相转移催化法合成糖苷化合物

糖苷化合物广泛存在于生物体内，中草药和天然药物中的许多抗病活性化合物也是糖苷化合物。根据糖苷化合物分子结构中的配糖体与糖环碳原子相连的原子类型可把糖苷化合物分为氧苷、氮苷、硫苷和碳苷等。未作特殊说明的糖苷化合物均指氧苷，且配糖体为羧酸的糖苷化合物亦称为糖酯。有关糖苷（酯）化合物和其合成方法的研究很多，其中应用相转移催化法较为常见。我们曾用相转移催化法合成过许多糖酯化合物并对其生理活性进行研究报道。本文在原合成糖酯的基础上通过相转移催化法，选用不同于文献报道催化剂及溶剂体系，     

过渡金属催化的偶联反应在合成C-糖苷中的应用

C-糖苷是指糖苷键的环外氧原子被碳所取代的一类化合物的总称,其结构单元广泛存在于天然产物和药物分子中.与相应的O-糖苷和N-糖苷相比,C-糖苷具有更好的酶稳定性以及耐水解性能.由于其独特的化学结构和广泛的应用价值,其合成方法的研究已经成为当今糖化学领域的一个研究热点.主要对过渡金属催化的偶联反应构建C-糖苷的方法进行综述,试图归纳总结出不同合成方法的特点以及不足,为过渡金属催化C-糖苷的进一步合成研究提供帮助.     

糖苷化的亚氨基糖:分离、合成与生物活性

本文系统总结了糖苷化亚氨基糖的分离、合成方法与生物活性。天然存在的糖苷化的亚氨基糖根据其亚氨基糖部分的结构可以分为五类,大部分均具有重要的生物活性,尤其是糖苷酶抑制活性。此类化合物潜在的药理活性促进了相关合成方法的研究,根据糖苷键的构建方式大致可以分为酶催化的转糖基化反应和化学合成法,两者主要区别在于反应条件。酶催化的转糖基化反应条件温和,且能够减少保护基的使用,但在反应效率和选择性上仍需改进。化学合成法普适性高,有大量普通糖苷的合成经验可供借鉴,但存在反复上保护-脱保护的问题。通过以上两种合成方法,大量衍生物和类似物被设计和合成出来,大大丰富了糖苷化亚氨基糖的种类和生物活性。糖苷化亚氨基糖的生物活性往往与糖基结构和亚氨基糖环均有密切关系。作为传统糖化学与亚氨基糖的交叉领域,糖苷化亚氨基糖的结构多样性为发展高活性和选择性的先导化合物提供了优良的修饰骨架。因此,此类化合物有望在相关新药创制领域得到重要应用。     

相转移催化法在糖苷化反应中的应用

综述了相转移催化法在糖苷化反应中的应用进展,重点介绍氧苷、硫苷、氮苷、糖酯和寡糖的合成。     

碳糖苷合成的新进展

本文介绍了近几年来有关碳糖苷合成的最新进展, 包括亲电取代、亲核糖取代、过渡金属催化、异头碳自由基反应、重排和环加成反应以及糖环形成反应等。     

融合糖苷水解酶在生物质转化中的研究进展

自然界中丰富的生物质多糖可被降解为低聚寡糖或单糖.利用这些小分子糖可生产乙醇、医药制品和其他化工原料.生物质多糖的结构非常复杂,它的降解涉及多种糖苷水解酶的协同催化作用.这些糖苷水解酶有木聚糖酶、葡聚糖酶和纤维素酶等.与单个酶或简单混合酶相比,通过共价结合的融合糖苷水解酶对多糖底物的降解效率更高,选择合适的融合酶构建策略还能提高酶的表达量、活性和稳定性.这种融合酶在利用生物质生产能源物质和其他化工原料时可达到过程集成的效果,从而简化生产步骤、节约成本,所以融合糖苷水解酶能有效解决生物质利用中的瓶颈问题.本文综述了采用融合技术对糖苷水解酶进行融合改造的研究进展,包括融合酶构建策略、融合酶的性能和优势以及融合糖苷水解酶的应用.最后对该领域的基础研究和应用前景进行了展望,为融合糖苷水解酶的进一步开发和利用提供参考.     

环钯化合物在Heck反应中的应用研究

钯催化交叉偶联反应在化学工业、合成天然产物及生物活性物质中有着广泛的应用.催化剂体系是交叉偶联反应研究的核心.环钯化合物结构简单、性能稳定,在催化交叉偶联反应中具有高活性、高选择性,引起研究者们的极大关注,不断有新的环钯化合物被合成出来,其催化性能也得到了研究.本文综述了环钯化合物的合成方法及其在Heck反应中的应用.     

环钯化合物在Heck反应中的应用研究

钯催化交叉偶联反应在化学工业、合成天然产物及生物活性物质中有着广泛的应用.催化剂体系是交叉偶联反应研究的核心.环钯化合物结构简单、性能稳定,在催化交叉偶联反应中具有高活性、高选择性,引起研究者们的极大关注,不断有新的环钯化合物被合成出来,其催化性能也得到了研究.本文综述了环钯化合物的合成方法及其在Heck反应中的应用.     

糖苷化学合成研究进展

糖苷是一类非常重要的化合物,广泛存在于天然产物中,并具有多样的生物活性。糖苷的高效合成引起了越来越多研究者的关注。目前研究最多的是不断探索更高效、高选择性的合成方法。本文主要介绍了近年来糖苷化学合成的研究进展,包括以卤代糖、硫代糖、三氯乙酰亚胺酯糖、全乙酰糖、原酸酯糖、葡萄糖、磷酸酯糖作为糖基供体的合成方法。     

对氯醌基碳糖苷的高区域选择性合成方法

本文报道了两条温和、高效、实用的实验室合成对氯代醌基碳糖苷化合物的方法：其一是以芳香碳糖苷1a (1b)为初始原料,在硝酸铵催化下,与N-氯代丁二酰亚胺(NCS)反应获得对氯代芳香碳苷2a (2b),继而经硝酸铈铵(CAN)氧化,得到氯代醌基糖苷3a (3b),总收率为88% (84％);另一路线是通过三甲基氯硅烷在三氟化硼•乙醚作用下对苯醌碳苷4a (4b)的催化加成和水解反应,获得对氯代氢醌基碳苷5a (5b),总收率为82% (76%), 而它与氯代醌基糖苷3a (3b)可以通过氧化与还原反应得以相互转化。     

新工科背景下湖南大学应用化学专业的改革与建设

It is necessary to develop new engineering-directed applied chemistry major on the basis of chemistry major and to remodel the current applied chemistry education according to the concept of emerging engineering. Herein, emendation in 2020 version of applied chemistry education plan and researches on teaching renovations for applied chemistry major in Hunan University is introduced. Through the adjustments of education goals, course systems, teaching contents and teaching models, we wish to highlight the central status of the educations that integrates morality and ability. In addition to the inheritance of the specialty in corrosion and protection, it is expected to further satisfy the need of graduates for the industries such as new materials, new energy, high-tech production, environmental protection, and new generation of information technique. At last, future trends and perspectives in emerging engineering applied chemistry is proposed.     

The electric field as a novel switch for uptake/release of hydrogen for storage in nitrogen doped graphene

Nitrogen-doped graphene was recently synthesized and was reported to be a catalyst for hydrogen dissociative adsorption under a perpendicular applied electric field (F). In this work, the diffusion of H atoms on N-doped graphene, in the presence and absence of an applied perpendicular electric field, is studied using density functional theory. We demonstrate that the applied field can significantly facilitate the binding of hydrogen molecules on N-doped graphene through dissociative adsorption and diffusion on the surface. By removing the applied field the absorbed H atoms can be released efficiently. Our theoretical calculation indicates that N-doped graphene is a promising hydrogen storage material with reversible hydrogen adsorption/desorption where the applied electric field can act as a switch for the uptake/release processes.     

微流控二维电泳芯片的电压控制优化

基于微流控二维电泳芯片(2D-EMC)的流路特点,建立等效电阻模型,以便给出各端电压的合理取值范围,成功实现微流控芯片二维电泳分离.经实验测定各微通道电阻,在各端电压合理取值范围内,通过电流测量调整(优化)电压,得到了一组优化的电压控制方案,在化学发光-2D-EMC系统中成功实现了精氨酸和甘氨酸衍生物的二维分离.本方法显著减小了实现微流控芯片二维电泳分离的实验次数.     

Differences between signal currents for both polarities of applied voltages on cavity ionization chambers

A difference between the surface potential of the charge collecting electrode and that of the guard electrode of an ionization chamber changes the charge collecting volume depending on the applied voltage. If the difference is large, the saturation curve of the signal current shows a maximum at a low applied voltage. Even when there is no electrical or mechanical defect, the signal current from a parallel plate ionization chamber irradiated with ⁶⁰Co γ-rays increases or decreases with the applied voltage beyond the recombination region depending on the polarity of the applied voltage. The variation in the signal current is explained as a result of the change in the stopping power of air due to the acceleration or deceleration of secondary electrons. These electrons are emitted from the polarizing electrode towards the collector as a result of Compton scattering. In a range of low applied voltages, the signal current from a cylindrical ionization chamber is expected to be smaller for a negative applied voltage than for a positive applied voltage. This is because epithermal electrons are expected to have a higher probability of being lost by back diffusion than positive ions which are originally produced in a thermal equilibrium condition. An experimental result, however, showed no difference in the polarities of the applied voltage. The result may be explained as a consequence of the fact that epithemal electrons do not drift for long distances and maintain their energies.     

The effect of electric field strength,buffer type and concentration on separation parameters in capillary zone electrophoresis

Summary Probe solutes were used to investigate the effect of buffer type, concentration and applied voltage on solute mobility, column efficiency and resolution in capillary zone electrophoresis. With low conductivity buffers higher concentrations and/or higher voltages could be used to improve column efficiency and resolution. Doubling the concentration of the buffer doubles the amount of heat generated inside the column while doubling the applied voltage cause a 4-fold increase. Solute migration time is approximately an inverse function of the charge density of the buffer's cation. Analysis time is increased by about 30% if the buffer concentration is doubled while it is cut in half if the applied voltage is doubled. Column efficiency is improved (higher theoretical plate count) with increasing buffer concentration and/or applied voltage as long as the heat generated is efficiently dissipated. The separation factor is directly related to analysis time and, therefore, selectivity improves with increasing buffer concentration but decreases with increasing applied voltage. Hence, resolution is optimized by increasing buffer concentration at a moderate applied voltage.     

Effects of Applied Electric Fields on Drop—Interface and Drop—Drop Coalescence*

In this work, coalescence of a single organic or aqueous drop with its homophase at a horizontal liquid interface was investigated under applied electric fields. The coalescence time was found to decrease for aqueous drops as the applied voltage was increased, regardless of the polarity of the voltage. For organic drops, the coalescence time increased with increasing applied voltage of positive polarity and decreased with increasing applied voltage of negative polarity. Under an electric field, the coalescence time of aqueous drops decreases due to polarization of both the drop and the flat interface. The dependency of organic drop-interface coalescence on the polarity of the electric field may be a result of the negatively charged organic surface in the aqueous phase. Due to the formation of a double layer, organic drops are subjected to an electrostatic force under an electric field, which, depending on the field polarity, can be attractive or repulsive. Pair-drop coalescence of aqueous drops in the organic phase was also studied. Aqueous drop-drop coalescence is facilitated by polarization and drop deformation under applied electric fields. Without applied electric fields, drop deformation increases the drainage time of the liquid film between two approaching drops. Therefore, a decrease in the interfacial tension, which causes drop deformation, accelerates drop-drop coalescence under an electric field and inhibits drop coalescence in the absence of an electric field.     

X‐ray photoelectron spectroscopic study of Tencel treated with a cationic β‐cyclodextrin derivative

The interaction and the durability to laundering of a cationic β‐cyclodextrin derivative applied to Tencel were examined by x‐ray photoelectron spectroscopy (XPS). The N1(s) XPS spectra of the cationic β‐cyclodextrin treated substrates revealed the presence of the applied finish on the fibre surface and that the durability of the applied finish to hand‐wash was good. However, the cationic β‐cyclodextrin derivative showed poor durability to the ISO CO6/C2S wash protocol. Copyright © 2009 John Wiley & Sons, Ltd.     

Effects of a constant electric field on the diffusional instability of cubic autocatalytic reaction fronts

An electric field applied in the direction of propagation of a chemical reaction-diffusion front can affect the stability of this front with regard to diffusive instabilities. The influence of an applied constant electric field is investigated by a linear stability analysis and by nonlinear simulations of a simple chemical system based on the cubic autocatalytic reaction A-+2B--->3B-. The diffusional stability of the front is seen to depend on the intensity E and sign of the applied field, and D, the ratio diffusion coefficients of the reactant species. Depending on E, the front can become more or less diffusively unstable for a given value of D. Above a critical value of E, which depends on D, electrophoretic separation of the two fronts is observed.     

Effective screening length of isotropic liquid samples submitted to an applied voltage

A cell of isotropic liquid in the shape of a slab of thickness d and containing ionic impurities is considered. It is shown that the screening effect produced by the ionic charges on the external field is characterized by an effective surface length, lambda(S)(U), depending on the applied voltage U. The analysis indicates that lambda(S)(U)) < lambda(D) when the applied voltage is very large, and lambda(S)(U) --> lambda(D) for very small values of the applied voltage, where lambda(D) is the Debye screening length. The presence of the ions is responsible also for a counterpotential, v, that for small U is such to cancel the effective electric field in the sample, whereas in the opposite limit it is inversely proportional to the applied difference of potential.     

30 years of research in thermal analysis and calorimetry

The research in thermal analysis and calorimetry, conducted by the author over the period 1964 to 1993, is summarised and concisely reviewed. The major investigations have focussed on thermal analysis studies of coordination compounds, particularly the metal dithiocarbamate complexes. A significant solution calorimetric study of some metal dithiocarbamate complexes has also been undertaken. DSC has been applied to determine the sublimation enthalpies of many metal dithiocarbamate and metal pentane-2,4-dionate complexes and solution calorimetry has been applied to study the thermochemistry of the latter group of complexes. Thermal analysis investigations of several inorganic molten salt systems have been initiated. Thermometric titrimetry has been applied to study metal-macrocyclic ligand systems in aqueous media and particularly those systems of environmental significance. Temperature calibration standards for TMA have been proposed and TMA has been applied to study the mechanical properties of several common inorganic compounds. DTA has been applied to study a wide variety of phenols and has subsequently been applied as an analytical technique to determine the components of solid state phenol mixtures. Thermometric titrimetry has been applied to determine the phenolic content of wines. A comprehensive thermal analysis study of Australian brown coal has been undertaken, involving the DSC determination of coal specific energy, a TG/DTA study of the coal pyrolysis and combustion processes and a TG/DTA and EGA study of the cation catalytic effect on the coal pyrolysis process. Thermal analysis and calorimetric techniques have been extensively publicised and promoted by the publication of specialist reviews, the presentation of symposia review papers and the oral presentation of short courses, particularly in the SE Asian region. This review essentially reveals the diversity of possible application of thermal analysis and calorimetric techniques and the primary significance of thermodynamic data in the fundamental rationalisation of chemical phenomena.