镧系元素杂多钼磷酸钾的合成与性质研究

本文首次报道了K_(17)[Ln(P_2Mo_(17)O_(61))_2]·xH_2O(Ln=La~(3+),Ce~(3+),pr~(3+),Nd~(3+),Sm~(3+),Eu~(3+),Gd~(3+),Tb~(3+),Yb~(3+))的合成方法,取测定结果表明,与(?)系离子配位的配体P_2Mo_(17)O♂♀~-为α_2-型,Ln的配位数为8,推测其结构类似于K_(16)[Ce(Ⅳ)(α_2-P_2W_(17)O_(61))_2]·xH_2O,还进行了UV光谱、CV、极谱、TG-DTA及磁化率等性质的研究。     

Structure of inhomogeneous attractive and repulsive hard-core yukawa fluid: grand canonical Monte Carlo simulation and density functional theory study

A density functional theory is proposed for an inhomogeneous hard-core Yukawa (HCY) fluid based on Rosenfeld's perturbative method. The excess Helmholtz energy functional is derived from a modified fundamental measure theory for the hard-core repulsion and a quadratic functional Taylor expansion for the long-ranged attractive or repulsive interactions. To test the established theory, grand canonical ensemble Monte Carlo simulations are carried out to simulate the density profiles of attractive and repulsive HCY fluid near a wall. Comparison with the results from the Monte Carlo simulations shows that the present density functional theory gives accurate density profiles for both attractive and repulsive HCY fluid near a wall. Both the present theory and simulations suggest that there is depletion for attractive HCY fluid at low temperature, but no depletion is found for repulsive HCY fluid. The calculated results indicate that the present density functional theory is better than those of the modified version of the Lovett-Mou-Buff-Wertheim and other density functional theories. The present theory is simple in form and computationally efficient. It predicts accurate radial distribution functions of both attractive and repulsive HCY fluid except for the repulsive case at high density, where the theory overestimates the radial distribution function in the vicinity of contact.     

Chromatographic separation and mass spectrometric identification of positional isomers of polyethylene glycol-modified growth hormone-releasing factor (1-29)

A one-step chromatographic method capable of separating all isomers of polyethylene glycol (PEG)-growth hormone-releasing factor (GRF) (1-29) conjugates was developed. The unmodified GRF (1-29) and seven different isomers of PEG-GRF (1-29) conjugates were separated by using a simple reversed-phase HPLC method depending on the differences of hydrophobicity due to the number and site of PEG attachment. The PEGylation sites of all isomers of PEG-GRF (1-29) conjugates were identified by determining the molecular masses of the Lys-C digested fragments with matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. This study is a first report for the separation of all PEG-conjugate isomers and would be useful for further studies to find the promising conjugate by evaluating biological activity and stability of each isomer.     

金属酞菁化合物在TiO2表面的分散研究

Dispersion of copper(Ⅱ) phthalocyanine (CuPc), copper(Ⅱ) phthalocyaninesulfonate (CuPcS) and cobalt(Ⅱ)phthalocyaninetetrasulfonate (CoPcTS) on the surface of titanium dioxide was investigated by XRD, XPS, FT-IR and UV-Vis techniques. Results show that interaction between CuPc and TiO2 was very weak and CuPc was difficult to disperse on the surface of the support. While partly sulfurized CuPcS could be dispersed on the surface of support through sulfo-groups and its dispersion capacity was determined to be 0.085 g CuPcS/g TiO2. Completely sulfurlzed CoPcTS could also be dispersed on the surface of TiO2 as a monolayer and its dispersion capacity was 0.12 g CoPcTS/g TiO2. Interactions of the sulfo-groups as well as the electrons of CoPcTS with the surface of TiO2 could be evidenced by FT-IR characterization. Therefore, it was suggested that CoPcTS molecules be adsorbed on the surface of TiO2 in a flat-lying mode while CuPcS in a slanting one. UV-Vis spectra show that the dispersed CuPcS and CoPcTS molecules exist in both forms of monomers and dimers.     

高效液相色谱荧光检测法测定瓜子中的4-氨基丁酸

在众多的氨基酸中，4-氨基丁酸是一种非蛋白质类氨基酸，它在医学上是一种抑制性神经递质，由于其自身的特点，一些常规的直接测定法灵敏度较低。尽管对其测定有较多报道，但采用柱前衍生的分离测定的报道相对较少，且测定结果不很理想。本实验采用新型荧光试剂咔唑-9-乙基氯甲酸酯(CEOC)作为衍生试剂在Hyperil C18柱上分离测定了4-氨基丁酸(GABA)。结果表明，所建立的方法简单、快速，灵敏度高。     

新的不对称双Schiff碱镍配合物

乙二胺中2个氨基具有相同的反应活性,易同时反应形成对称的双Schiff碱,随着不对称配合物的设计和金属酶模型化合物的不断开发,业已发现严格控制反应条件和改变反应物摩尔比,可以有效地实现单个氨基的选择性反应,例如,在低温、稀的反应液中,乙酰丙     

气液色谱法研究Ni[(C8H17)O)2PS2]2与脂肪胺加合反应的热力学性质

The equilibium constants of acid-base interaction between Mi(Octyl_dtp)_2 and alkylamine were determined by GLC method at several temperatures. Thermodynamic parameters △H and △S were evaluted as follows:ethylamine: △H=-11.5kJ mol~(-1) △S=-22.7J K~(-1) mol~(-1)diethylamine: △H=-18.1kJ mol~(-1) △S=-42.1J K~(-1) mol~(-1)The variations of logK versus temperature fit following equations:ethylamine: lgK=-1.19+598.9/Tdiethylamine: lgK=-2.20+945.6/T     

QuEChERS/超高效液相色谱-串联质谱法同时测定水产品中四溴双酚A与六溴环十二烷

建立了同时测定水产品中四溴双酚A(TBBPA)和六溴环十二烷(HBCD)的超高效液相色谱-串联质谱方法。样品前处理采用QuEChERS方法,均质生物样品用水分散后加乙腈提取,经C_(18)分散固相萃取净化。采用CORTECS~?C_(18)色谱柱(4.6 mm×100 mm×2.7μm)分离,以甲醇-水为流动相进行梯度洗脱,流速为0.7 mL/min。采用电喷雾离子源,在负离子模式下以多反应监测(MRM)方式检测。结果表明,TBBPA和3种HBCD单体在0.5～500μg/L范围内线性良好,相关系数(r)大于0.998,检出限(LOD,S/N=3)和定量下限(LOQ,S/N=10)分别为0.04～0.16μg/kg和0.12～0.55μg/kg。在5、20、50μg/kg加标水平下的平均回收率为74.0%～121%,相对标准偏差(RSD)为0.20%～23%。该方法操作简单、快速、重现性好,适用于水产品中TBBPA和HBCD的快速检测。     

2,5-二甲基-4-羟基-3(2H)呋喃酮的合成

以乙酰丙酮(1)为原料，经电解氧化偶联，Paal-Knorr闭环，Baeyer-Villiger氧化，水解等步骤，合成了一种重要的杂环香料，2,5-二甲基-4-羟基-3(2H)呋喃酮(6)。     

Poly[μ‐aqua‐μ4‐naphthalene‐1,8‐dicarboxylato‐zinc(II)]

In the title complex, [Zn(C₁₂H₆O₄)(H₂O)]_n, a Zn^II polymer based on naphthalene‐1,8‐dicarboxylate (1,8‐nap), the Zn^II atoms adopt an elongated octahedral coordination geometry. A zigzag chain is formed by μ₂‐aqua ligands and μ₂‐carboxylate groups of the 1,8‐nap ligands. Adjacent parallel chains are further linked by 1,8‐nap ligands, forming a twisted two‐dimensional layer structure along the (100) plane.