R-branch high-lying transition emission spectra of SbNa molecule

The calculation results of the R-branch transition emission spectra of(0–0) band of the A21 → X21 transition system of Sb Na molecule are presented in this paper. These R-branch high-lying transitional emission spectral lines are predicted by using the difference converging method(DCM). Our results show excellent agreement between DCM spectral lines and the experimental values, and the deviations are controlled within 0.0224 cm-1. What is more, based on the principle of over-determined linear equations, the prediction error is quantified in this work, which provides reliable theoretical support for our predicted DCM calculations. This work provides a lot of useful information for understanding the microstructure of Sb Na molecule.     

可溶性人源含硒抗体酶GPx的研究

对噬菌体展示人单链抗体库进行筛选,得到与半抗原S-二硝基苯取代的谷胱甘肽二丁酯特异结合的单链抗体3B10。用计算机模拟分析了单链抗体的空间结构,发现抗原结合的CDR3区位于抗体的表面,推测其可能进一步参加硒化反。利用突变引物,在大肠杆菌中表达了可溶性抗体蛋白,并用化学方法将催化必需基团硒代半胱氨酸（Sec）组装到3B10抗原结合部位,获得了具有谷胱甘肽过氧化酶活力的人源抗体酶。动力学研究结果表明,抗体酶和天然酶一样,符合乒乓反应机制。     

溶胶-凝胶法合成有机/无机杂化材料进展——1.组分间以化学键作用的有机/无机杂化材料

介绍了溶胶－凝胶法（Sol-gel process)制备组分间以化学键作用的有机／无机杂化材料的基本情况,根据合成方法进行分类,并指出其发展趋势。     

膜反应器中萘普生甲酯的动态拆分

在碱催化连续原位消旋条件下,利用CRL脂肪酶（Candida rugosa lipase）催化的萘普生甲酯立体选择性水解反应。动态拆分制备（S）－普生。使用硫水硅橡胶膜隔离生物催化拆分反应和碱催化消旋反应,解决了常规动态拆分反应中生物催化剂难以承受原位化学消旋苛刻反应条件的难题。为了利于从水－有机溶剂乳化体系中分离产物和克服产物抑制,将亲水半透膜引入搅拌罐反应器,在该膜反应器中进行动态拆分反应。当转化率超过60％时,产物（S）－萘普生的对映体过量值（eep)仍在96％以上,在反应过程中还发现CRL脂肪酶同工酶的转化。     

H2CO和NO2反应机理的密度泛函理论计算研究

用密度泛函理论方法在UB3LYP/ 6-311++G(d,p)并包含零点能水平上计算得到了H2CO和NO2反应的势能面.在势能面上找到了由H2CO和NO2反应生成HCO和trans-HONO的两条反应通道.直接H迁移反应通道的势垒只有90.54 kJ*mol-1,是主要的反应通道,其TST速率是7.9 cm3*mol-1*s-1,与文献值相符;另一条通道是H2CO异构化为trans-HCOH,然后C位H迁移,最后生成的HOC分子异构化为HCO,这条通道反应势垒高达348.03 kJ*mol-1,是一条次要反应通道.     

Synthesis, structure and characterization of M---Sn (M=Mo, W) bonded heterobimetallic complexes containing bis(pyrazol-1-yl)methane ligands

The reaction of bis(pyrazol-1-yl)methane tetracarbonylmolybdenum(0) or tungsten(0) complexes with RSnCl₃ (R=Ph, Cl) at room temperature yielded heterobimetallic complexes CH₂(Pz)₂M(CO)₃(Cl)(SnCl₂R) (Pz represents substituted pyrazole; M=Mo or W; R=Ph or Cl) in good yields, which have been characterized by elemental analysis, ¹H NMR and IR spectroscopy. The reaction of bis(3,5-dimethyl-4-halopyrazol-1-yl)methane tetracarbonyl tungsten with PhSnCl₃ did not take place even in refluxing CH₂Cl₂. The electronic and steric characteristics of substituents on the pyrazole ring remarkably influence the structures of the products. The structures of CH₂(3,5-Me₂-4-BrPz)₂W(CO)₃(Cl)(SnCl₃) (8) and CH₂(4-BrPz)₂Mo(CO)₃(μ-Cl)(SnCl₂Ph) (17) (Pz: pyrazole) determined by X-ray crystallography show that no chlorine-bridged W---Sn bond is observed in complex 8, while one chlorine-bridged Mo---Sn bond exists in complex 17. The Sn---M bond length is 2.7438(5) Å in complex 8 (W---Sn) and 2.7559(4) Å in complex 17 (Mo---Sn).     

An improved derivatization method for sensitive determination of fatty acids by high-performance liquid chromatography using 9-(2-hydroxylethyl)-carbazole as derivatization reagent with fluorescence detection

Summary Tagging techniques with reagents used for fluorescent detection for short and long-chain fatty acids using high-performance liquid chromatography are evaluated in terms of the tagging reactions, handing, flexibility, stability of the reagents. Emphasis is given to the applications of the tagging techniques to relatively high molecular mass fatty acids. The fatty acids or carboxylic compounds were derivatized to their corresponding esters with 9-(2-hydroxy ethyl)-carbazole (HEC) in acetonitrile at 60°C with N, N′-carbonyldiimidazole (CDI) as a coupling agent in the presence of 4-dimethylaminopyridine (DMAP). A mixture of esters of C₁−C₂₀ fatty acids was completely separated with 45 min using gradient elution on a reversed-phase C₁₈ column. The maximum fluorescence emission for the derivatized fatty acids is at 365 nm (λ_ex 293 nm). Studies on derivatization conditions indicated that fatty acids react rapidly and smoothly with HEC in the presence of CDI and DMAP in acetonitrile to give the corresponding sensitively fluorescent derivatives. The application of this method to the analysis of long chain fatty acids in plasma is also investigated. The LC separation shows good selectivity and reproducibility for fatty acids derivatives. The relative standard deviations (n=6) for each fatty acid derivative are <5.0%. The detection limits are at 38–57 fmol levels for C₁₄−C₂₀ fatty acids and lower levels for <C₁₄ fatty acids.     

含吡唑啉酮酰肼类衍生物的合成与结构

报道了PMBP-NTH(NTH为烟酰肼)与PMBP-PAH(PAH为对甲氧基苯甲酰肼)的合成、表征和晶体结构分析,PMBP-NTH晶体属三斜晶系,具有P1空间群,a=0.9024(2)nm,b=1.0953(2)nm,c=1.1635(2)nm,α67.070(10)°,β=68.220(10)°,γ=84.770(10)°,V=0.9816(3)nm^3,Z=2,Dc=1.345g/cm^3,μ=0.090mm^-1,F(000)=416,R=0.0363,ωR=0.0870.PMBP-PAH属单斜晶系,具有P21/c空间群,a=1.2715(4)nm,b=0.91710(10)nm,c=1.8979(3)nm,β=106.890(10)°,V=2.1177(8)nm^3,Z=4,Dc=1.338g/cm^3,μ=0.090mm^-1,F(000)=896,R=0.0414,ωR=0.0972.这两个化合物在分子内都形成了大的共轭体系,由于分子间氢键力的作用,又使它们在晶体中以二聚体形式存在.     

新型锂离子电池阳极材料Li2.7Mg0.3N的研究

以氮化锂和镁金属为原料,制备了Li2.7Mg0.3N样品,利用XRD、原子吸收、库仑滴定等方法研究了锂离子电池阳极材料Li2.7Mg0.3N的组成、结构及电化学性能。样品Li2.7Mg0.3N经成分分析组成为Li2.74Mg0.26N;其结构为四方晶系,晶胞参数a=0.388nm,c=0.547nm;比容量为1695(mA.h)/g,嵌入量x最大可达2.5276,室温时锂离子嵌入Li2.7Mg0.3N的嵌入自由能为-397.51kJ/mol,锂离子在Li2.7Mg0.3N中的化学扩散系数为5.90×10^-^11～7.23×10^-^10cm^2/s,并得到一系列热力学和动力学参数。