金属卟啉配合物与吡啶的轴向配位反应及其紫外-可见光谱的研究

用光度法测定了Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Zn(Ⅱ)、Cd(Ⅱ)原卟啉Ⅸ二甲酯(PP)配合物与轴向配体吡啶(Py)反应的化学平衡常数及产物分子的组成比,解释了实验结果,并探讨了Py轴向配位对上述金属卟啉配合物的紫外-可见光谱的影响。     

Synthesis of 1-(3',4'-dihydroxyphenyl)-7-(4"-hydroxyphenyl)- 4hepten-3-one

Natural diarylheptanoids have significant bioactivities. Some of them are potent inhibitors against prostaglandin biosynthesizing enzyme (PG synthetase) and 5-lipoxygenase (LT synthetase)1-2. Compound 1 was firstly isolated from Alnus rubra bark3. So far its synthesis has not been reported yet. Herein, we report the synthesis of compound 1. Meantime, compound 24 was also obtianed as an intermediate. Compound 7 and 16 were converted to compound 10 and 18 respectively, because compound 1…     

A Novel Bimetallic Tetrahedron Cobalt Complex Promoting the Addition of Diethylzinc to Benzaldehyde

Asymmetric catalytic addition of dialkyzinc to aldehyde using chiral ligands has become one of the most active areas in asymmetric synthesis. In recent years, various chiral ligands have exhibited good results in promoting this asymmetric addition1, such asβ- amino alcohol and chiral amine which possess chiral carbon centers, chiral ((6-arene) chromium complexes2, derivatives of Ferrocene3, which possess planar chirality, and BINOL and NOBIN4. Further development of novel catalysts is sti…     

壳聚糖希夫碱铜多相催化剂催化苯乙烯环丙烷化反应研究

壳聚糖希夫碱铜催化剂催化苯乙烯环丙烷化反应，得到了非常好的化学收率，同时还得到了17.1%ee和33.3:66.7的顺反比。此外，催化剂重复使用数次仍保持很高的活性。     

甲基弯菌IMV 3011整细胞催化甲烷氧化合成甲醇的研究

研究了在甲基弯菌（Methylosimus trichosporium)IMV 3011整细胞催化甲烷制甲醇的反应过程中，菌体浓度、阻断剂乙二胺四乙酸（ethylenediamine tetraacetic acid,简称EDTA）浓度、外源性电子给体、混合气组分及压力与甲醇积累的关系。批式反应的实验结果表明，在菌体浓度为7.4mg/mL时，以2mmol/L EDTA作阻断剂效果最好；作为电子给体，甲酸钠（20mmol/L)的效果优于琥珀酸钠（40mmol/L)，使用前者时的甲醇积累量是用后者时的2.8倍左右；当甲烷与空气的体积比为1：1.7时，转化率为6.0%，甲醇积累量最大；压力选用0.16MPa。连续反应中，于培养基中无铜离子培养的细胞与有铜离子的相比，持续时间长，甲醇积累高（最大产量达374μmol),前者是后者的2倍。     

具有新颖嵌合作用的金属配合物的微波合成、晶体结构及性质研究

在微波辐射条件下合成了两种新的离子液体金属配合物[Ni(m-HNDA)2(H2O)4](1),[Zn(m-HNDA)2(H2O)4]·H2O(2),用元素分析、红外光谱、紫外光谱对它们进行了表征,通过X射线单晶衍射测定了它们的晶体结构.在晶体结构中,标题物通过基团间的嵌合作用,π-π相互作用和分子间氢键自组装成了三维网状的多孔结构.由氢键和π-π相互作用的强弱推测标题物的稳定性次序2>1,与实测热稳定性次序完全吻合;电化学性质表明,金属的配位改变了配体的循环伏安性质.另外,两种配合物可在水溶液中高选择性的识别氟离子.     

Characterization and performance of Cu/ZnO/Al_2O_3 catalysts prepared via decomposition of M(Cu,Zn)-ammonia complexes under sub-atmospheric pressure for methanol synthesis from H_2 and CO_2

Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M(Cu,Zn)-ammonia complexes (DMAC) at various temperatures.The catalysts were characterized in detail,including X-ray diffraction,N2 adsorption-desorption,N2O chemisorption,temperature-programmed reduction and evolved gas analyses.The influences of DMAC temperature,reaction temperature and specific Cu surface area on catalytic performance are investigated.It is considered that the aurichalcite phase in the precursor plays a key role in improving the physiochemical properties and activities of the final catalysts.The catalyst from rich-aurichalcite precursor exhibits large specific Cu surface area and high space time yield of methanol (212 g/(Lcat·h);T=513 K,p=3MPa,SV=12000 h-1).     

经典锥壳理论的新发展

本文在评述前人有关锥壳理论研究的基础上,介绍了我国学者近年来的一系列研究成果.      

有限温度下Na4团簇的异构化

在紧密结合分子动力学模型基础上,对Ｎａ４的两种异构体Ｄ２ｈ和Ｃ２Ｖ和结构性质随温度的进行了系统性研究。发现在低温时,这两划构体具有明显有不同;在较高温度时,能够发现Ｃ２Ｖ和Ｄ２ｈ两种异构体之间的转变;在更高温度时,这两种异构体Ｃ２ｖ和Ｄ２ｈ都处于液态。     

纳米LaF3微粒对聚酰亚胺粘结固体润滑涂层摩擦学性能及抗腐蚀性能的影响

采用MHK-500型摩擦磨损试验机考察了含纳米LaFa微粒的聚酰亚胺粘结固体润滑涂层在干摩擦条件下同GCr15钢环配副时的摩擦学性能，评价了涂层的耐腐蚀性能，重点探讨了纳米LaFa填料对涂层耐磨性及耐腐蚀性能的影响．结果表明：含1％～2％纳米LaF3的涂层的耐磨性最佳，而纳米LaF3填料对涂层减摩性能的影响不大；含2％纳米LaF3的涂层的耐腐蚀性最好．