抗癌药物紫杉醇的全合成-Nicolaou法全合成紫杉醇的剖析

介绍和剖析了用Nicolaou法全合成紫杉醇的方法,包括合成的战略和路线,关键反应和保护基的应用等.     

紫杉醇研究进展

紫杉醇是目前最新的具有很好疗效的抗癌药物, 本文对自紫杉醇发现以来的最新研究进展进行了比较详尽的综述。包括以下几个部分: 1.紫杉醇的发现和历史; 2. 紫杉醇的来源; 3. 紫杉醇的全合成研究; 4. 紫杉醇的生物合成; 5. 通过真菌生产紫杉醇; 6.通过植物细胞培养生产紫杉醇; 7. 紫杉醇化学研究的展望。     

紫杉醇的合成进展

紫杉醇是一种重要的抗癌药物,它具有复杂新颖的化学结构,为三环二萜类化合物.本文综述了紫杉醇的半合成和紫杉烷环的各种合成方法.     

近年来紫杉醇的合成研究进展

紫杉醇和多烯紫杉醇是目前销量最大的临床抗癌药物.近年来围绕紫杉醇所进行的高水平研究仍然层出不穷.综述了2008年以来紫杉醇的合成研究进展,主要涉及紫杉醇6-8-6骨架的构建、环系的合成以及侧链的制备.     

紫杉醇全合成

评论了紫杉醇合成了合成战略，合成路线，逆合成分析及展望，参考文献９篇。     

紫杉醇生物合成综述

本文对近年来紫杉醇生物合成的途径中关键酶的研究进展进行了评述。目前紫杉醇的生物合成途径已初见端倪,其生物合成途径中环化酶的基因已经克隆成功。在分子及基因水平上生产紫杉醇的曙光开始出现。     

血清白蛋白对紫杉醇的化学修饰

采用两种方法由牛血清白蛋白和人血清白蛋白修饰紫杉醇,提高了水溶性.红外和紫外数据证实了修饰结果.     

抗癌药物多烯紫杉醇载体

多烯紫杉醇(docetaxel)是一种具有良好疗效的抗癌药物,由于其低的水溶性和溶媒所带来的严重副作用,使其临床应用受到限制。基于此问题,通过化学合成的方法,构建抗癌药物多烯紫杉醇载体,一直吸引着科学工作者的广泛关注。本文通过检索近十年来国内外相关文献报道,对多烯紫杉醇载体进行分类,综述其研究进展,并对当前面临的问题进行总结探讨,以期对DTX载体的研发和应用提供参考。     

6α-羟基紫杉醇的合成

以紫杉醇为原料,经过羟基保护、磺酸化、烯化、双羟基化、构型翻转、去除保护基,得到6α-羟基紫杉醇。目标化合物和中间体的结构经1H NMR、MS确证,总收率为3.97%。     

HPLC-MS联用测定发酵液中的紫杉醇

用HPLC-MS测定发酵液中的紫杉醇,分别考察了实验条件下(+)ESI和(-)ESI方式的MS检测灵敏度,苯基柱和C18柱的分离效果,研究表明以(-)ESI方式的MS检测灵敏度较(+)ESI方式优,苯基柱的分离效果优于C18柱,本文报道的实验方法用于测定发酵液中的紫杉醇效果快速、准确、可靠.     

Contributions to the Chemistry of the Binary Compounds of the Transition Elements

Phase and structural relationships of the sulfur, selenium, and tellurium compounds of the 4d and 5d transition elements of groups IV to VII of the periodic system are discussed. Homologous elements behave very similarly with respect to the chalcogens, and this is particularly the case for niobium and tantalum, and for molybdenum and tungsten. However, zirconium, niobium, and molybdenum have a greater tendency towards formation of chalcogen-poor phases than their homologues hafnium, tantalum, and tungsten. Subchalcogenides are known only for zirconium and niobium. The number of phases and the tendency towards formation of solid solutions are considerably smaller among the tellurides than among the sulfides and selenides. The crystal structures of the telluride phases also differ from those of the sulfide and selenide phases of analogous composition. In addition, a review of the phase and structural relationships of the arsenic and antimony compounds of the 4d and 5d transition elements of groups V to VII is given.     

纳米粒子的精准组装

纳米材料由于其独特的光、电、磁、力学等性质,成为了构建功能材料与器件的理想基元。实现纳米粒子的精确组装,是探究粒子之间的耦合聚集性质和制备宏观功能器件的基础。但是由于纳米粒子的小尺寸以及在溶液中运动的随机性与复杂性,精准控制纳米粒子组装体的形貌以及在空间中的相对位置仍存在巨大挑战。为了将纳米粒子组装成理想的有序结构,许多控制粒子组装的策略与方法得到发展。本文首先概述了纳米粒子自组装的控制方法与典型形貌,着重分析了影响粒子精准排布的因素与控制方法,并对纳米粒子及其组装体的光学性质与器件应用的最新研究进展进行了讨论,最后对目前纳米粒子精准组装所面临的挑战以及未来发展的方向进行了展望。     

“蛋黄-蛋壳”结构纳米反应器的设计、调控及在锂硫电池正极中的应用研究

锂硫电池具有理论能量密度高等优势,被认为是最有前景的一类新型二次电池.硫正极存在硫和硫化锂的导电性差、可溶性多硫化物的扩散/穿梭、循环过程中硫的体积膨胀以及氧化还原过程慢等问题,严重制约着电池的活性和循环稳定性.设计“蛋黄-蛋壳”结构纳米反应器应用于锂硫电池正极,可通过调控其“蛋黄”、“蛋壳”和“空腔”结构缓解充放电过程中电极的体积变化,为离子/电子输运提供快速通道,强化对多硫化物的吸附和催化转换作用等,进而提高电极的活性和循环性能,有利于推进锂硫电池的商业化进程.本文总结了“蛋黄-蛋壳”结构纳米反应器的设计和调控策略,包括单核-单壳、单核-多壳、多核-单壳以及多核-多壳等,并结合锂硫电池的工作特点和目前应用存在的问题,对未来发展前景进行了展望.     

表面活性剂与叶酸的相互作用及其对光氧化降解的影响

表面活性剂与有机小分子作用不仅能提高表面活性剂的聚集能力,还能提高小分子的溶解度、稳定性等应用性能,因此研究二者之间的相互作用机理对于促进表面活性剂的发展和实际应用具有重要意义。本工作提出了一种利用功能有机小分子调控表面活性剂聚集行为,进而提高不稳定小分子自身稳定性的新策略。利用表面张力、紫外可见吸收光谱、荧光光谱、动态光散射、等温滴定量热和核磁共振技术研究了在p H为7.0时,叶酸分别与十二烷基硫酸钠(SDS)、十二烷基三甲基溴化铵(DTAB)、季铵盐Gemini 12-6-12和季铵盐线性三聚12-3-12-3-12四种表面活性剂之间的相互作用及其导致的叶酸光氧化降解性能的变化,结果表明,阴离子表面活性剂SDS抑制叶酸光氧化降解的效率较低,而阳离子表面活性剂都能够显著抑制叶酸的光氧化降解,且随着表面活性剂寡聚度的增加,抑制效果增强,所需表面活性剂的浓度显著降低,寡聚表面活性剂12-3-12-3-12的抑制效率高达96%。     

纳米粒子与细胞相互作用的力学-化学偶联研究进展

纳米粒子在生物医学和大气环境领域的广泛研究使得其生物安全性越来越受到重视。目前已经有许多研究关注纳米粒子与细胞的相互作用及细胞毒性问题。本综述从细胞力学-化学偶联的角度总结了近五年来有关纳米粒子与细胞相互作用的研究进展。首先介绍了与细胞力学-化学偶联性质相关的分子基础以及目前检测细胞机械性质的纳米技术,然后重点讨论了纳米粒子对细胞粘附、骨架、刚度和迁移性质的影响。在此基础上,进一步指出了纳米生物力学-化学偶联的挑战与展望。     

离子的极化和形变

离子的极化和形变是无机化学教学中的一对重要概念,这对概念可以用于解释化合物的结构及许多物理和化学性质。然而一些教科书在介绍这对概念时,大都把极化作用限于阳离子,把形变作用限于阴离子,而忽略了阴离子的极化作用和阳离子的形变作用。同时,在应用这对概念解释化合物结构和性质时,条理上也不十分清晰,甚至还出现自相矛盾的情况,使得学生在学习这对概念时感到困惑。本文介绍了离子的极化和形变这对概念的基本含义,讨论了影响极化能力和形变程度的因素,分析了一些化合物的结构以及溶解度、颜色和热稳定性等物理和化学性质。特别是对一些教学中有争议的问题给出了合理解释。在分析小分子结构时,极化和形变概念的运用可以弥补杂化轨道理论和价层电子对互斥理论的不足。     

An integrated strategy of secondary metabolomics and glycomics to investigate multi-component variations in wine-processing of medicinal herbs and functional foods: A case study on Fructus Corni

Fructus Corni (FC), as a promising Chinese medicinal herb, has aroused considerable interest. Generally, FC needs to be processed according to the limited standard policy in China before clinical application, while the investigations on the specific processing methods (such as wine steaming or high-pressure wine steaming) are unclear. A comprehensive metabolomics strategy based on integrated non-targeted metabolomics and targeted glycomics in this paper was implemented to investigate the influences of the different processing technologies such as steaming, wine steaming, high-pressure steaming, high-pressure wine steaming, wine immersion, and wine stir-frying on FC, respectively. UHPLC-Q-TOF-MS/MS was employed for identifying and distinguishing the secondary metabolites. A total of 85 components were identified in all groups. The results of PCA score plots showed that the crude and processed samples had a complete separation, and wine steamed and high-pressure wine steamed samples could be a category, indicating that the two processed products had a similar quality. Multiple chromatography including HPLC (C₁₈)-PDA, HPLC (NH₂)-ELSD, and HPGPC-ELSD was used for determining the molecular weight distributions, the monosaccharide compositions of polysaccharides, and the contents of free monosaccharides and oligosaccharides. The results indicated that the content and composition of saccharides were different in crude and different processed FC. The polysaccharides were composed of fucose, arabinose, galactose, glucose, galacturonic acid, mannose and rhamnose, and the free monosaccharides were composed of fucose, arabinose, galactose, glucose, mannose, rhamnose and fructose in all FC samples. The PCA score plots of the glycomics indicated that the crude and high-pressure wine steamed FC could be a category, showing that the two groups had similar chemical compositions. Ultimately, the simulation processing experiments indicated that the transformation of morroniside, polysaccharides, oligosaccharides, fructose, and glucose to 5-HMF through the reactions of dehydration and deglycosylation was the potential mechanism of enhancing the effects by processing. Conclusionly, the saccharides should be investigated as thoroughly as the secondary metabolites, and the high-pressure wine steamed FC could be an alternative to wine steamed FC.     

Elemental Characterization of Ciders and Other Low-Percentage Alcoholic Beverages Available on the Polish Market

Seventy-three samples of alcoholic beverages and juices that were purchased on the Polish market and home-made were analyzed for their elemental profiles. The levels of 23 metals were determined by ICP-MS (Ag, Ba, Bi, Cd, Co, Cr, Li, Mn, Ni, Pb, Sr and Tl), ICP-OES (Al, B, Ca, Cu, Fe, K, Mg, Na, Ti and Zn) and CVAAS (Hg) techniques in twenty-five samples of ciders widely available on the Polish market; six samples of home-made ciders; two samples of juices used in the production of these ciders; and forty samples of low-percentage, flavored alcoholic beverages based on beer. The gathered analytical data confirmed that the final elemental fingerprint of a product is affected by the elemental fingerprint of the ingredients used (apple variety) as well as the technology and equipment used by the producer, and in the case of commercial ciders, also the impact of type of the packaging used was proven. These factors are specific to each producer and the influence of the mentioned above parameters was revealed as a result of the performed analysis. Additionally, the inclusion of the home-made ciders in the data set helped us to understand the potential origin of some elements, from the raw materials to the final products. The applied statistical tests revealed (Kruskal–Wallis and ANOVA) the existence of statistically significant differences in the concentration of the following metals: Ag, Al, B, Bi, Co, Cr, Cu, Fe, K, Li, Mg, Na, Ni, Ti and Zn in terms of the type of cider origin (commercial and home-made). In turn, for different packaging (can or bottle) within one brand of commercial cider, the existence of statistically significant differences for Cu, Mn and Na was proved. The concentrations of all determined elements in the commercial cider from the Polish market and home-made cider samples can be considered as nontoxic, because the measured levels of elements indicated in the regulations were lower than the allowable limits. Moreover, the obtained results can be treated as preliminary for the potential authentication of products in order to distinguish the home-made (fake) from the authentic products, especially for premium-class alcoholic beverages.     

多弧离子镀TiN与不同金属基材间的接触界面与表面特性

用多弧离子镀技术在不同金属基材上进行TiN镀膜实验,制备了TiN/Fe、 TiN/Cu和TiN/Cr/Cu复合膜.借助扫描电子显微镜(SEM)、 X射线衍射仪(XRD)和光电子能谱(XPS),研究了TiN与Fe、 Cu和Cr/Cu三种不同衬底接触界面的形貌、结构及其表面特性.SEM观察发现,在一定离子镀膜条件下, TiN涂层可与Fe、 Cu和Cr/Cu金属基材形成均匀平整的接触界面,在铜基上TiN界面清晰,在Fe与Cr/Cu界面有明显的层状晶界微结晶分布.XRD分析显示, Fe、 Cu和Cr/Cu表面生成的薄膜都包含TiN、 Ti2N等多晶相,在Cr/Cu界面还包含Ti-Cr的金属间化合物.XPS结果表明,表面除了TiN膜外,还生成TiO2和TiOxNy等氧化膜.Ar+刻蚀5 min后, TiO2消失, TiOxNy减少, TiN则呈增加趋势.TiN与Cr/Cu界面形成明显的Ti-Cr和Cr-Ni互扩散层,这有助于增强薄膜附着力,形成较牢固的TiN涂层.     

纳通道的物质传输特性及应用

近年来,随着材料科学、微纳加工技术和微纳尺度物质传输理论的发展,纳通道技术得到了越来越多的研究和关注。纳通道包括生物纳通道和人工纳通道,其孔径通常为1~100 nm。在这一尺度下,通道表面与通道内物质之间的作用概率大大增强,使得纳通道表现出许多与宏观体系不同的物质传输特性,例如通道表面电荷与通道内离子之间的静电作用产生了离子选择性,通道内电化学势的不对称分布产生了离子整流特性,物质传输过程中占据通道产生了阻塞脉冲特性等。纳通道中的这些物质传输特性在传感、分离、能源等领域具有广泛应用,例如通过对纳通道进行功能化修饰可以实现门控离子传输;利用亚纳米尺度的通道可以实现单分子传感;利用通道与传输物质之间的相互作用可以实现离子、分子、纳米粒子的分离;利用纳通道的离子选择性可以在通道内实现电荷分离,将不同形式的能量（如光、热、压力、盐差等）高效转化为电能。纳通道技术是化学、材料科学、纳米技术等多学科的交叉集合,在解决生物、环境、能源等基本问题方面具有良好的前景。该文综述了近10年来与纳通道物质传输理论以及纳通道技术应用相关的前沿研究,梳理了纳通道技术的发展过程,并对其在各个领域的应用进行了总结与展望。