SYNTHESIS AND THERMAL PROPERTIES OF POLYBENZOXAZOLE FROM SOLUBLE PRECURSOR WITH HYDROXY-SUBSTITUTED POLYENAMINONITRILE

Aromatic polybenzoxazole (PBO) precursor, hydroxy-substituted polyenaminonitrile, was prepared by direct polycondensation of 1,4-bis(l-chloro-2,2-dicyanovinyl)benzene (CCB) and 4,6-diaminoresorcinol dihydrochloride (DAR) using pyridine and N,N-dimethylacetamide as condensing agent and solvent. The precursor has good solubility in polar aprotic solvent which is due to the strong dipolar nature of the main chain. The soluble precursor was subjected to thermal cyclization in an inert atmosphere to convert it into the corresponding PBO, which has its 5% weight loss temperature at 540℃ The fully cyclized PBO were characterized by FT-IR and TGA. The introduction of 10% mol 1,3,5-benzenetricarboxylic chloride (BTC) into the main chain not only has little effect on the solubility of PBO precursor but also raises its 5% weight loss temperature to 552℃ and char yield at 700℃ for the cyclized PBO with BTC.     

Photorefractivity of hyperbranched polyisophthalate endcapped with pendant carbazolyl and azobenzene groups

A novel hyperbranched polyisophthalate containing pendant carbazolyl and azobenzene groups at the terminals was synthesized, and its photorefractivity has also been evaluated by the effective electro-optic (EO) coefficient, two-beam couple (TBC) coefficient, diffraction efficiency and photorefractive (PR) response time. This PR polymer has a low glass transition temperature of 21 °C without any extra plasticizer added, which provides a necessary free volume for EO chromophore reorientation during the recording process at room temperature. The obtained PR film exhibited an effective EO coefficient of 30 pm V⁻¹, a TBC coefficient of 59 cm⁻¹, a diffraction efficiency of 17%, and a modulation index of 1.67 × 10⁻³ at the wavelength of 632.8 nm with an applied electric field of 80 V μm⁻¹ at room temperature. The TBC coefficient was found to be beam-intensity dependent, compared with what is found in inorganic crystals. Moreover, a fast PR response time of 10 ms was deduced at an erasing beam intensity of 1.0 W cm⁻².     

Ag-CV的表面增强共振散射光谱研究

采用共振散射光谱和紫外可见光谱研究了银胶与结晶紫的相互作用。在ＰＨ为４．０的ＨＡｃ－ＮａＡｃ缓冲溶液中,奶胶在３４５ｎｍ和７００ｎｍ有两个共振散射峰;当加入带下辈民的阳离子染料结晶紫后,产生表面增强效应,３４５ｎｍ和７００ｎｍ处的共振散身信号大为增强,从而获得灵敏的表面增强共振散射光谱。     

基于荧光内滤效应的锂离子荧光化学传感器研究

报道了一种基于荧光内滤效应的荧光增强型锂离子光化学传感器,将荧光试剂、亲脂性pH指示剂和锂离子中性载体结合在增塑的PVC膜中,Li⁺与H⁺在膜相中的竞争萃取效应引起受亲脂性pH指示剂调制的敏感膜荧光值的变化.推导了有关理论关系式,研究了该传感器的响应特性,并对人工合成样品进行测试,结果较为满意.     

烷基紫精/五氧化二钒插层化合物的组装、表征及磁性的研究

以烷基紫精(alkylviologens; 又称紫精或紫罗精)为有机客体、层状五氧化二钒为无机主体, 在液、固两相反应体系中, 利用I^－与V^5＋的氧化还原反应, 使烷基紫精阳离子通过静电引力作用进入被还原的五氧化二钒层板之间, 形成一系列新颖的无机-有机插层化合物. 并运用X射线粉末衍射(XRD)、红外(FT-IR)、X射线光电子能谱(XPS)、紫外-可见漫反射(UV-vis DRS)等方法对其进行了表征. XRD分析结果证明, 五氧化二钒的层间距随着烷基紫精中烷基链的增长而增大, 但其结晶度随着烷基紫精阳离子中烷基链的增加而降低. XPS研究表明, 该类材料中的钒是以V^4＋和V^5＋两种混合价态存在, 氧原子处于三种不同的化学环境, 这些现象说明烷基紫精阳离子的引入对五氧化二钒的骨架结构影响不大, 主体五氧化二钒的层状结构保存完好; 氮原子处于两种不同的化学环境, 证实插层化合物中主客体之间相互修饰的协同效应, 有可能起到了稳定客体分子激发态的作用, 同时FT-IR光谱中芳香环特征谱带强度的变化也进一步证明了这一结论. UV-vis DRS分析发现由于主客体的相互作用使插层化合物在紫外和可见光区域产生特殊的光吸收性质. 从磁性研究的结果可以看出, 在温度低于15 K时, 插层化合物RV2为反铁磁性的有序结构; 当温度高于15 K时, 转变为顺磁性, 表现出磁无序结构.     

氨基酸分子构象稳定性与光电离解离动力学的氢键效应*

本文综述了氨基酸分子内氢键种类和数目对分子构象稳定性和光电离解离动力学的各种效应：得出分子内含有N···H–O和C=O···H–O氢键的构象具有较高的热力学稳定性; N···H–O氢键导致分子第一电离能数值的增加,同时可以导致电离过程中的质子转移以及后续二氧化碳释放的解离过程。氨基酸分子正离子的稳定性或碳碳化学键断裂解离动力学也不尽相同,丝氨酸分子在电离阈值附近解离过程中表现出奇特的立体效应。     

纳米雄黄研究进展

矿物中药雄黄临床应用历史悠久,近些年来更是引起广泛关注。然而也存在雄黄的潜在毒性较大, 雄黄的难溶性使其生物利用度低等问题。采用纳米技术制成纳米雄黄,可以提高难溶性雄黄的生物利用度和降低毒副作用;与普通雄黄比较,纳米雄黄的药代动力学也发生显著变化。本文在文献总结基础上结合我们的研究工作,对纳米雄黄的制备方法及表征、纳米雄黄药代动力学、纳米雄黄抗肿瘤作用、纳米雄黄的活性物种及纳米雄黄中药复方制剂等方面作了综述,并对纳米雄黄的进一步研究做了展望。     

Vibrational isotope effect by the low rank perturbation method

Mathematical formalism of the Low Rank Perturbation method (LRP) is applied to the vibrational isotope effect in the harmonic approximation with a standard assumption that force field does not change under isotopic substitutions. A pair of two n-atom isotopic molecules A and B which are identical except for isotopic substitutions at ρ atomic sites is considered. In the LRP approach vibrational frequencies ω _k and normal modes of the isotopomer B are expressed in terms of the vibrational frequencies ν _i and normal modes of the parent molecule A. In those relations complete specification of the normal modes is not required. Only amplitudes at sites τ affected by the isotopic substitutions and in the coordinate direction s (s = x, y, z) are needed. Out-of-plane vibrations of the (H,D)-benzene isotopomers are considered. Standard error of the LRP frequencies with respect to the DFT frequencies is on average . This error is due to the uncertainty of the input data (± 0.5 cm⁻¹) and in the absence of those uncertainties and in the harmonic approximation it should disappear. In comparing with experiment, one finds that LRP frequencies reproduces experimental frequencies of (H,D)-benzene isotopomers better () than scaled DFT frequencies () which are designed to minimize (by frequency scaling technique) this error. In addition, LRP is conceptually and numerically simple and it also provides a new insight in the vibrational isotope effect in the harmonic approximation.     

3-甲基环状乙撑磷酸二酯醇解的反应途径的理论研究

采用密度泛函理论和MP2方法研究了3-甲基环状乙撑磷酸二酯(MEP)与甲醇的反应途径:(Ⅰ)CH3O-+MEP;(Ⅱ)CH3OH+MEP;(Ⅲ)CH3O-+HMEP(MEP的质子化形式);(Ⅳ)CH3OH+HMEP.在B3LYP/6-31++G(d,p)水平上优化了四条反应途径的反应物、中间体、过渡态及产物的几何构型,并在同水平上进行了自然电荷分析,然后在MP2/6-311++G(3df,2p)水平上计算了各驻点的单点能.采用极化连续介质模型(PCM)研究了各途径在苯、甲醇和水溶液中的溶剂化效应.计算结果表明,溶剂效应使途径(Ⅰ)的自由能垒降低,而使途径(Ⅱ)和(Ⅳ)的决速步骤的自由能垒升高.在气相和苯溶剂中途径(Ⅳ)是反应的优势途径,在甲醇和水溶剂中途径(Ⅰ)则成为最优.研究结果进一步表明实验条件下途径(Ⅱ)与(Ⅳ)对总醇解反应的贡献相当.     

Theoretical studies on the infrared spectrum of the tetrahedral molecules R<Subscript>2</Subscript>MH<Subscript>2</Subscript> (R = D(H), CH<Subscript>3</Subscript>, OH; M = Ti,Zr, Hf)

Using Stuttgart/Dresden effective core potentials MWB28, MWB60, and GTO valence basis sets (8s7p6d)/[6s5p3d], (8s7p6d)/[6s5p3d] for Zr and Hf atoms and 6-311++G(3df,3pd) basis set for C, H, O, and Ti atoms, tight convergence criteria geometry optimizations and harmonic frequency calculations are performed at B3LYP and B3LYP/IEF-PCM levels of theory so as to model the gas phase and argon matrix infrared spectra of the tetrahedral molecules R₂MH₂ (R = D(H), CH₃, OH; M = Ti, Zr, Hf). Influence of the transition metal and/or substituent group on the symmetric and asymmetric stretching frequencies of the MH₂ fragment of the R₂MH₂ molecules is investigated at both the levels of theory. The modelling of the argon matrix effect improves the agreement between the calculated frequencies and the experimental ones. The calculated argon matrix to gas phase frequency shifts is compared reasonably to the experimental argon to neon matrix shifts.