Synthesis of fluorescent coumarin triazolylglycosides

A series of coumarin triazolylglycosides were synthesized in good yields using copper-mediated 1,3-dipolar cycloaddition reactions of carbohydrate azides and 4-alkynyl-substituted coumarins. Several of the products show strong luminescence in the 490-560 nm region and are compatible with surface imaging applications.     

Sialylation reactions with N,N-dibenzylthiosialoside donor

A new sialyl donor, N,N-dibenzyl-protected p-toluenethiosialoside, was synthesized and its sialylation reaction was investigated. This reaction proceeded in a preactivation manner and preferred to provide β-anomeric coupling products. The β-selectivity was rationalized based on the assumption that N,N-dibenzylamino group could serve as an oriented group to activate the hydroxyl group of acceptor from β-face.     

Thermotropic Poly(Ester-Amides) Based on Naphthalene Monomers

The structure and properties of a range of thermotropic poly(ester-amides) derived from 2,6-naphthalene derivatives is described. Many of these polymers may be melt-processed into fibers, monofils, and molded structures having very attractive physical and mechanical properties. A variety of monomers has been used and structure/composition/property relationships are described along with details of synthesis and processing conditions. Both fibers and molded articles may be heat-treated to enhance their tensile properties. Molded articles and extruded rods have exceptional tensile moduli in the unfilled state.     

Noncovalently galactose imprinted polymer for the recognition of different saccharides

Molecularly imprinted polymers (MIPs) represent a new class of materials possessing high selectivity and affinity for the target molecule. The main goal of this study was to prepare a galactose imprinted polymer and its potential application for the recognition of different saccharides. The selectivity of galactose imprinted polymer for several saccharides; glucose, mannose, fructose, maltose, lactose, sucrose and raffinose was investigated. Macroporous polymer was prepared utilizing ethyleneglycoldimethacrylate as a crosslinking agent, in the presence of galactose as a template molecule with acrylamide as a functional monomer. After the synthesis of polymer, galactose was removed by methanol:acetic acid washing. The selectivity of galactose imprinted polymer for other saccharides was utilized by batch rebinding assay. The arrangement of functional groups within cavities versus shape selectivity is discussed. The results showed that, the orientation of the functional groups was the dominating factor for the selectivity of galactose imprinted polymer. The dissociation constants of polymer were determined by Scatchard analysis.     

糖芯片的检测及应用

糖芯片技术具有样品少、通量高和特异性强等优点,是一种糖组学研究的新的技术平台和强大的分析工具,已经广泛用于糖和蛋白质的特异性作用、酶活性和抑制剂、病毒入侵机理、细菌检测和免疫反应等方面的研究.本文简要介绍了糖芯片的原理、制备和信号的检测技术(荧光标记法、质谱法、SPR法等),分析了糖芯片在各个领域的应用及其发展前景.     

Synthesis of novel macrocyclic crown ethers from D-glucose

A simple and efficient synthetic protocol for an easy access of carbohydrate-linked crown ethers from cheap and readily available D-glucose in good yields has been devised. The base-mediated cyclization of sugar-linked bis-iodo podands in CH₃CN with amines, including ethylamine and furfurylamine afforded the novel chiral monoaza-15-crown-5-type macrocyclic crown ethers anellated to 3-O-benzyl-1,2-O-isopropylidene-α-D-glucofuranose and 3-O-benzyl-1,2-O-isopropylidene-α-D-allofuranose. The glucose-based crown ethers have been characterized by spectroscopy techniques including IR, ¹H NMR, and ¹³C NMR.     

几种糖衍生物分子的THz光谱研究

分子间氢键等振动可以出现在THz波段。糖类是重要的生物分子,是研究氢键的典型体系。糖的衍生物分子具有重要的功能,同时由于它们的特殊的分子结构,通常有大量氢键存在,使得它们在THz波段表现出一定的光谱特征。文章测定了几种糖衍生物分子的THz光谱,结果表明不同分子具有不同的光谱,异丙基-β-D-硫代葡萄糖具有1.17,1.35,1.93,2.23 THz等多个吸收峰;异丙基-β-D-硫代半乳糖的吸收峰位于1.93 THz处;甲基-(四-氧-乙酰基-β-D-半乳糖)的吸收峰位于1.87 THz处;氧-(2, 3, 4, 6-四-氧-乙酰基-β-D-葡萄糖)-氮-羟基琥珀酰亚胺具有1.23,1.70,1.84,2.23 THz等多个吸收峰。对结构相似的分子,尤其对于异构体来说,它们具有不同的峰位,这些低频振动为包含氢键在内的整个分子的振动,说明THz方法能够鉴别异构体,是对结构变化、空间构型等很敏感的技术,是红外光谱的有益补充。这也为大分子的光谱研究提供了基础。     

The synthesis of the molecular chaperone 2,5-dideoxy-2,5-imino-d-altritol via diastereoselective reductive amination and carbamate annulation

The iminosugar 2,5-dideoxy-2,5-imino-d-altritol (DIA, 2) is a powerful competitive inhibitor of α-galactosidase A and has shown much promise as a pharmacological chaperone for the treatment for Fabry disease. Notwithstanding, syntheses of DIA are in want of optimisation. Accordingly, we report on the total synthesis of DIA in 7 steps and in 22% overall yield from readily available d-tagatose. This is the shortest and most efficient synthesis of DIA to date, with key steps in our synthetic strategy including a diastereoselective reductive amination and an I₂-mediated carbamate annulation.     

Simulated counter-current moving column chromatography used in the continuous separation of carbohydrate mixtures

Summary A moving column-bundle counter-current chromatographic system consisting of twelve 0.9 cm id×72.5 cm long glass columns has been used for the separation of glucose-starch and glucose-maltose mixtures. The system was packed with Spherosil XOBO75 for the glucose-starch separation and with Dowex-5OW-X4K⁺ for the glucose-maltose separation.Purities of up to 100% were obtained and the operating throughputs were up to 4.4 kg sugar solids/m³ resin/hr.     

Sequential Baylis-Hillman reaction and radical cyclization of furanose derivatives: expeditious approach to enantiopure benzo-fused nine-membered oxacycles

A regioselective 9-endo-trig aryl radical cyclization of d-glucose derived diastereomeric Baylis-Hillman reaction products with Bu₃SnH led to highly functionalized tricyclic benzannulated ethers incorporating cis- and trans-9,5 bicyclic systems in good yields. Degradation of one of the products afforded an enantiopure multifunctionalized benzoxonine derivative.