一种新型可溶性高聚物负载手性配体的合成及其催化烯烃的不对称双羟化反应研究

在碱性条件下, 聚乙二醇单甲醚(HO\|OPEG\|OMe)与1,4-二氟蒽醌进行亲核单取代反应生成中间体F\|AQN-OPEG-OMe, 产率88%. F-AQN-OPEG-OMe与奎宁锂进行亲核取代反应, 以95.6%的产率得到新型手性配体QN\|AQN\|OPEG-Me. QN-QN\|OPEG-Me与OsO4原位配位生成的均相催化剂在4种烯烃的不对称双羟化反应中表现出较高的对映选择性(92%~99%e.e.)和化学产率(80%~94%). 催化活性和立体选择性与Sharpless手性配体(DHQ)2AQN相当. 反应结束后, 配体可用乙醚沉淀回收, 循环使用5次, 催化剂的催化活性和立体选择性无明显改变, 配体的回收率均在95%~97%之间.     

Synthesis of 2,2＇-（Substituted Arylmethylene）bis（1,6,6-trimethyl 6,7,8,9-tetrahydrophenanthro[1,2-b]furan-10,11-dione） Derivatives

The reactions of tanshinone IIA with aromatic aldehydes have been investigated and several 2, T-（substituted arylmethylene） bis （1,6,6-trimethyl-6,7,8,9-tetrahydrophenanthro[1,2-b]- furan- 10, 11-dione） derivatives were obtained,     

Synthesis of the Biomimetic Polymer： Aliphatic Diamine and RGDS Modified Poly（d,l-lactic acid）

A novel poly（d, /-lactic acid） （PDLLA） based biomimetic polymer was synthesized by grafting maleic anhydride, butanediamine and arg-gly-asp-ser （RGDS） peptides onto the backbone of PDLLA, aiming to overcome the acidity and auto-accelerating degradation of PDLLA during degradation and to improve its biospecificity and biocompatibility. The synthetic copolymer was characterized by FTIR, ^13C NMR and amino acid analyzer （AAA）.     

有机溶剂性质及其水含量对酶催化合成含D－氨基酸残基的二肽衍生物的影响

有机溶剂性质及其水含量对酶催化合成保护的寡肽及其衍生物有显著影响。系 统地研究了有机溶剂性质及在不同有机溶剂中水含量对α－胰凝乳蛋白酶催化合成 含D－氨基酸残基的二肽衍生物产率的影响。用α－胰凝乳蛋白酶、枯草杆菌蛋白 酶和嗜热杆菌蛋白酶在有机溶剂中催化合成了一系列保护的二肽及其衍生物，并研 究了水含量对反应产率的影响，得到了十分有意义的结果。     

Studies on the Total Synthesis of Hainanolide (VII) - Analysis of the Relative Stereochemistry of key Intermediate 2

The natural product, hainanolide 1, also under the name harringtonolide2 demonstrated antitumor and antiviral activities in preliminary test. Its structure was determined by X-ray diffraction. The total synthesis of 1 was reported recently by Mander3. A different scheme of its synthesis has been studied in our laboratory4. Here the determination of the stereochemical structure of the key intermediate 2 in the synthesis was reported. HMBC and HMQC spectra identified the skeleton and H,…     

两性离子流动相测定杂多酸中的磷酸根、氯离子和硫酸根

采用离子色谱法测定杂多酸中痕量阴离子。由于常规的淋洗液(如Na2CO3,NaOH)呈碱性,使杂多酸迅速分解生成磷酸根,致使测定结果偏高。实验通过在常规淋洗液中加入适量两性离子后,调节淋洗液的pH为中性,从而能准确测定杂多酸中磷酸根氯离子和硫酸根的含量值。经过比较分别用去离子水和流动相稀释的样品中磷酸根的测定结果,确定淋洗液的最佳条件为2.5mmol/LNa2CO3-9.0mmol/LCHES,在该条件下测定,快速、准确、灵敏,且有较好的灵敏度和重现性。     

杂环光化学——Ⅺ.1,3-二甲基-6-氮杂胸腺嘧啶和丙酮的光反应

研究了1,3-二甲基-6-氮杂胸腺嘧啶和丙酮的光反应。反应机理中包含有三线态激基复合物和由此相继形成的两个不同结构的双自由基作为反应中间体。最终得到了1:2的加成产物, 即2,2,4,4,6,8,10-七甲基-7,9-二氧代-3,5-二氧杂-1,8,10-三氧杂双环[4,4,0]癸烷(Ⅰ)。     

Sensitive Determination of DNA by Resonance Light Scattering with Pentamethoxyl Red

A novel sensitive method for the determination of nucleic acid (DNA) using the resonance light scattering (RLS) spectra of pentamethoxyl red has been developed. It is based on the effects on the resonance light scattering of Pentamethoxyl Red. The effective factors and the optimum conditions were studied, and the enhanced intensity of RLS is in proportion to the concentration of nucleic acids in the range of 0–2.54 µg mL⁻¹ for ct-DNA, 0–4.54 µg mL⁻¹ for hs-DNA. The limits of detection are 1.1 and 2.1 ng mL⁻¹, respectively. Most foreign substances do not interfere in the determination, and the method has good selectivity and high sensitivity. It has been applied to the determination of DNA in synthetic samples and in real samples with satisfactory results.     

Microcalorimetric study on micellization of nonionic surfactants with a benzene ring or adamantane in their hydrophobic chains

The micellization of a novel family of nonionic surfactants poly(oxyethylene) glycol alkyl ethers has been studied by microcalorimetry. One of the surfactants has adamantane, and the other nonionic surfactants have a benzene ring in their hydrophobic chains, which moves from the terminal of the hydrophobic chain toward the headgroup. Moreover, the alkyl chain of the nonionic surfactants is straight or branched. Both the critical micelle concentration (cmc) and the thermodynamic parameters associated with the micelle formation have been obtained. The cmc decreases and the enthalpy of micelle formation (deltaH(mic)) becomes less positive gradually as the length of hydrophobic chain increases, whereas the values of cmc and deltaH(mic) tend to increase for the surfactants with a longer ethylene oxide chain. However, the deltaH(mic) value of the surfactant with seven carbon atoms in a hydrophobic chain is more positive than that of the surfactant with six carbon atoms in a hydrophobic chain. Comparing with the nonionic surfactant with a methylene hydrophobic chain, the surfactants with benzene rings and adamantane groups have larger cmc values and the cmc values increase with the size of the groups. Furthermore, moving the phenyl group from the terminal of the hydrophobic chain to the neighbor of the hydrophilic headgroup leads to the decreased cmc. Both the variation of hydrophobic interaction from the movement of phenyl group and pi-pi interaction among adjacent phenyl groups affect deltaH(mic) values.     

DFT study and Monte Carlo simulation on proton transfers of 2-amino-2-oxazoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline in the gas phase and in water

Density functional theory (DFT) and Monte Carlo (MC) simulation with free energy perturbation (FEP) techniques have been used to study the tautomeric proton transfer reaction of 2-amino-2-oxazoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline in the gas phase and in water. Two reaction pathways were considered: the direct and water-assisted transfers. The optimized structures and thermodynamic properties of stationary points for the title reaction system in the gas phase were calculated at the B3LYP/6-311+G(d, p) level of theory. The potential energy profiles along the minimum energy path in the gas phase and in water were obtained. The study of the solvent effect of water on the proton transfer of 2-amino-2-oxozoline, 2-amino-2-thiazoline, and 2-amino-2-imidazoline indicates that water as a solvent is favorable for the water-assisted process and slows down the rate of the direct transfer pathway.