光散射技术在蛋白质晶体生长研究中的应用和进展

光散射技术广泛应用于生物大分子的晶体生长研究中,它包括静态光散射和动态光散射两种。利用静态光散射可以测定蛋白质溶液渗透的第二维里系数;利用动态光散射可以测定蛋白质溶液的平动扩散系数,获得溶液中蛋白质粒子的流体力学半径及分布情况,分离蛋白质结晶的成核与生长过程,研究大分子的聚集行为和晶体生长的动力学。借助光散射技术可以实现蛋白质晶体生长过程的动态控制。近些年光散射仪器向着小型化、轻便化的方向发展,光散射技术不断得到改进,日益完善,不仅用于地面实验,也应用于空间领域蛋白质晶体生长的研究中。     

光散射技术在研究高分子溶液和凝胶方面的应用

从溶液中的高分子、凝胶粒子及微乳胶粒子形态结构的表征和凝胶化过程、微乳液聚合及大分子缔合等动态过程的跟踪等方面的研究综述了近十几年来光散射技术在高分子溶液和凝胶领域的应用,并简单介绍了光散射技术的基本原理、发展简史和仪器及使用方法。     

多检测GPC/SEC技术在高分子表征中的应用Ⅷ.超支化高分子的溶液性质

采用体积排斥色谱法/示差折光指数/直角激光光散射/示差粘度三检测联用技术在25 ℃的THF中表征了超支化高分子的溶液性质;结果表明 超支化高分子符合普适标定规律,体积排斥色谱法/示差折光指数/直角激光光散射/示差粘度三检测联用技术能解释传统SEC/RI技术不能解释的溶液行为.     

建筑用梳形共聚物分散剂溶液行为的光散射研究

采用激光光散射研究了一种主链为聚丙烯酸侧链为聚乙二醇的梳形共聚物分散剂的一些溶液行为.从静态光散射得出了较为合理的表观重均分子量、均方旋转半径等参数.动态光散射给出了流体力学半径分布及其角度和浓度依赖性.结合静态和动态光散射,上述梳形共聚物分散剂在溶液中的构象也得到初步的表征.通过与描述梳形聚合物的Gay-Raphae模型进行比较表明,这类梳形共聚物溶液在低盐离子和低pH值条件下存在聚集行为,形成以PAA主链为核PEG为壳层的类胶束聚集.     

多检测GPC／SEC技术在高分子表征中的应用：Ⅷ.超支化高分子？…

采用体积排斥色谱法／示差折光指数／直角激光光散射／示差粘度三检测联用技术在２５℃的ＴＨＦ中表征了超支化高分子的溶液性质;结果表明超支化高分子符合普适标室规律,体积排斥色谱法／示差折光指数／直角激光光散射／示差粘度三检测联用技术能解释传统的ＳＥＣ／ＲＩ技术不能解释的溶液行为。     

目视式散射光度计

光散射法测定高聚物的分子量和高分子在溶液里的形态参数(均方半径 (?)或均方末端距 (?))在目前已经得到广泛的应用。在光散射实验中需要测定的量是高分子溶液的瑞利比(Rayleigh ratio)R_θ.R_θ=r~2(I_θ/I_0),式中 r 是散射中心到测量点间的距离,I_0是入射光强度,I_θ是对入射光方向成θ角度处的散射光强度。对一般高分子稀溶液来说,溶液的瑞利比大致在10~(-3)—     

激光光散射表征寡链聚苯乙烯微胶乳粒子的方法

本文阐述了利用激光光散射表征寡链（ｐａｕｃｉ－ｃｈａｉｎ）聚苯乙烯微胶乳的方法。在静态光散射中，可测得微胶乳粒子的重均摩尔质量，结合粒子内所含高分子链的重均分子量，进而计算出每个微胶乳粒子内高分子链的平均数目；在动态光散射中，通过对时间相关光谱的拉普拉斯反演求出粒子的平动扩散系数分布Ｇ（Ｄ），进而得到流体力学半径（Ｒｈ）及分子量的分布。通过综合分析静态与动态光散射的结果，建立了计算球形粒子密度的光散射方法，并发现，寡链聚苯乙烯微胶乳的密度低于通常的胶乳粒子以及本体聚苯乙烯的密度     

动静态光散射技术在蛋白质研究中的应用进展

动静态光散射技术是研究蛋白质等大分子物质尺寸、分布、形态及构象的一种重要手段,以其快速、便捷、对样品无干扰等特点,逐步深入到生化、物理、医药病理等领域,具有良好的应用前景。本文简要阐述了光散射技术的发展,主要介绍了动静态光散射技术的原理,从流体力学半径、重均分子量、均方根回旋半径以及渗透第二维里系数4个重要的物理参数出发,对近年来动静态光散射技术在蛋白质研究中的应用进行了调研和综述,并对该技术的发展进行了展望。     

一种四臂聚苯乙烯凝胶的激光光散射研究

采用原子转移自由基方法(ATRP)合成窄分布的末端基为巯基的四臂星型聚苯乙烯(4-PS-SH).巯基容易被空气中的氧气氧化生成二硫键,会引起四臂星型聚苯乙烯分子间交联.利用激光光散射研究了四臂聚苯乙烯在亚浓溶液中氧化交联生成大的胶束进而生成宏观化学凝胶的过程.静态激光光散射测量结果表明四臂聚苯乙烯亚浓溶液以及凝胶样品的时间平均散射光强不随测量位置的变化而涨落,说明此凝胶是结构均一的化学凝胶.动态光散射结果表明在四臂聚苯乙烯亚浓溶液氧化生成凝胶的过程中,动态强度-强度时间相关函数的慢运动衰减的贡献最初随着氧化时间的增加逐渐增强,当氧化反应进行到一定程度时慢运动的贡献又逐渐减弱,最终慢运动消失.生成的化学凝胶的相关函数与最初亚浓溶液的相关函数几乎重合.静态和动态激光光散射结果表明生成的四臂聚苯乙烯凝胶是结构均匀的化学凝胶.     

激光光散射测量荧光/磷光体系溶液结构的原理和方法

通过对商业化激光光散射谱仪改造升级,以4种不同波长的激光785、632.8、532和457 nm作为独立光源,可以根据不同的荧光体系选择不同的入射激光,有效避免荧光、磷光对散射光信号的干扰,从而使激光光散射谱仪能用于荧光/磷光等吸光材料溶液结构的测定.非荧光和荧光聚苯乙烯小球标准样品的测定都验证了改造后仪器测量结果的准确性和精确性.实验结果表明,当荧光体系对入射光有吸收时,动态光散射的相关函数与静态光散射得到的均方回转半径都不能反映荧光样品的真实溶液结构,此时的结果只能作为定性参考,只有选择样品无吸收的入射光波长,符合(准)弹性散射时,所测结果才能反映样品的真实结构.单分子荧光谱仪的对照实验证实了改造光散射谱仪的正确性与必要性.     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.