A theoretical study of the formation of the parent phosphinine C5H5P from the flash vacuum thermolysis of diallylvinylphosphine

The gas-phase decomposition of diallylvinylphosphine 1 into C5H5P 12 is studied by DFT/6-311+G(d,p) calculations with the B3LYP functional, followed by single-point energy-only calculations at the CCSD(T)/6-311+G(d,p) level. According to these calculations, the first step involves a retro-ene elimination that yields 3-phosphahexatrienes 2Z and 2E. Both compounds equilibrate through the formation of 1,2- and 3,4-dihydrophosphetes 3 and 4, and it is shown that the formation of 2Z is favored by the exothermic formation of the 3,4-dihydrophosphinine 5 through a 6pi-electrocyclization. Though 5 can easily isomerize into 2,3- (6) and 1,2-diyhydrophosphinines (7) by successive 1,5-hydrogen shifts, the formation of 12 from 5, 6, or 7 through an elimination of H2 is found to be a high energy process. It is also shown that the elimination of H2 from lambda5-phosphinine 8 following a C2v pathway is a symmetry-forbidden process. Finally, 1,4-dihydrophosphinine 9, which can be formed through a 1,4-hydrogen shift from lambda5-phosphinine 8, is found to be a convenient precursor of 12 through a 1,4-elimination of H2. The formation of 9 from 5 involves the intermediary formation of 3-phosphabicyclo[3.1.0]hex-2-ene 10. The mechanism eventually proposed for the formation of 12 from 2Z is given in Scheme 16 at the CCSD(T) level.     

Amperometric flow-injection method for the assay of l-ascorbic acid based on the photochemical reduction of Methylene Blue

Ascorbic acid (AA) is determined by amperometric detection based on the photochemical reduction of Methylene Blue (MB(+)) in 0.1 M phthalate buffer at pH 3.8. In this medium, MB(+) using flow-injection analysis. The carrier stream is 1 mM MB(+) is reduced quasi-reversibly at a glassy carbon electrode at -0.34 V vs. Ag/AgCl, while AA is oxidized irreversibly at about 0.3 V. The reactor is irradiated with a 500 W halogen lamp to facilitate the development of the photochemical reaction. A laboratory-built wall-jet electrode system was used. The Leucomethylene Blue formed in the reaction is detected at +0.050 V. At 2.2 ml min(-1) and using a sample loop of 43 mul, the method allows the determination of AA in the range 5.0-90.0 mug ml(-1), with a relative standard deviation of 1.3-4.8%, a detection limit of 1.9 mug ml(-1) and a sampling frequency of 45-50 h(-1).     

Immobilization of protein on ferromagnetic Dacron

Ferromagnetic Dacron (polyethyleneterephthalate) is proposed as a matrix to immobilize proteins covalently. Dacron in powder was magnetized by reacting ferrous (Fe+2) and ferric (Fe+3) ions with its hydrazide form at pH 8.3. Ferromagnetic hydrazide Dacron was converted to ferromagnetic azide Dacron and amyloglucosidase (E.C. 3.2.1.3) was covalently bound through the latter group. The catalytic property of the enzyme was preserved (8% of the specific activity estimated for the soluble enzyme) and all the magnetic amyloglucosidase Dacron derivative was recovered by using a magnetic field. No activity was detected in the supernatant.     

基于核酸探针的光学传感方法和细胞成像研究

许多疾病的特征在于各种生物分子表现出的异常活性,这些物质通常在细胞内外显示过表达现象,因此对其灵敏靶向识别可以提供诊断和治疗效用。由于基因诊疗和化学传感技术的发展,用于灵敏检测细胞内外生物化学物质的核酸探针突显优势。核酸探针可以在稳定进入细胞的同时,特异性地结合目标物质,通过光学方法检测或通过成像技术标识出来。本文综述了采用光学传感方法和成像技术,基于核酸探针检测生物分子的新进展。根据检测对象进行分类,概括分析了几个代表性体系:核酸序列、蛋白质和酶、化学物质和物理化学条件,并详细阐述其关键设计原理、灵敏度及样品检测等结果,同时指出了各类核酸探针的优缺点。     

New mono- and bis-carbene samarium complexes: synthesis, X-ray crystal structures and reactivity

New samarium carbene complexes have been synthesized and characterized by X-ray diffraction analysis; the carbenic nature was assessed by reactivity studies.     

磺化聚苯醚离聚体的溶液性质

研究了磺化度为20.9mol％的磺化聚苯醚(S-PPO)的钠盐和锂盐在四氢呋喃/甲醇混合溶剂中的离聚体行为。S-PPO离聚体在溶液中的链聚集状态与聚合物浓度、阳离子半径密切相关。当Na-SPPO的浓度高于3g/dL时,在30～40℃范围内其聚集度DA与浓度C的关系为:DA=ke~(εc)常数K和β分别表示为与发现链聚集的起始浓度和链聚集速率相关的常数。     

Quaternarisation de l'atome d'azote de systemes tautomeres de la serie des oxo-4 thiazoles. Cycloadditions dipolaires 1,3 des thiazoles mesoioniques formes in situ

4-Hydroxythiazoles and N-acylimino 4-thiazolidinones show similar tautomeric behaviour to azlactones. However, the mechanism of their reaction with dimethylacetylenedicarboxylate or with ethyl vinyl ether differs fundamentally. In the thiazole series, the first step is the quaternization of the nitrogen atom. The mesoionic thiazole intermediate is then trapped by a second molecule of the dipolarophile.     

19F NMR chemical shifts of n-F-alkyl compounds

The examination of ¹⁹F chemical shifts for ca. 650 F-alkylated compounds of general formula CF₃(CF₂)_nCF₂X led to the following conclusions: the CF₂ groups α to X are very sensitive to the nature of X, and are spread over a range of 85 ppm. The effect of the length of the F-alkyl chain decreases rapidly, so that δCF₂(α) can already be considered as characteristic of X for n = 1 or 2 for most practical purposes. Solvent effects (in 9 different solvents having ε = 1.8 to 52.1) were found to be rather small except for the F-alkyl iodides. A chart which indicates the domain in which the CF₂(α) resonance signal is to be expected is given for 42 different series of F-alkylated compounds; it is expected to provide the synthetic chemist with a useful tool for the identification and characterization of such compounds.     

Selective Determination of Nanogram γ-Globulin in Human Blood Serum by Resonance Light Scattering of Functionalized Nano-PbS

Functionalized nano-PbS has been prepared and characterized. The functionalized nanoparticles have good dispersibility in water. Reaction of functionalized nano-PbS with γ-globulin (γ-IgG) results an enhanced resonance light scattering (RLS) around 385nm.However, when the content of HSA is lower than 0.5μg/ml^-1 the RLS enhancement is very weak and is nonlinear to concentration of HSA. Based on these results, a new direct quantitative determination method for γ-globulin in blood serum samples without separation is established.Under optimal conditions, the enhanced RLS intensity is in proportion to the γ-IgG concentration in the range 10-500ng/mL. The limit of detection is 2.75ng/mL. This method is proved to be very sensitive, rapid, simple and selective for detection of γ-IgG in blood serum.     

Exposure dose assessment and discussion on radioisotope production and application

The exposure dose status on radioisotope production and application in China has been assessed in the paper. The average annual occupational exposure dose received by workers in the radioisotope production is about one tenth of the annual dose limit in normal situation. It is less than one twentieth for workers in the radioisotope applications. However, the annual collective dose for the latter is higher than the former by one oder of magnitude due to the larger number of workers in the application field. Although the output of radioisotopes increased doubly in 1980's as compared with 1970's, the increase on the annual collective dose was not obvious. For exposure to the public,¹³¹I for example, the collective dose in the radioisotope production decreased by one to two orders of magnitude and the releasing factor reduced by two orders of magnitude. Therefore, the exposure dose received by workers in radioisotope production and application is lower in normal situation. However, the facts worth paying attention to are that there were many events and accidents which happened in the radioisotope applications, especially at the irradiation facilities. The probability of fatal accident was as high as 10^–3 per irradiator year. In order to improve the radiation safety situation, it is imperative to conduct the safety assessment for irradiation facilities, to enhance management of the radioactive wastes and spent sources and to establish the experience feedback system.