铜(Ⅱ)-2,2′-联吡啶-铬天菁S三元络合物极谱吸附波及应用

本文提出了一个灵敏的具有选择性的溶出伏安法测超痕量铜的方法。在0.01mol／LNH3·H2O-NH4Cl溶液中（pH＝9．3），铜（Ⅱ）－2，2′-联吡啶（Dipy）-铬天菁S（CAS）能生成具吸附性的电活性三元络合物，在＋0.1V（vs．SCE）电位下富集，阴极溶出峰电位是一0．18V，峰电流与Cu（Ⅱ）的浓度在9．0×10－9～7.0×10－7mol／L范围内成正比，检测限是3．0×10－9mol／L，这一方法已用于测定环境水中痕量铜，回收率在98．5％，102．5％之间。     

A simulation of thermal characteristic parameters with an inverse “S” type curve

A synthetical equation is proposed to characterize the essential features of the inverse “S” type curve on the basis of summing-up simulation approach of “S” type curve. The two physical variables in the model obtained are discussed and the detailed method used to determine the parameters is given. The model is then presented to describe the crystallization of poly(caryleher ether ketone) (PEEK) and thermal decomposition of poly(amide-imide) (PAI) respectively. It is found that some thermal characteristic parameters can be well estimated from the model simu-lated in computer.     

新型铕双β-二酮红光材料的合成与发光性质

通过分子设计,合成了一种新颖的双β-二酮有机配体9-乙基-3,6-二（乙酰基-3-苯甲酰基）咔唑（H2L）及其铕配合物,红外光谱和电子光谱表明Eu^3＋与H2L发生配位。配合物的溶液荧光光谱不仅有613 nm处的中心离子Eu^3＋的特征红光,属^5D0→^7F2跃迁带,还有445nm处配体的宽带蓝色发光,属H2L^＊→H2L跃迁带,而配合物的光致发光光谱只有611 nm处为中心离子Eu^3＋的特征红光,属^5D0→^7F2跃迁带,峰形尖锐,半峰宽仅7 nm,单色性好,表明该固体铕双β-二酮配合物是一种潜在的红色发光材料。     

Density functional study of the l-proline-catalyzed α-aminoxylation of aldehydes reaction: The reaction mechanism and selectivity

The reaction mechanism of the l-proline-catalyzed α-aminoxylation reaction between aldehyde and nitrosobenzene has been investigated using density functional theory (DFT) calculation. Our calculation results reveal following conclusions [1]. The first step that corresponds to the formation of C–O bond, is the stereocontrolling and rate-determining step [2]. Among four reaction channels, the syn-attack reaction channel is more favorable than that of the anti one, and the TS-ss channel dominates among the four channels for this reaction in the step of C–O bond formation [3]. The intermolecular hydrogen bond between the acidic hydrogen of l-proline and the N atom of the nitrosobenzene in an early stage of the process catalyzes very effectively the C–O bond formation by a large stabilization of the negative charge that is developing at the O atom along the electrophilic attack [4]. The effect of solvent decreases the activation energy, and also, the calculated energy barriers are decrease with the enhancement of dielectric constants for C–O bond formation step. These results are in good agreement with experiment, and allow us to explain the origin of the catalysis and stereoselectivity for l-proline-catalyzed α-aminoxylation of aldehyde reaction. The addition of H₂O to substituted imine proline, intermolecular proton-transfer steps, and the l-proline elimination process were also studied in this paper.     

Theoretical investigation of the decarbonylation of acetaldehyde by Fe+ and Cr+.

We report a comprehensive theoretical study on the decarbonylation of acetaldehyde by Fe+ and Cr+. Various intermediates, transition states, and products involved in the decarbonylation reactions are fully optimized at the B3LYP/6-311+G(2df,2pd) level of theory. The potential energy surfaces (PESs) corresponding to [M,O,C2,H4]+(M=Cr and Fe) are examined in detail using B3LYP and CCSD(T) methods, respectively. The validity of these theoretical methods is calibrated with respect to the available thermochemical data. Calculations suggest that the Cr+ mediated decarbonylation of acetaldehyde takes place in four steps on the sextet surface: encounter complexation, C-C activation, aldehyde H-shift, and nonreactive dissociation, in good accordance with the Co+ mediated decarbonylation of acetaldehyde [Zhao, Zhang, Guo, Wu, Lu, Chem. Phys. Lett. 2005, 414, 28], while for the Fe+/acetaldehyde system decarbonylation can occur on both the quartet and the sextet PESs. The quartet pathway, which experiences spin-orbit coupling between the two surfaces, is energetically more favorable; whereas along the sextet decarbonylation coordinate several high-energy barriers are revealed. The theoretical results are compared with the experimental product kinetic energy and angular distributions of decarbonylation of acetaldehyde by Fe+ and Cr+ measured using a crossed-beam technique [Sonnenfroh, Farrar, J. Am. Chem. Soc. 1986, 108, 3521].     

Aerobic oxidation assisted by ligand-free palladium catalysts

Aerobic oxidation of electron-rich benzylic and phenyl allylic alcohols was achieved with high yields with only 0.1 mol.% of Pd(OAc)2 catalyst in the absence of any ligand. This procedure was expected to be valuable for realistic industrial-scale applications from both economic as well as environmental points of view.     

稀土在鼠肝中的物种分布

采用 ICP-MS、微量蛋白层析分离技术 ,研究了长时间、低剂量混合稀土及短时间、高剂量硝酸镧分别对大鼠及小鼠作用后 ,稀土在鼠肝中的代谢累积及其物种分布 .结果表明 ,鼠肝中各稀土含量随给药剂量的增加而增大 ,其累积速度大小顺序为 La>Ce>Nd>Pr;经柱层析分离未得到与稀土特异结合的鼠肝蛋白 ;稀土可与多种鼠肝蛋白 (包括多种重要的酶 )结合 ,在一定条件下 ,稀土与其结合蛋白可发生解离     

Study of urinary nucleosides as biological marker in cancer patients analyzed by micellar electrokinetic capillary chromatography

Thirteen normal and modified nucleosides, primarily degradation products of transfer ribonucleic acid (tRNA), were evaluated as potential tumor markers for cancer patients. Their urinary concentrations were determined by means of micellar electrokinetic capillary chromatography (MEKC) in the urine from 54 healthy adults and 70 cancer patients, then quantitatively expressed as a function of creatinine excretion. It was found that urinary nucleosides for cancer patients were on the average significantly higher than those for healthy controls, however, no significant differences were found between male and female or between different ages. Based on 13 urinary nucleoside concentrations, principal component analysis (PCA) could be used to classify 72% of cancer patients from the healthy controls. The present study shows that the precise measurement of urinary nucleosides by MEKC in combining with PCA technique may provide a clinically useful approach for diagnosis of cancer.     

Stereoselective Synthesis of Piperamide Alkaloids by Modified Ramberg-Bcklund Reaction

A convenient and rapid approach for the synthesis of piperamide alkaloids la ~ h by the recently developed one-flask Ramberg-Backlund reaction was described. The synthesis of 1e was reported for the first time.