氨基甲酸酯型脱氧胆酸分子钳对中性分子的识别性能研究

利用差紫外光谱法考察了新型分子钳1～6对苯胺、对硝基苯胺、对甲氧基苯胺等中性分子的识别性能, 测定了25 ℃下, 在CHCl₃中主客体间的结合常数(K_a)和自由能变化(ΔG⁰). 结果表明, 所有分子钳主体对所考察的客体分子显示良好的识别作用, 主客体间形成1∶1型主客体络合物. 识别作用的主要推动力为多重氢键和π-π重叠等的作用. 讨论了主客体间形状、大小匹配和几何互补及识别模式等因素对识别能力的影响, 并利用核磁共振氢谱与计算机模拟作为辅助手段对实验结果进行了解释.     

一种新颖1D链状聚合物[Ni(acac)2(dadpm)]∞的合成与晶体结构

The title compound [Ni(acac)₂(dadpm)]_∞ (acac=acetylacetonate, dadpm=4,4′-diaminodiphenylmethane) was synthesized from Ni(acac)₂·2H₂O with dadpm in DMF. The structure was characterized by elemental analysis, IR spectroscopy, thermal analysis and single-crystal X-ray diffraction. X-ray analysis revealed that the central Ni atom is at a center of symmetry, and is octahedrally coordinated by four O atoms from two acac anions and two N atoms from two dadpm ligands. Each dadpm ligand, which has a two-fold axis passing through its methylene C atom, bridges two Ni atoms to form a 1D polymeric chain. Neighboring chains connect via H bonding interactions to generate a 2D network. It crystallizes in the monoclinic system, space group P2/c with a=0.556 79(7), b=0.896 06(12), c=2.187 3(3) nm, β=94.942(3)°, V=1.087 2(3) nm³, Z=2, D_c=1.390 g·cm^-3, F(000)=480, M_r=455.17, μ(Mo Kα)=0.924 mm^-1, R(F)=0.036 0, wR(F²)=0.101 0, S=1.013. CCDC: 254565.     

纳米晶构筑一维多孔氧化锌的合成与表征

One-dimensional porous zinc oxide was prepared via the calcination of zinc oxalate precursor obtained by solvothermal method. The products were characterized by XRD, SEM, TEM, photoluminescence (PL) spectrum and nitrogen adsorption-desorption. The results show that the obtained zinc oxide sample is porous and constructed by nanoparticles about 30 nm in size. The specific surface area and total pore volume are 126 m²·g^-1 and 0.13 cm³·g^-1, respectively． The PL properties related with defects in ZnO nanoparticles were discussed for porous zinc oxide samples.     

Adsorption Study of Methane on Activated Meso-carbon Microbeads by Density Functional Theory

A combined method of density functional theory (DFT) and statistics integral equation (SIE) for the determination of the pore size distribution (PSD) is developed based on the experimental adsorption data of nitrogen on activated mesocarbon microbead (AMCMB) at 77K. The pores of AMCMB are described as slit-shaped with PSD.Based on the PSD, methane adsorption and phase behavior are studied by the DFT method. Both nitrogen and methane molecules are modeled as Lennard-Jones spherical molecules, and the well-known Steele‘s 10-4-3 potential is used to represent the interaction between the fluid molecule and the solid wall. In order to test the combined method and the PSD model, the Intelligent Gravimetric Analyzer (IGA-003) was used to measure the adsorption of methane on the AMCMB. The DFT results are in good agreement with the experimental data. Based on these facts,we predict the adsorption amount of methane, which can reach 32.3ω at 299K and 4 MPa. The results indicate that the AMCMBs are a good candidate for adsorptive storage of methane and natural gas. In addition, the capillary condensation and hysteresis phenomenon of methane are also observed at 74.05K.     

半开口立方烷型簇合物[WOS3Cu3I(4-bpy)3]·0.25EtOH的合成及晶体结构(4-bpy=4-叔丁基吡啶)

Reaction of (NH₄)₂[WOS₃] with CuI and 4-tert-butylpyridine (4-bpy) in EtOH afforded a tetranuclear neutral cluster [WOS₃Cu₃I(4-bpy)₃]·0.25EtOH. This compound was characterized by elementary analysis, IR, ¹H NMR, TGA, and its crystal structure was determined by X-ray single crystal diffraction. It belongs to monoclinic, space group P2/c with a=2.220 9(2) nm, b=1.364 66(11) nm, c=2.490 6(2) nm, β=104.953(2)°, V=7.292 9(12) nm³, Z=4. The title compound may be viewed as having a half-open cubane-like structure in which three [Cu(4-bpy)]⁺ units are linked by a triply-bridging [WOS₃]^2- unit and a doubly-bridging iodine atom. CCDC: 266412.     

具有生物活性有机硅化合笺的研究（Ⅵ）：含硅四配位双（单）硫…

共合成了１３个含硅四配位二硫代磷酸酯和２个含硅四配位单硫代磷酸酯的新化合物，经元素分析，ＩＲ，＾１ＨＮＭＲ，ＭＳ确定了新化合物结构。对部分化合物进行了生物活性的测定，结果表明个别化合物有较好的生物活性。     

鲍鱼多糖Hal-A的甲醇解研究

从鲍鱼中分离出一种鲍鱼多糖Hal-A，并用改进甲醇解方法研究了Hal-A的组成 ，该多糖甲醇解产物经三甲硅醚衍生后，进行GC/MS，结果表明鲍鱼多糖Hal-A主要 由葡萄糖、半乳糖、甘露糖和少量木糖、岩灌糖和半乳糖醛酸组成。     

松香酯的新型乳化剂的合成

松香酯主要是作为增粘剂树脂来使用[1],因具有石油树脂无法替代的"天然、无毒、多功能"的特点,目前已经成为生产粘合剂、涂料、油墨等产品的不可缺少的原材料,并可应用于油漆、造纸、肥皂、食品、医药、农药、电子工业等诸多领域.松香及其衍生物通常状态下是固体,作为增粘剂来使用一般是用有机溶剂溶解后添加到主剂中,生产粘合剂时使用量约占胶粘主剂的2%～7%,用量很大.随着人们对环保意识的增强,逐步少用或不用有机溶剂已成为国际主流.水性粘合剂将成为我国各类粘合剂中发展得最快的胶种.宋湛谦等[2]和南京林业大学的谢晖等[3]分别采用熔融逆相乳化法制备了低软化点松香酯乳液,用溶剂助溶乳化法和高压高温乳化法制备了高软化点松香酯乳液.但是,用溶剂助溶乳化法制得的乳液中残留有部分的有机溶剂.由于松香酯类具有特殊的环状结构、空间位阻很大,难以乳化,且分子的极性较大,即使被乳化又容易形成聚集体,稳定性差,使用商品乳化剂很难将松香酯形成稳定的O/W型乳液.因此开发研制松香酯乳化剂具有很大的现实意义和应用价值.     

稠杂环化合物的研究（X）──3－芳基－6－苯甲酰氨基均三唑并［3，4－b］－1，3，4－噻二唑类化合物的合成及生物活性

本文利用３－芳基－４－氨基－５－巯基－１，２，４－均三唑和苯甲酰异硫氰酸酯在无水丙酮中反应，得到一系列３－芳基－６－苯甲酰氨基均三唑并［３，４－ｂ］－１，３，４－噻二唑，用元素分析、ＩＲ、１ＨＮＭＲ和ＭＳ确定了其结构，提出了可能的反应机制。并对其代表产物２ｈ进行了初步的抗菌和除草实验。     

三种偶氮化合物的荧光光谱研究

近年来 ,一些重要的有机染料探针在生物大分子光度分析、荧光分析和共振光散射分析方面得到了日益广泛地应用[1,2 ] ,深入研究这些有机染料的结构和光谱特性 ,探讨这些有机染料与生物大分子之间的作用 ,对于筛选性能优良的分子光谱探针 ,设计更加灵敏简便的分子光谱检测器件 ,是现代分析化学十分重要的课题。本文测定了偶氮胂Ⅱ (Ａｒｓｅｎａｚｏ)、铬黑Ｔ(ＥｒｉｏｃｈｒｏｍｅｂｌａｃｋＴ)、铬蓝黑 (ＥｒｉｏｃｈｒｏｍｅｂｌｕｅｂｌａｃｋＲ)等 3种化合物的荧光光谱 ,并用量子化学半经验方法ＡＭ1和ＰＭ3对3种化合物分子进行包括构型…