly biomass carbonaceous solid acid as catalyst. The Royal Society of Chemistry.
- Gorityala, Bala Kishan,Ma, Jimei,Pasunooti, Kalyan Kumar,Cai, Shuting,Liu, Xue-Wei
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supporting information; experimental part
p. 573 - 577
(2011/05/06)
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- Efficient glycosylation of unprotected sugars using sulfamic acid: A mild eco-friendly catalyst
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Sulfamic acid, a mild and environmentally benign catalyst has been successfully used in the Fischer glycosylation of unprotected sugars for the preparation alkyl glycosides. A diverse range of aliphatic alcohols have been used to prepare a series of alkyl glycosides in good to excellent yield.
- Guchhait, Goutam,Misra, Anup Kumar
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experimental part
p. 52 - 57
(2012/01/15)
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- Synthesis of a glycodendrimer incorporating multiple mannosides on a glucoside core
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The synthesis of a glycodendrimer by incorporating repetitive mannoside units onto a glucoside core was carried out to multivalently probe fundamental carbohydrate-protein interactions. The dendritic structure was constructed by a modified procedure that
- Wang, Chao,Sanders, Brian,Baker, David C.
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experimental part
p. 959 - 963
(2011/10/10)
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- COMPOUND RETAINED IN TUMOR
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A novel compound which specifically resides in a tumor, a method for allowing it to reside in a tumor, and a method for detecting, diagnosing, and treating tumor with use thereof are provided. The present invention relates to a compound represented by chemical formula (I) wherein R is an anionic group binding to hydrogen, R1 is OH, OCOH, OCO(CH2)hCH3, or an acting group, h being an integer of 0 or more, R2 is H, OH, OCOH, OCO(CH2)iCH3, or an acting group, i being an integer of 0 or more, R3 is OH, SO3H, or an acting group, R4 is OH, SO3H, or an acting group, and R5 is OH, SO3H, or an acting group, at least one of R1, R2, R3, R4, and R5 containing an acting group, or pharmaceutically acceptable salts thereof.
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Page/Page column 48
(2011/12/03)
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- Total synthesis of the fully lipidated glycosylphosphatidylinositol (GPI) anchor of malarial parasite Plasmodium falciparum
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We report a new and convergent strategy for the total synthesis of fully lipidated glycosylphosphatidylinositol (GPI) anchor, the major pro-inflammatory factor of malarial parasite (Plasmodium falciparum). The key features of our approach include, the acc
- Ali, Asif,Vishwakarma, Ram A.
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scheme or table
p. 4357 - 4369
(2010/07/06)
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- A kit for the investigation of live Escherichia coli cell adhesion to glycosylated surfaces
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A combination of microtiter plate functionalization techniques and two facile bacterial adhesion inhibition assays form a flexible toolbox for the investigation of bacterial adhesion mechanisms on glycosylated surfaces.
- Hartmann, Mirja,Horst, Andrea K.,Klemm, Per,Lindhorst, Thisbe K.
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supporting information; experimental part
p. 330 - 332
(2010/05/01)
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- The Glc2Man2-fragment of the N-glycan precursor - A novel ligand for the glycan-binding protein malectin?
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The Glcα(1→3)Glcα(1→3)Manα(1→2)Man tetrasaccharide (Glc2Man2-fragment), a substructure of the natural N-glycan precursor, was synthesized. The interaction of this fragment with the protein malectin, a carbohydrate binding protein localized in the endoplasmatic reticulum, was investigated by 1H15N HSQC experiments and isothermal calorimetry. The chemical shift perturbations of nuclei in the protein's backbone caused by the binding of the Glc 2Man2-fragment to malectin suggest a binding mode like the known ligand nigerose. The Royal Society of Chemistry 2010.
- Mueller, Lisa N.,Muhle-Goll, Claudia,Biskup, Moritz B.
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supporting information; scheme or table
p. 3294 - 3299
(2010/08/21)
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- Total synthesis of 3,3-difluorinated 1-deoxynojirimycin analogues
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Difluorination of 1-deoxynojirimycin at position C(3) creates a competitive inhibitor 15 of 10 times higher activity against an α-glucosidase than the parent compound. Its screening against a panel of human cell lines showed a low cytotoxicity therefore m
- Csuk, René,Prell, Erik,Korb, Claudia,Kluge, Ralph,Str?hl, Dieter
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scheme or table
p. 467 - 472
(2010/04/04)
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- Olefin cross-metathesis on proteins: Investigation of allylic chalcogen effects and guiding principles in metathesis partner selection
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Olefin metathesis has recently emerged as a viable reaction for chemical protein modification. The scope and limitations of olefin metathesis in bioconjugation, however, remain unclear. Herein we report an assessment of various factors that contribute to productive cross-metathesis on protein substrates. Sterics, substrate scope, and linker selection are all considered. It was discovered during this investigation that allyl chalcogenides generally enhance the rate of alkene metathesis reactions. Allyl selenides were found to be exceptionally reactive olefin metathesis substrates, enabling a broad range of protein modifications not previously possible. The principles considered in this report are important not only for expanding the repertoire of bioconjugation but also for the application of olefin metathesis in general synthetic endeavors.
- Lin, Yuya A.,Chalker, Justin M.,Davis, Benjamin G.
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supporting information; experimental part
p. 16805 - 16811
(2011/02/17)
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- Synthesis of benzaldehyde-functionalized glycans: A novel approach towards glyco-SAMs as a tool for surface plasmon resonance studies
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In recent years the interest in tools for investigating carbohydrateprotein (CPI) and carbohydrate-carbohydrate interactions (CCI) has increased significantly. For the investigation of CPI and CCI, several techniques employing different linking methods are available. Surface plasmon resonance (SPR) imaging is a most appropriate tool for analyzing the formation of self-assembled monolayers (SAM) of carbohydrate derivatives, which can mimic the glycocalyx. In contrast to the SPR imaging methods used previously to analyze CPI and CCI, the novel approach reported herein allows a facile and rapid synthesis of linker spacers and carbohydrate derivatives and enhances the binding event by controlling the amount and orientation of ligand. For immobilization on biorepulsive amino-functionalized SPR chips by reductive amination, diverse aldehyde-functionalized glycan structures (glucose, galactose, mannose, glucosamine, cellobiose, lactose, and lactosamine) have been synthesized in several facile steps that include olefin metathesis. Effective immobilization and the first binding studies are presented for the lectin concanavalin A.
- Kopitzki, Sebastian,Jensen, Knud J.,Thiem, Joachim
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supporting information; experimental part
p. 7017 - 7029
(2010/09/10)
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- Synthesis of a glycosylphosphatidylinositol anchor bearing unsaturated lipid chains
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A GPI anchor bearing unsaturated fatty acid lipid chains (1) was synthesized by a highly convergent strategy employing the para-methoxybenzyl group for permanent hydroxyl protection. The final global deprotection was achieved by an efficient three-step, one-pot procedure to give an 81% isolated yield of the target structure.
- Swarts, Benjamin M.,Guo, Zhongwu
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supporting information; experimental part
p. 6648 - 6650
(2010/07/04)
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- Hydrogen atom transfer experiments provide chemical evidence for the conformational differences between C-and O-disaccharides
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The glycopyran-6-O-yl radical promoted hydrogen atom transfer reaction (HAT) between the two pyranose units of α-D-Manp-(1→4)-α-D-Glcp and α-D-Manp-(1→4a)-4a-carba-α-D-Glcp disaccharides provides supporting chemical evidence for the conformational differe
- Leon, Elisa I.,Martin, Angeles,Perez-Martin, Ines,Quintanal, Luis M.,Suarez, Ernesto
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supporting information; experimental part
p. 5248 - 5262
(2010/11/02)
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- Exploiting the cross-metathesis reaction in the synthesis of pseudo-oligosaccharides
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An approach to the synthesis of pseudo-oligosaccharides based on the cross-metathesis reaction between distinct sugar-olefins, followed by intramolecular cyclization of the obtained heterodimer, is presented. In particular, the relative efficiency of two
- Ronchi, Paolo,Vignando, Stefano,Guglieri, Sara,Polito, Laura,Lay, Luigi
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body text
p. 2635 - 2644
(2009/10/30)
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- Green glycosylation using ionic liquid to prepare alkyl glycosides for studying carbohydrate-protein interactions by SPR
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Several simple glycosides of d-glucose (Glc) and N-acetyl-d-galactosamine (GalNAc) were prepared in a single step glycosylation reaction using unprotected and unactivated sugar donors. The resulting GalNAc glycoside, containing a bifunctional linker, was used to immobilize this glycoconjugate to a self assembled monolayer on a gold biosensor chip. Surface plasmon resonance (SPR) experiments demonstrated that this immobilized glycoconjugate bound to GalNAc specific lectin, Viscum album agglutinin.
- Javier Munoz,Andre, Sabine,Gabius, Hans-Joachin,Sinisterra, Jose V.,Hernaiz, Maria J.,Linhardt, Robert J.
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experimental part
p. 373 - 379
(2010/04/22)
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- Ionic liquid promoted atom economic glycosylation under Lewis acid catalysis
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Straightforward glycosylation of various alcohols with unprotected and non-activated monosaccharides were performed under scandium triflate catalysis. Rate and yield of glycosylation were highly improved when using 1-butyl-3-methylimidazolium trifluoromethanesulfonate as a green solvent. This ionic liquid was allowed to be recycled at least three times without loss of activity. The possibility of drastically reducing the amounts of catalyst (down to 1 mol%) and aglycone (down to 1 equiv) when performing the reaction in ionic liquid opens new perspectives in O-glycosylation, as a direct coupling between an aglycone and free sugars.
- Auge, Jacques,Sizun, Gwenaelle
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scheme or table
p. 1179 - 1183
(2010/05/02)
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- Glycosylation using unprotected alkynyl donors
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(Chemical Equation Presented) Gold(III) activation of unprotected propargyl glycosyl donors has been shown to be effective for the synthesis of saccharides. Terminal propargyl glycosides of glucose, galactose, and mannose required heating at reflux in ace
- Mamidyala, Sreeman K.,Finn
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experimental part
p. 8417 - 8420
(2010/01/16)
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- Synthesis of |β-(1→2)-linked oligomannosides
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β-(1→2)-Linked oligomannosides constitute an important class of carbohydrate structures located on the cell surface of several Candida species, including C. albicans. As a result of the immunostimulating properties of such compounds, the upscaling of their synthesis is relevant. In this paper, a highly stereoselective synthesis of |β-(1→2)-linked oligomannosides was performed by further development of and modifications to the methodologies described earlier in the literature. In addition to the synthesis of fully deprotected β-(1→2)-linked mannobiose and mannotriose, some preliminary modifications to the oligosaccharide core, resulting in close analogues with biological potential, are presented. The fully deprotected products form potential targets for screening against C. albicans and may also result in new model structures for vaccine development.
- Polakova, Monika,Roslund, Mattias U.,Ekholm, Filip S.,Saloranta, Tiina,Leino, Reko
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experimental part
p. 870 - 888
(2009/07/17)
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- Allyl sulfides are privileged substrates in aqueous cross-metathesis: Application to site-selective protein modification
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Allyl sulfides undergo efficient cross-metathesis in aqueous media with Hoveyda-Grubbs second generation catalyst 1. The high reactivity of allyl sulfides in cross-metathesis was exploited in the first examples of cross-metathesis on a protein surface. S-Allylcysteine was incorporated chemically into the protein, providing the requisite allyl sulfide handle. Preliminary efforts to genetically incorporate S-allylcysteine into proteins are also reported. Copyright
- Lin, Yuya A.,Chalker, Justin M.,Floyd, Nicola,Bernardes, Goncalo J. L.,Davis, Benjamin G.
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supporting information; experimental part
p. 9642 - 9643
(2009/02/04)
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- Montmorillonite K-10 as a reusable catalyst for fischer type of glycosylation under microwave irradiation
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Montmorillonite K-10-catalyzed Fischer type glycosylation was studied for various monosacharides with different alcohols under microwave irradiation. The method was found to be efficient, economic, simple, and time saving and the catalyst montmorillonite K-10 was reused three times without loss of catalytic activity and anomeric selectivity. With glycerol, the method gave products glycosylated at primary alcohols only.
- Bordoloi, Manobjyoti
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p. 300 - 308
(2008/12/21)
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