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71.
This article describes the design and optimization of the first entirely modular, parallel solid-phase synthetic approach for the generation of well-defined polyamine oligoboronic acid receptors and fluorescence sensors for complex oligosaccharides. The synthetic approach allows an effective building of the receptor polyamine backbone, followed by the controlled diversification of the amine benzylic side chains. This approach enabled the testing, in a modular fashion, of the effect of different arylboronic acid units substituted with unencumbering para electron-withdrawing or electron-donating groups. The feasibility of this approach toward automated synthesis was also investigated with the assembly of a sublibrary of receptors by means of the Irori MiniKan technology. Several sublibraries of anthracene-capped sensors containing two or three arylboronic acids were synthesized, and their binding to a series of model disaccharides was examined in neutral aqueous media. The calculation of association constants by fluorescence titrations confirmed that subtle changes in the structures of the interamine spacers in the polyamine backbone can have a significant effect on the stability of the resulting complexes. Most importantly, this study led to the determination of the preferred electronic characteristics for the arylboronate units, and suggests that a new generation of receptors containing very electron-poor arylboronic acids could lead to a significant improvement of binding affinities. 相似文献
72.
Bernardi A Arosio D Potenza D Sánchez-Medina I Mari S Cañada FJ Jiménez-Barbero J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(18):4395-4406
The design and synthesis of two GM1 glycomimetics, 6 and 7, and analysis of their conformation in the free state and when complexed to cholera toxin is described. These compounds, which include an (R)-cyclohexyllactic acid and an (R)-phenyllactic acid fragment, respectively, display significant affinity for cholera toxin. A detailed NMR spectroscopy study of the toxin/glycomimetic complexes, assisted by molecular modeling techniques, has allowed their interactions with the toxin to be explained at the atomic level. It is shown that intramolecular van der Waals and CH-pi carbohydrate-aromatic interactions define the conformational properties of 7, which adopts a three-dimensional structure significantly preorganized for proper interaction with the toxin. The exploitation of this kind of sugar-aromatic interaction, which is very well described in the context of carbohydrate/protein complexes, may open new avenues for the rational design of sugar mimics. 相似文献
73.
The Lewis(y)-Lewis(x) heptasaccharide, modified by an artificial aminopropyl spacer, was synthesized by an approach that employed two orthogonally protected lactosamine building blocks. A p-(benzoyl)-benzyl glycoside was used as a novel anomeric protecting group, which could be selectively removed at a late stage in the synthesis, thus offering the benefit of enhanced flexibility. The artificial aminopropyl moiety was modified by a thioacetyl group, which allowed an efficient conjugation to keyhole limpet hemocyanin (KLH) that had been activated with electrophilic 3-(bromoacetamido)-propionyl groups. Mice were immunized with the Le(y)Le(x)-BrAc-KLH antigen. Analysis of the sera by ELISA established that a strong helper T-cell immune response was raised against the Le(y)Le(x) saccharide. Further ELISA analysis showed that the titer for monomeric Le(y) tetrasaccharide was tenfold lower whereas recognition of the Le(x) trisaccharide was negligible. 相似文献
74.
Fürstner A Jeanjean F Razon P Wirtz C Mynott R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(1):320-326
The completion of the first total synthesis of the complex resin glycoside woodrosin I (1) is outlined using the building blocks described in the preceding paper. Key steps involve the TMSOTf-catalyzed coupling of diol 2 with trichloroacetimidate 3 which leads to the selective formation of orthoester 5 rather than to the expected tetrasaccharide. Diene 5, on treatment with catalytic amounts of the Grubbs carbene complex 6 or the phenylindenylidene ruthenium complex 7, undergoes a high yielding ring closing olefin metathesis reaction (RCM) to afford macrolide 8. Exposure of the latter to the rhamnosyl donor 4 in the presence of TMSOTf under "inverse glycosylation" conditions delivers compound 9 by a process involving glycosylation of the sterically hindered 2'-OH group and concomitant rearrangement of the adjacent orthoester into the desired beta-glycoside. This transformation constitutes one of the most advanced applications of the Kochetkov glycosidation method reported to date. Cleavage of the chloroacetate followed by exhaustive hydrogenation completes the total synthesis of the targeted glycolipid 1. 相似文献
75.
3-氨基-9-乙基咔唑衍生化寡糖混合物的高效液相色谱分离及激光解吸电离飞行时间质谱分析 总被引:1,自引:0,他引:1
建立了以3-氨基-9-乙基咔唑(AEC)为衍生化试剂对寡糖的标记方法。寡糖的还原端与AEC的伯氨基反应生成烯胺,再被NaBH3CN还原为二级胺,使得寡糖被AEC标记。衍生物通过反相高效液相色谱分离纯化,采用的色谱柱为Waters Symmetry C18柱(3.9 mm×150 mm,5 μm),乙腈和乙酸铵水溶液(pH 4.5)为流动相,梯度洗脱,在254 nm波长处检测,并以基质辅助激光解吸电离飞行时间质谱进行分析。在此衍生化条件和色谱条件下,葡寡糖衍生物分离良好,并且AEC衍生可显著提高葡寡糖的质谱检测灵敏度。该方法适用于寡糖的分离纯化和结构分析,并与生物质谱具有良好的兼容性,表明该方法在微量寡糖链分析方面有广阔的应用前景。 相似文献
76.
The successful separation of the disaccharide lactose from a complex mixture of human milk oligosaccharides (HMOS) with the continuous chromatography of simulated moving bed (SMB) technique is described. Since lactose is the main carbohydrate in human milk with well-known functions for the infant, it is necessary to separate it from the rest of the oligosaccharides to divide them into less complex fractions and analyse their partial unknown functions. For separation of lactose from HMOS two different stationary phases (size-exclusion gel as well as ion-exchange gel) were used. As the main result, it is shown that a size-exclusion gel with the particle size of 50-100 microm and porosity of 50 A was the preferred stationary phase for our separation process with almost complete lactose separation and stable conditions. 相似文献
77.
78.
Kajihara Y Suzuki Y Yamamoto N Sasaki K Sakakibara T Juneja LR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(4):971-985
We describe herein the preparation of 24 pure asparagine-linked oligosaccharides (Asn-oligosaccharides) from asparagine-linked biantennary complex-type sialylundecasaccharide [(NeuAc-alpha-2,6-Gal-beta-1,4-GlcNAc-beta-1,2-Man-alpha-1,6/1,3-)(2)-Man-beta-1,4-GlcNAc-beta-1,4-GlcNAc-beta-1-asparagine, 2] obtained from egg yolk. Our synthetic strategy aimed at adapting branch specific exo-glycosidases digestion (beta-D-galactosidase, N-acetyl-beta-D-glucosaminidase and alpha-D-mannosidase) of the individual asialo-branch after preparation of monosialyloligosaccharides obtained from 2 by acid hydrolysis of NeuAc. In order to perform branch specific exo-glycosidase digestion, isolation of pure monosialyloligosaccharides obtained was essential. However, isolation of two kinds of monosialyloligosaccharides are difficult by HPLC due to their highly hydrophilic nature. Therefore, we examined chemical protection with hydrophobic protecting (Fmoc and benzyl) groups. These chemical protection enabled us to separate the monosialyloligosaccharides by use of a HPLC column (ODS) on synthetic scales. Using these pure monosialiloligosaccharides enable us to obtain 24 Asn-linked oligosaccharides (100 mg scale) within a few weeks by branch specific exo-glycosidase digestions (alpha-D-neuraminidase, beta-D-galactosidase, N-acetyl-beta-D-glucosaminidase and alpha-D-mannosidase). In addition, solid-phase synthesis of glycopeptide having Asn-linked sialyl-undeca- and asialo-nonasaccharides thus obtained, was also performed on an acid labile HMPA-PEGA resin. 相似文献
79.
80.
R. K. Rakhmanberdyeva 《Chemistry of Natural Compounds》2004,40(3):215-217
Galactomannan with a galactose:mannose ratio 1:1.1 and molecular weight 79,000 was obtained from Gleditsia delavayi seeds by fractional precipitation of the water-soluble polysaccharides. Methylation, oxidation by chromic acid and periodate, and partial acid hydrolysis established that the principal galactomannan macromolecule consisted of -1.4 mannopyranose units substituted at C-6 by -galactopyranoses. 相似文献