Heterobimetallische phosphanido-verbrückte Zweikern-Komplexe - Synthese von cis-rac-[(η-C5H4R)2Zr{μ-PH(2,4,6−iPr3C6H2)}2M(CO)4] (RMe,MCr,Mo; RH,MMo)

Heterobimetallic Phosphanido-bridged Dinuclear Complexes - Syntheses of cis-rac-[(η-C₅H₄R)₂Zr{μ-PH(2,4,6-ⁱPr₃C₆H₂)}₂M(CO)₄] (R?Me, M?Cr, Mo; R?H, M?Mo) The zirconocene bisphosphanido complexes [(η-C₅H₄R)₂Zr{PH(2,4,6-ⁱPr₃C₆H₂)}₂] (R?Me, H) react with [(NBD)M(CO)₄] (NBD?norbornadiene, M?Cr, Mo) to give only one diastereomer of the phosphanido-bridged heterobimetallic dinuclear complexes cis-rac-[(η-C₅H₄R)₂Zr{μ-PH(2,4,6-ⁱPr₃C₆H₂)}₂M(CO)₄] [R?Me, M?Cr ( 1 ), Mo ( 2 ); R?H, M?Mo ( 3 )]. However, no reaction was observed between [(η-C₅H₅)₂Zr{PH(2,4,6-^tBu₃ C₆H₂)}₂] and [Pt(PPh₃)₄]. 1—3 were characterised spectroscopically. For 1—3 , the presence of the racemic isomer was shown by NMR spectroscopy. No reaction was observed at room temperature for 3 and CS₂, (NO)BF₄, Me₃NO or PH(2,4,6-Me₃C₆H₂)₂. With Et₂AlH or PhC?CH decomposition of 3 was observed.     

苯并异硒唑酮氨基酸衍生物的合成及抗脂质过氧化作用

在已知具有氧化作用的2-苯基-1,2-苯并异硒唑-3(2H)-酮(Ebselen)的基础上, 将其2-位苯环更换成氨基酸乙酯, 设计并合成了9个苯并异硒酮的氨基酸衍生物3～11. 这类化合物的抗氧化作用药理研究表明,它们对Fe^2^+/半胱氨酸及维生素C诱发的大鼠肝微粒体脂质过氧化有抑制活性, 部分化合物活性比母体化合物Ebselen更优.     

Non-radioactive determination of PTH and dabsyl phosphoamino acids by capillary electrophoresis

Summary Capillary electrophoresis is a novel technique in the non-radioactive determination of phosphoamino acids. The main advantage of the method presented is the high selectivity and the ability to separate all phosphoamino acid derivatives. Non-radioactive determination of PTH or dabsyl phosphoamino acids by capillary electrophoresis provides a fast and simple screening procedure for all O-phosphorylated amino acids in protein and peptides in the low picomolar range.     

Two 3D supramolecular polymers constructed from an amino acid and a high-nuclear Ln6Cu24 cluster node

The first successful attempt to construct 3D supramolecular frameworks with high-nuclear 3d-4f heterometallic clusters as a node is reported. The self-assembly of Ln3+, Cu2+ and amino acid in solution leads to the formation of two polymers, 35-nuclear complex [Sm6Cu29] 1 with a primitive cubic net-like structure and 36-nuclear complex [Nd6Cu30] 2 with a face-centred cubic network type structure. Glycine and L-proline, respectively, were used as ligands. It should be noted that 2 has a chiral framework. X-ray structure analyses show that 1 crystallizes in the triclinic P1 space group (a=19.6451(8), b=20.4682(8), c=20.7046(8) A, alpha=89.453(1), beta=66.290(1), gamma=68.572(1) degrees, V=7003.0(5) A3 and Z=1) and 2 belongs to the cubic P2(1)3 space group (a=b=c=32.4341(3) A, V=34 119.7(5) A3 and Z=4). Both complexes utilize Ln6Cu24 octahedral clusters as nodes and trans-Cu(amino acid)2 groups as bridges. Electrical conductivity measurements reveal that both polymers behave as semiconductors.     

Efficient, highly regioselective, and stereospecific conversion of glycidol systems into C2-O-acylated vicinal halohydrins

Glycidyl esters and ethers undergo a regioselective and stereospecific opening of the oxirane ring upon treatment in chloroform in the presence of pyridine with trimethylsilyl halide (TMSX, X = Cl, Br, or I) and a mixture of carboxylic acid (CA)-trifluoroacetic anhydride (TFAA), to produce the corresponding C2-O-acylated vicinal halohydrins in high yields.     

Determination of low-molecular-weight carboxylic acids in aqueous samples by gas chromatography and nitrogen-selective detection of 2-nitrophenylhydrazides

A gas chromatographic method was developed for the determination of low-molecular-weight carboxylic acids in aqueous samples based on a derivatization procedure compatible with aqueous solutions. The technique uses nitrogen-selective detection with a thermionic-specific detector after derivatization of carboxylic acids as 2- nitrophenylhydrazides. The hydrazides were extracted with ethyl acetate prior to injection into the gas chromatograph. The derivatives appear to be stable in ethyl acetate at 0–5° C for long periods and, therefore, can be stored for analysis at a later date. The detection limits of different short-chain acids are in the range 0.8–1.4 pmol per injected sample. The relative standard deviation is less than 10% at the 1 μM level. Examples of the use of the method are given for the determination of carboxylic acids in anoxic marine sediment pore waters, coastal sea water and Black Sea water samples.     

Procedures for the enhancement of selectivity in liquid phase chemiluminescence detection

An overview of liquid phase chemiluminescence (CL) processes is presented and the potential for CL detection in liquid chromatography (LC) is discussed, with particular reference to the luminol and peroxyoxalate reactions. Post column ion displacement from a solid phase reagent [a cation exchange resin in the copper(II) form] followed by catalysis of the luminol reaction is used for the quantification of mixtures of weak acids after separation by ion-exclusion chromatography. Polyaromatic hydrocarbons (PAHs) released during the combustion of biomass fuels are separated by reversed-phase chromatography and quantified by their sensitizing effect on the peroxyoxalate reaction. This procedure is also used for the determination of carboxylic acids in non-aqueous media after selective pre-column derivatization with a fluorescent label (9-anthracenemethanol).     

A simple, rapid and efficient protocol for the synthesis of methylthiomethyl esters under Swern oxidation conditions

A rapid, mild and high yielding method for the synthesis of methylthiomethyl esters is reported from the corresponding aliphatic, aromatic and unsaturated carboxylic acids under Swern oxidation conditions using dimethylsulfoxide, oxalyl chloride and triethylamine at low temperature.     

卟啉作为信号传递介质的紫外可见光谱研究

合成了6种氨基酸水杨醛席夫碱(Sal-AA)：Sal-Gly(甘氨酸)、Sal-Phe(苯丙氨酸)、Sal-Arg(精氨酸)、Sal-Tyr(酪氨酸)、Sal-Met(甲硫氨酸)、Sal-Glu(谷氨酸)及其金属铜配合物。并分别在2种不同介质(三氯甲烷和甲醇)中，与四苯基卟啉TPP进行反应，研究了其紫外可见光谱性质，讨论了卟啉作为人工信号转导体系的传递介质，与氨基酸水杨醛席夫碱铜配合物的反应中，实现信号分子铜离子进一步传递的可能性以及溶剂对该信号传递的影响。结果表明，在三氯甲烷为溶剂时，除了Sal-Met的铜配合物之外，其余均能被TPP夺取而形成Metal TPP。而在以甲醇为溶剂时，只有Sal-Gly的铜配合物能被TPP所夺取。     

Zirconyl chloride promoted highly efficient solid phase synthesis of amide derivatives

An efficient solid phase route for the synthesis of amide derivatives by the reaction of carboxylic acids with urea in the presence of catalytic amount of zirconyl chloride under microwave irradiation conditions was described.In this way,a range of interesting amide derivatives was obtained in good to excellent yields.The catalyst was recycled with fresh reactants and it gave almost similar results without significant loss of activity up to the third run.