High-fidelity Recognition of Organotrifluoroborate Anions (R−BF3−) as Designer Guest Molecules

The recognition of boron compounds is well developed as boronic acids but untapped as organotrifluoroborate anions (R−BF₃⁻). We are exploring the development of these and other designer anions as anion-recognition motifs by considering them as substituted versions of the parent inorganic ion. To this end, we demonstrate strong and reliable binding of organic trifluoroborates, R−BF₃⁻, by cyanostar macrocycles that are size-complementary to the inorganic BF₄⁻ progenitors. We find that recognition is modulated by the substituent's sterics and that the affinities are retained using the common K⁺ salts of R−BF₃⁻ anions.     

Novel,organosoluble, light‐colored fluorinated polyimides based on 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl or 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐1,1′‐binaphthyl

Two series of fluorinated polyimides were prepared from 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)biphenyl ( 2 ) and 2,2′‐bis(4‐amino‐2‐trifluoromethylphenoxy)‐1,1′‐binaphthyl ( 4 ) with various aromatic dianhydrides via a conventional, two‐step procedure that included a ring‐opening polyaddition to give poly(amic acid)s, followed by chemical or thermal cyclodehydration. The inherent viscosities of the polyimides ranged from 0.54 to 0.73 and 0.19 to 0.36 dL/g, respectively. All the fluorinated polyimides were soluble in many polar organic solvents, such as N,N‐dimethylacetamide and N‐methylpyrrolidone, and afforded transparent and light‐colored films via solution‐casting. These polyimides showed glass‐transition temperatures in the ranges of 222–280 and 257–351 °C by DSC, softening temperatures in the range of 264–301 °C by thermomechanical analysis, and a decomposition temperature for 10% weight loss above 520 °C both in nitrogen and air atmospheres. The polyimides had low moisture absorptions of 0.23–0.58%, low dielectric constants of 2.84–3.61 at 10 kHz, and an ultraviolet–visible absorption cutoff wavelength at 351–434 nm. Copolyimides derived from the same dianhydrides with an equimolar mixture of 4,4′‐oxydianiline and diamine 2 or 4 were also prepared and characterized. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2416–2431, 2004     

大焦深成像系统仿真实验研究

如何增大非相干光学成像系统的焦深是应用光学研究领域的热点问题.本文对采用高次非球面光学掩模板与图像处理相结合增大成像光学系统焦深的新方法进行了深入分析,建立了大焦深成像系统仿真实验模型,并进行了大焦深成像系统仿真实验.实验结果证明了该方法在维持原相对孔径的同时使光学系统在较大的离焦范围内有好的成像质量.实际应用中还要综合考虑模板参量、信噪比等关键因素.     

F+H2→HF+H反应的全量子态分辨的散射动力学研究

利用高灵敏度的氢原子里德堡飞渡时间谱方法研究了 F H_2→HF H 反应碰撞能在5.02kJ/mol 下的交叉分子束反应态态散射动力学.所有在时间飞渡谱中被观测到的谱峰可以归属为 HF 产物的振转态结构.还观测到了明显的 HF(v’=3)前向散射,以及少许的 HF(v’=2)前向散射.     

CsBr高压X光研究

 采用同步辐射X光源和能散法，对CsBr粉末样品进行高压原位X光衍射实验。由金刚石对顶压砧高压装置（DAC）产生高压，用已知状态方程的Pt粉末作内标，由Pt的衍射数据确定样品压力，最高压力达64.4 GPa。实验结果表明：室温常压下原始CsBr样品是具有简单立方结构的晶体，其晶格常数α＝0.428 5 nm。高压下CsBr的结构有所变化，在51.3~58.4 GPa的压力范围内，(110)线和(211)线发生劈裂，从而形成了四方相。     

正已醇-邻、间、对二甲苯二元系固液相平衡

Melting temperatures have been measured and the solid-liquid phase diagrams constructed for 1-hexanol＋o-xylene, 1-hexanol＋m-xylene and 1-hexanol＋p-xylene. They are simple eutectic systems. Excess mole Gibbs free energies were calculated at 298.15K, showing larger positive deviations from ideal-solution behavior. The largest values of GmE are 711、 650 and 800 J•mol-1 for {o-C6H4(CH3)2＋C6H13OH}、 {m-C6H4(CH3)2 ＋ C6H13OH} and {p-C6H4(CH3)2＋C6H13OH} respectively.     

基于磁泳的生物分离分析技术

利用磁场诱导的微粒运动即磁泳对磁响应性粒子进行精细分离,是近年来发展起来的选择性分离细胞和高分子量核酸的有效技术。本文在阐明磁泳分离原理的基础上,介绍了磁泳分离的分流薄层分级技术、四极磁场流动分离技术和微芯片上的自由流磁泳分离技术的装置构造、工作原理及其在生物分离分析中的应用。     

螯合型二甘醇钛酸酯的合成及其催化性能研究

报导了两种新的螯合型二甘醇钛酸酯的合成方法，进行了ＩＲ和ＵＶ鉴定，并作为酯化反应催化剂催化合成了邻苯二甲酸二辛酯。研究了酯化反应转化率与反应时间、反应温度及催化剂用量的关系，探讨了催化剂结构与催化性能的关系。     

Impact of azaproline on Peptide conformation

The amino acid analog azaproline (azPro) contains a nitrogen atom in place of the C(alpha) of proline. Peptides containing azPro were shown to stabilize the cis-amide conformer for the acyl-azPro bond and prefer type VI beta-turns both in crystals and in organic solvents by NMR. The increased stability for cis-amide conformers was relatively minor with respect to the trans-conformers. Further, their conformational preferences were depended on solvent. To elucidate the impact of azPro substitution on amide cis-trans isomerism and peptide conformation, this paper reports ab initio studies on azPro derivatives and a comparison with their cognate Pro derivatives: 1-acetyl-2-methyl pyrrolidine (1), 1-acetyl-2-methyl pyrazolidine (2), Ac-Pro-NHMe (3), Ac-azPro-NHMe (4), Ac-azPro-NMe(2) (5), Ac-azAzc-NHMe (6), and Ac-azPip-NHMe (7). Conformational preferences were explored at the MP2/6-31+G** level of theory in vacuo. Solvation effects for 1 and 2 were studied implicitly using the polarizable continuum model and explicitly represented by interactions with a single water molecule. An increase in the conformational preference for the cis-amide conformer of azPro was clearly seen. An intramolecular hydrogen bond occurred solely in the trans-amide conformer that reduced the preference for the cis-conformer by 2.2 kcal/mol. The larger ring homolog aza-pipecolic acid (azPip), in which this internal hydrogen bond was diminished, significantly augmented stabilization of the cis-amide conformer. In aqueous solution, the preference for the cis-amide conformers was greatly reduced, mainly as a result of interaction between water and the lone pair of the alpha-nitrogen in the trans-amide conformer that was 3.8 kcal/mol greater than that in the cis-conformer. In the azPro analog, the energy barrier for cis-trans amide isomerization was 6 kcal/mol less than that in the cognate Pro derivative. Because the azPro derivatives can stabilize the cis-amide bond and mimic a type VI beta-turn without incorporation of additional steric bulk, such a simple chemical modification of the peptide backbone provides a useful conformational constraint when incorporated into the structure of selected bioactive peptides. Such modifications can scan receptors for biological recognition of reverse turns containing cis-amide bonds by the incorporation of type VI beta-turn scaffolds with oriented appended side chains.     

高效液相色谱检测Zn（Ⅱ）、Cd（Ⅱ）、Co（Ⅱ）、Pb（Ⅱ）、Ni（Ⅱ）、Cu（Ⅱ）、Hg（Ⅱ）

用双-(2-羟乙基)二硫代甲酸铵(HEDC)在反相液相色谱中作检测某些金属离子的衍生化试剂，HEDC的金属螯合物微溶于水，可直接水样注射于C18柱中进行检测，范围为0．006～10mg／L相对偏差1％～2％，检测波长254nm，金属汞的整合物在HPLC分析前进行浓缩富集检测限可低至0．06～25μg／L，相对偏差小于2％。