单链高分子通过薄膜上纳米孔隙的输运过程: 链间相互作用的影响

从理论上研究了高分子链通过位于薄膜上的一个纳米孔隙的输运问题. 考虑在膜的一侧引入与传输高分子链有特殊相互作用的高分子链段, 研究链间相互作用致使高分子链构型的改变对其平均首次通过时间的影响, 进而在不同条件下进行了相应的数值模拟, 并讨论了其它一些相关问题.     

FTIR-ATR技术研究聚氨酯类文物保护材料的光降解

Polyurethanes are one kind of relic protection materials commonly used. During artificial photo-ageing, three polyurethanes, HDI-based polyurethane, MDI-based polyurethane and TDI-based polyurethane, have been considered to undergo UV radiation. Photochemical degradation of the polyurethanes has been monitored by means of Fourier transform infrared spectroscopy with attenuated total reflection accessory （FTIR-ATR）. It was proved that the mechanism of the photochemical degradation of polyurethanes might be the scissions of carbamate （urethane） groups and the re-reactions of radical groups formed in the scission reactions. From the experiment results HDI-based polyurethane, an aliphatic diisocyanate, could be considered to be more suitably used as relic protection materials among these three polyurethanes for its ageing products with less color.     

Stereoselective total syntheses and reassignment of stereochemistry of the freshwater cyanobacterial hepatotoxins cylindrospermopsin and 7-epicylindrospermopsin

A stereoselective total synthesis of the structure 1 proposed for the freshwater cyanobacterial heptatotoxin cylindrospermopsin has been accomplished in approximately 30 operations starting from commercially available 4-methoxypyridine. Utilizing methodology developed by Comins, the tetrasubstituted piperidine A-ring unit of the hepatotoxin was efficiently constructed. The two remaining stereocenters in the natural product were then set by a stereospecific intramolecular N-sulfinylurea Diels-Alder cyclization/Grignard ring opening/allylic sulfoxide [2,3]-sigmatropic rearrangement sequence previously developed in these laboratories, leading to key intermediate 29. The stereochemical assignment of alcohol 29, which contains all six of the stereogenic centers of the natural product, was confirmed by an X-ray crystal structure determination of a derivative. Installation of the D-ring uracil moiety was effected by using our new methodology developed for this purpose, and construction of the C-ring guanidine completed the total synthesis of racemic structure 1. However, the (1)H NMR data for this compound do not match that of cylindrospermopsin, but instead agree with the data reported for 7-epicylindrospermopsin, a minor toxic metabolite that co-occurs with cylindrospermopsin. Therefore, we propose a revision of the stereochemical assignments of these natural products such that cylindrospermopsin is now represented as structure 2 and 7-epicylindrospermopsin is 1. This reassignment was further confirmed by Mitsunobu inversion of the C-7 alcohol 51 to epimer 52, and conversion of this compound to tetracyclic diol 57, which has previously been transformed to cylindrospermopsin (2).     

不同构象铂(Ⅱ)配合物与G-肌动蛋白作用的光谱研究

The cyclohexamethylene-diamine squaric acid platinum(Ⅱ) complexs(R,R, S,S) binding to G-actin and the consquence conformation change were studied by N-(1-pyrenyl) maleimide(NPM) labeled fluorescence and intrinsic fluorescence. The binding and chemical kinetics were determined by fluorometry. The results showed that when R (Pt/actin molar ratio) was lower than 30, the Pt binded to G-actin strong binding sites(-SH), when R was larger than 30, the Pt binded to G-actin weaker binding sites. The consquence conformation changes were determined by CD. The CD results showed that R was smaller than 60, G-actin α-helix contents decreased slowly, R was larger than 60, G-actin conformation changed obviously. The reaction of R,R complex of platinum(Ⅱ) S,S complex of platinum(Ⅱ) with G-actin was similar to that of with S,S complex of platinum(Ⅱ).     

稀溶液中环型聚苯乙烯的激基缔合物荧光效应

采用乙酸乙酯为环型和线型聚苯乙烯的非良溶剂, 确定了Mark-Houwink方程分别为[η]_r=1.91×10~(-2)·M~(0.607)和[η]_l=4.06×10~(-2)·M~(0.572)。研究了环型和线型聚苯乙烯的激基缔合物的荧光效应。通过稀溶液中环型和线型高分子线团在柔顺性上存在着差异, 解释了二者之间在荧光效应方面的差异, 并根据实验结果,确定了(I_E/I_M)c→0～M关系式分别为(I_E/I_M)r,c→0=1.91+3.40×10~(-6)M和(I_E/I_M)l,c→0=2.15+3.05×10~(-6)M。     

NRET from naphthalene labels in multilayer shell wall on melamine formaldehyde microparticles fabricated with layer-by-layer self-assembly to pyrene-labeled polyelectrolyte in solution

Core-shell colloidal particles were prepared with the core of monodisperse melamine formaldehyde particles (MF) with a diameter of 3.5 μm. The shell deposited on the core by the layer-by-layer (LbL) self-assembly was made with a copolymer ANp3 of 2-acrylamido-2-methylpropanesulfonate sodium (AMPS) and 3 mol% naphthalene label monomer and poly(diallyldimethylammonium chloride) (PD). Nonradiative energy transfer (NRET) from the naphthalene labels deposited on the MF particles to pyrene labels at a polyelectrolyte APy3, a copolymer of AMPS and 3 mol% pyrene label monomer, or to an ionic pyrene probe 1-pyrenemethylamine hydrochloride (PyMeA · HCl) in water was observed. The NRET efficiency was expressed as the emission intensity ratio I/I₀ of naphthalene with and without existence of pyrene in the surrounding solution. With increasing pyrene concentration, I/I₀ decreased down to about 0.2 and the mechanism for this NRET from the inner naphthalene label to the pyrene labels in solution is still ambiguous.     

Spectrophotometric determination of lead in vegetables with dibromo-p-methyl-carboxysulfonazo

A new highly sensitive and selective chromogenic reagent dibromo-p-methyl-carboxysulfonazo (DBMCSA) was synthesized and studied for the spectrophotometric determination of lead in detail. In 0.25 M phosphoric acid medium, which greatly increases the selectivity, lead reacts with DBMCSA to form a 1:2 blue complex, having a sensitive absorption peak at 648 nm. Under the optimal conditions, Beer's law is obeyed over the range from 0 to 0.8 μg ml⁻¹ Pb(II) and the apparent molar absorptivity is 1.04×10⁵ l mol⁻¹ cm⁻¹. The detection limit and the variation coefficient were found to be 2.14 ng ml⁻¹ and 1.0%, respectively. It is found that, except for Ca(II) and Ba(II), all foreign ions studied do not interfere with determination. The interference caused by Ca(II) and Ba(II) can be easily eliminated by prior extraction with potassium iodide-methylisobutylketone. The method has been applied to the determination of lead in vegetables with satisfactory results.     

一种基于流动注射梯度技术识别异常峰及校正的方法

基于流动注射梯度信息提出了一种利用梯度比均值进行定量的校正方法。方法具有在线自动判别和修复异常峰并自行校正的功能，和通用的标准系列定量方法相比，两者测定精度相当。但本文提出的方法抗干扰能力明显优于后者，可适用于在线过程监测。     

氧杂环丁烷热解机理的量子化学研究

本文利用半经验分子轨道理论研究了氧杂环丁烷热解为甲醛和乙烯的反应机理计算是采用半经验方法AM1进行的, 各种驻点全部运用Berny梯度方法优化. 同时, 对过渡态的结构进行了振动分析的确证. 计算表明: 1)不存在协同的同面-同面反应途径的过渡态, 其驻点只是一个二级鞍点; 2) 协同的同面-异面反应途径需要经过一个能量很高的过渡态; 3)有利的反应途径是包含了双自由基中间体的分步过程。     

Synthesis and Mesogenic Properties of Liquid Crystals Containing Terminal Cyclohexylmethanol,Cyclopentylmethanol, Cyclobutylmethanol and Cyclopropylmethanol Moiety

Four series of compounds 11?50 containing terminal alicyclic rings such as cyclohexylmethyl, cyclopentylmethyl, cyclobutylmethyl, and cyclopropylmethyl rings were synthesized and their liquid crystal behavior studied. The ring size and the length of flexible alkoxy chain influence the phase formation in different ways. While the smaller ring and the shorter alkoxy chain tend to favor the formation of the N phase, the larger ring and the longer alkoxy chain tend to favor the formation of the SmC phase. All the compounds except 11 and 21 exhibit SmA phases. The widest temperature range of the N, SmA, and SmC phases are found in the compounds 41 , 46 , and 20 , respectively, which are 75 °C for 41 , 115 °C for 46 , and 100 °C for 20 .