Search results for "Glycosyl"
showing 10 items of 317 documents
Synthesis of glycosylated β3-homo-threonine conjugates for mucin-like glycopeptide antigen analogues
2010
Glycopeptides from the mucin family decorated with tumour-associated carbohydrate antigens (TACA) have proven to be important target structures for the development of molecularly defined anti-cancer vaccines. The strategic incorporation of β-amino acid building blocks into such mucin-type sequences offers the potential to create pseudo-glycopeptide antigens with improved bioavailability for tumour immunotherapy. Towards this end, TN and TF antigen conjugates O-glycosidically linked to Fmoc-β3-homo-threonine were prepared in good yield via Arndt–Eistert homologation of the corresponding glycosyl α-amino acid derivative. By incorporation of TN-Fmoc-β3hThr conjugate into the 20 amino acid tand…
Modulation Theory of Adhesion: Role of the Ectoenzymes Glycosidase and Glycosyltransferase
1986
It is amazing, but still plausible, that in all animal systems hitherto studied there is only one basic principle by which cell-cell recognition occurs. From sponges to higher eukaryotes there is only a small number of cell adhesion molecules which are involved in cell-cell adhesion. Specificities and histogenetic patterning are achieved by modulating processes acting on cell adhesion molecules. In sponges (secondary aggregation system) and in other eukaryotes, the activity and function of cell adhesion molecules are assumed to be modulated by enzymatic processes (glycosylation and deglycosylation). Strong evidence from experiments with sponges is available which indicates that modulation c…
Contribution of Protein Flexibility to the Foaming Properties of Casein
1990
The effect of biopolymer flexibility on the foaming properties of casein was investigated. Flexibility was altered by: (1) chemical modification (covalent binding of a monosaccharide on the lysyl residues) or (2) pH change. Electron Spin Resonance was used to measure the reorientational frequency of casein residues labeled with nitroxide radicals. High levels of glycosylation induced increased protein flexibility and improved the foaming capacity. Good agreement was observed between higher values of flexibility and improved surface properties near the isoelectric point.
Synthetic Tumor-Associated Glycopeptide Antigens from the Tandem Repeat Sequence of the Epithelial Mucin MUC4
2004
In cancer research, the development of vaccines against tumor-associated antigens is of particular interest. Epithelial cells express mucin type glycoproteins, which are extensively O-glycosylated. In case of cancer, the expression of these mucins is increased, and their carbohydrate side chains show an aberrant glycosylation pattern. A set of single and double glycosylated hexadecapeptides representing the tandem repeat sequence of the epithelial mucin MUC4 carrying different tumor-associated carbohydrate antigens was prepared by sequential solid-phase glycopeptide synthesis. The crucial glycosyl amino acid building blocks containing the T N , T, sialyl-T N and (2,6)-sialyl-T antigens were…
Impact of amino acids 22-27 of Rho-subfamily GTPases on glucosylation by the large clostridial cytotoxins TcsL-1522, TcdB-1470 and TcdB-8864
1999
Here we report data describing some principles of the interaction between small GTP-binding proteins and large Clostridial cytotoxins (LCTs). Our investigation was based on the differential glucosylation of Rac1 versus RhoA by LCTs TcsL-1522, TcdB-1470 and TcdB-8864. Chimeric RhoA/Rac1 proteins and GTPases mutated at defined regions or single amino acids were used as substrates. Starting with chimeric Rac/Rho proteins we demonstrated that proteins containing the N-terminal 73 amino acids of Rac1 (but not those of RhoA) were efficiently glucosylated. Within this stretch, three regions differ significantly in Rac1 and RhoA. Regions containing amino acids 41-45 and 50-54 had no effect on toxin…
ChemInform Abstract: Glycoside Synthesis via Electrophile-Induced Activation of N-Allyl Carbamates.
2010
Abstract O-Benzyl-, O-acyl-, N-acyl- and isopropylidene-protected glycosyl N-allylcarbamates, obtained from anomerically unprotected monosaccharides and allyl isocyanate, are activated by an electrophile-induced cyclisation and react with hydroxyl compounds to form the corresponding glycosides.
Glycosidsynthese mit 2,3,4,6-Tetra-O-pivaloyl-α-D-glucopyrancsylbromid
1982
Die Glycosylierung von Benzylalkohol und Cholesterin gelingt mit 2,3,4,6-Tetra-O-pivaloyl-α-D-glucopyranosylbromid (2) in Gegenwart von Silbersalzen in hoher Ausbeute. Die bei Koenigs-Knorr-Synthesen mit 2,3,4,6-Tetra-O-acetyl-α-D-glucopyranosylbromid (5) storende Orthoesterbildung wird beim Einsatz von 2 weitgehend unterdruckt. Die Lenkung der Reaktion zugunsten der Glycosidbildung wird dadurch erklart, das der tert-Butyl-Substituent im zwischenzeitlich gebildeten Acyloxoniumion A den nucleophilen Angriff am Acyloxoniumkohlenstoff sterisch behindert. Glycoside Synthesis Using 2,3,4,6-Tetra-O-pivaloyl-α-D-glucopyranosyl Bromide In the presence of silver salts the glycosylation of benzyl alc…
Synthesis of fluorinated Thomsen-Friedenreich antigens: direct deoxyfluorination of αGalNAc-threonine tert-butyl esters.
2011
Selectively 6-fluorinated analogs of the tumor-associated T(N) antigen Fmoc-Thr(α-O-GalNAc)-OtBu can be efficiently prepared using DAST-mediated de(hydr)oxyfluorination reactions of preformed and orthogonally protected glycosyl amino esters without affecting the labile protecting groups and O-glycosidic linkages. The resulting mono- and difluorinated T(N) analogs are interesting building blocks for non-hydrolyzable mucin-type antigen mimetics, as illustrated by the unprecedented synthesis of two different multiply fluorinated Thomsen-Friedenreich derivatives. The reported deoxyfluoro antigen analogs represent important functional probes for carbohydrate-binding proteins and glycosyl-process…
Stereoselective synthesis of C-glycosyl compounds via Michael addition of trimethylsilyl enol ethers and enamines to hex-1-enopyran-3-uloses
1987
Abstract The titanium(IV)-catalyzed addition of trimethylsilyl enol ethers to 2,4,6-tri- O -acylhex - 1 - enopyran - 3 - uloses ( 3 and 4 ) gave stereoselectively 3,6 - di - O - acyl - 4 - deoxy - β - d - glycero -hex-3-enopyranosyl-2-ulose derivatives. The formation of the C -glycosyl bond was accompanied by a 2→3 acyl shift, followed by the elimination of the 4-acyloxy substituent. Similarly, the reaction of 1-pyrrolidinocyclohexene with 3 and 4 also led stereoselectively to 2-(2,4,6-tri- O -acyl-β- d - ribo -hexopyranosyl)cyclohexanones. In this Michael addition, among the eight possible diastereomers, only one was formed. The high stereocontrol of both C -glycosyl compound syntheses is …
Synthetic Glycopeptides of the Tandem Repeat Sequence of the Epithelial Mucin MUC4 with Tumour-associated Carbohydrate Antigens
2004
Glycohexadecapeptides representing the tandem repeat sequence of the epithelial mucin MUC4 were prepared by applying a solid-phase methodology. The required glycosyl amino acid building blocks containing the tumour-associated saccharide antigens T N -, T,- sialyl-T N , (2,6)- and (2,3)-sialyl-T were synthesized according to a straightforward biomimetic strategy by stepwise extension of the saccharide side chain of a Fmoc-protected galactosamine threonine tert-butyl ester.