MOLECULAR STRUCTURE OF DINUCLEAR COBALT COMPLEX WITH CHELATING 1, 3-BIS (DIPHENYLPHOSPHINO ) PROPANE LIGAND

<正> Co2 ( CO ) 6 (dppp ) Cdppp = 1,3-bis ( diphenylphosphino ) propane = Ph2P(CH2)3PPh2D, Mr=698. 38, monoclinic, space group P21/c, a=14. 952(8) , b = 13.44(2), c = 16. 72(1) A. β=110.56(4)°, V=3147(9) A3, Z = 4, A=1. 47 g/cm3, λ(MoXα) = 0. 71069 A, F(000) = 1424, λ(MoKα) = 11. 93 cm-1, R = 0. 032 and Rw = 0. 044 for 4553 observed independent reflections with I>4. 0σ(I). The molecular structure of the complex shows that the dppp ligand chelates one of the two cobalt atoms of the complex molecule, and there are two bridging carbonyl groups between the two cobalt atoms. The Co-Co bond length is 2. 534(3) A . The chelating dppp ligand results in the asymmetrization of the molecule.     

三羰基铬苯乙烯甲酰衍生物的质谱研究

近年来,随着对金属有机化合物的研究的不断深入,人们对它们的兴趣已由对结构、化学性质的探讨而扩展到对物理性质的研究,如磁性质、导电性、光学性质,并从中发现某些金属有机化合物,如某些芳基三羰基铬络合物及二     

Voltammetric determination of 5-hydroxydole-3-acetic acid in human gastric juice

A method for the determination of the major serotonin metabolite — 5-hydroxyindole-3-acetic acid (5-HIAA) in human gastric juice by cyclic voltammetry was described. The measurement conditions were investigated. The potential window was chosen from +0.1 to +0.9 V, the supporting electrolyte was 0.025 M PBS solution (pH 2.0). The method allowed determination in the concentration range from 2.0 ×10⁻⁷ to 2.0 ×10 ⁻⁵ M and a detection limit of 80 nM. When samples of gastric juice were analyzed with the method, we obtained the mean content of 5-HIAA in the gastric juice. Meanwhile, interference from other ions and substances were examined. The experimental results indicate that the method for the determination of gastric juice samples is successful.     

Nanoscale fluorescent sensors for intracellular analysis

There is a growing interest in the development of submicron optochemical sensing devices. Miniaturization of sensors to nano-dimensions decreases their typical response time down to the millisecond time scale. Their penetration volume is reduced to a few cubic micrometers and they exhibit a spatial resolution at the nanometer scale. In this review the fabrication of submicron optical fiber fluorescent sensors and particle-based fluorescent nanosensors is described. The functional characteristics of these exciting miniaturized fluorescent sensors and their applications for quantitative measurement of intracellular analytes are demonstrated.     

Mo2C膜表面粗糙化规律的计算机模拟

引入晶粒边界修正,改进了Mo2C膜表面粗糙化物理模型,将DT2模型推广到包括有温度的情况,对Mo2C膜表面形态进行计算机模拟并统计模拟图的高度分布,确定表面粗糙度随沉积时间和基底温度的变化规律。结果表明：引入晶粒边界修正大大促进了理论与实验结果的一致,Mo2C膜表面粗糙化属快速粗造化,粗造度随基底温度升高而非线性地增大。     

新型功能材料有机钌络合物和有机钌聚合物

有机钌络合物和有机钌聚合物具有特殊的光、电性能,是一种新型功能材料,正在形成一个新的研究领域。本文介绍有机钌络合物和有机钌聚合物的光致电子转移、光致发光和电致发光等现象以及它们在发光二极管、发光电池、氧化传感器等方面的应用。     

Conjugate addition reactions of alpha-aminoalkylcuprates with alpha, beta-alkenyl-, alpha,beta-alkynyl-, alpha,beta-beta,gamma-allenyl-, and alpha,beta-gamma,delta-dienyl carboxylic acid derivatives, nitriles, and sulfoxides

alpha-Aminoalkylcuprates prepared from alpha-lithio carbamates and CuCN.2LiCl participate in 1,4-addition reactions with alpha, beta-unsaturated esters, thiol esters, imides, and nitriles in poor to excellent yields depending upon the electron-withdrawing substituent and the substitution pattern of the unsaturated substrate. These reagents also undergo conjugate addition reactions with alpha,beta-alkynyl esters, sulfoxides, and nitriles and with alpha,beta-beta,gamma-unsaturated allenyl esters. Excellent stereocontrol is achieved in the conjugate additions of alpha-aminoalkylcuprates to the allenyl esters, while poor stereoselectivity results in the conjugate additions to the alkynyl derivatives. Deprotection and cyclization of the alkynyl adducts affords pyrrolin-2-ones, while similar treatment of the allenyl adducts affords 4-alkylidine- pyrrolidin-2-ones and pyrrolizidinones.     

Determination of manganese in brain samples by slurry sampling graphite furnace atomic absorption spectrometry

A simple procedure for the determination of manganese in different sections of human brain samples by graphite furnace atomic absorption spectrometry has been developed. Brain sections included cerebellum, hypothalamus, frontal cortex, vermix and encephalic trunk. Two sample preparation procedures were evaluated, namely, slurry sampling and microwave-assisted acid digestion. Brain slurries (2% w/v) could be prepared in distilled, de-ionized water, with good stability for up to 30 min. Brain samples were also digested in a domestic microwave oven using 5 ml of concentrated HNO₃. A mixed palladium+magnesium nitrate chemical modifier was used for thermal stabilization of the analyte in the electrothermal atomizer up to pyrolysis temperatures of 1300 °C, irrespective of the matrix. Quantitation of manganese was conducted in both cases by means of aqueous standards calibration. The detection limits were 0.3 and 0.4 ng ml⁻¹ for the slurry and the digested samples, respectively. The accuracy of the procedure was checked by comparing the results obtained in the analysis of slurries and digested brain samples, and by analysis of the NIST Bovine Liver standard reference material (SRM 1577a). The ease of slurry preparation, together with the conventional set of analytical and instrumental conditions selected for the determination of manganese make such methodology suitable for routine clinical applications.     

NMR analysis of lignins in CAD-deficient plants. Part 1. Incorporation of hydroxycinnamaldehydes and hydroxybenzaldehydes into lignins

Peroxidase/H2O2-mediated radical coupling of 4-hydroxycinnamaldehydes produces 8-O-4-, 8-5-, and 8-8-coupled dehydrodimers as has been documented earlier, as well as the 5-5-coupled dehydrodimer. The 8-5-dehydrodimer is however produced kinetically in its cyclic phenylcoumaran form at neutral pH. Synthetic polymers produced from mixtures of hydroxycinnamaldehydes and normal monolignols provide the next level of complexity. Spectral data from dimers, oligomers, and synthetic polymers have allowed a more substantive assignment of aldehyde components in lignins isolated from a CAD-deficient pine mutant and an antisense-CAD-downregulated transgenic tobacco. CAD-deficient pine lignin shows enhanced levels of the typical benzaldehyde and cinnamaldehyde end-groups, along with evidence for two types of 8-O-4-coupled coniferaldehyde units. The CAD-downregulated tobacco also has higher levels of hydroxycinnamaldehyde and hydroxybenzaldehyde (mainly syringaldehyde) incorporation, but the analogous two types of 8-O-4-coupled products are the dominant features. 8-8-Coupled units are also clearly evident. There is clear evidence for coupling of hydroxycinnamaldehydes to each other and then incorporation into the lignin, as well as for the incorporation of hydroxycinnamaldehyde monomers into the growing lignin polymer. Coniferaldehyde and sinapaldehyde (as well as vanillin and syringaldehyde) co-polymerize with the traditional monolignols into lignins and do so at enhanced levels when CAD-deficiency has an impact on the normal monolignol production. The implication is that, particularly in angiosperms, the aldehydes behave like the traditional monolignols and should probably be regarded as authentic lignin monomers in normal and CAD-deficient plants.     

Resolution of the non-steady-state kinetics of the elimination of HBr from 2-(p-nitrophenyl)ethyl bromide in alcohol/alkoxide media

Non-steady-state kinetic studies reveal that the elimination of HBr from 2-(p-nitrophenyl)ethyl bromide in alcohol/alkoxide media, the classical concerted E2 reaction, actually takes place by a two-step mechanism involving the intermediate formation of the carbanion.