Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

Separation of 23 dansylated amino acids by micellar electrokinetic chromatography at low temperature

Summary The baseline separation of 23 dansylated amino acids (including 3 didansylated species) is reported. Lowering of the analysis temperature and fine control of the surfactant concentration were essential in obtaining this result. Calibration graphs with good linearity were obtained.     

紫外波段CH2I2分子的光解离动力学研究

利用离子速度成像方法,研究CH2I2分子在277—305nm范围内若干波长处的光解离动力学.通过同一束激光经(2+1)共振多光子电离(REMPI)过程探测光解碎片I(2P32)和I(2P12),得到了不同激发波长处的离子速度分布图像,从而获得CH2I2光解产物的能量分配和角分布.实验发现,碎片CH2I自由基有很高的内能激发,约占总可资用能的80%,该能量分配可以较好地用冲击模型来解释.实验还发现,产物I(2P32)和I(2P12)具有很不相同的平动能分布,结合所得到的碎片能量分配和角分布,我们对碎片I(2P32)和I(2P12)生成机理进行了分析,指出CH2I2分子电子激发态的绝热和非绝热解离决定了碎片的平动能分布. 关键词： CH2I2 离子速度成像 绝热和非绝热解离     

Consequence for Wavefunction Collapse Model of the Sudbury Neutrino Observatory Experiment

It is shown that data on the dissociation rate of deuterium obtained in an experiment at the Sudbury Neutrino Observatory provides evidence that the Continuous Spontaneous Localization wavefunction collapse model should have mass–proportional coupling to be viable.     

胶束荧光法测定维生素B_2含量

维生素B_2(核黄素)为人体内黄酶类辅基的组成部分,参与人体内的生物氧化作用。药典规定其含量测定用分光光度法,文献报道有高效液相色谱法、荧光法等。但因维生素B_2(V_(B2))遇光易分解,尤其在碱性水溶液中,极易变质。其降解产物为感光黄素,二氢核黄素,光化色素等,因此给测定的准确度和灵敏度造成一定的麻烦,为了提     

A numerical study of time-dependent schr?dinger equation for multiphoton vibrational interaction of NO molecule, modelled as Morse oscillator, with intense far-infrared femtosecond lasers

For the NO molecule, modelled as a Morse oscillator, time-dependent (TD) nuclear Schr?dinger equation has been numerically solved for the multiphoton vibrational dynamics of the molecule under a far-infrared laser of wavelength 10503 nm, and four different intensities,I = 1 × 10⁸, 1 × 10¹³, 5 × 10¹⁶, and 5 × 10¹⁸ W cm⁻² respectively. Starting from the vibrational ground state at zero time, various TD quantities such as the norm, dissociation probability, potential energy curve and dipole moment are examined. Rich high-harmonics generation (HHG) spectra and above-threshold dissociation (ATD) spectra, due to the multiphoton interaction of vibrational motions with the laser field, and consequent elevation to the vibrational continuum, have been obtained and analysed. Dedicated to Professor C N R Rao on his 70th birthday An erratum to this article is available at .     

Micellar effect in hydroformylation of high olefin catalysed by water-soluble rhodium complexes associated with sulfonated diphosphines

High linear alkenes (1-octene and 1-decene) have been hydroformylated using water-soluble rhodium complexes associated with sulfonated diphosphines in the presence of ionic surfactants or methanol. In all cases, the hydroformylation activities were higher than in experiments without additives. The selectivity in aldehydes was higher when we used cetyltrimethylammonium hydrogensulfate (CTAHSO₄) as the surfactant or methanol as the co-solvent.     

Optimized Method for the Determination of Prednisolone, Zn-Bacitracin and Phenylephrine in Local Pharmaceutical Preparations by Micellar Electrokinetic Capillary Chromatography

Summary A new, rapid and simple method is described and applied to resolve and quantify mixtures of prednisolone, Zn-bacitracin and phenylephrine. The determination was accomplished by MEKC. The separation was carried out at 25 °C and 30 kV, using a 5 mM phosphate-5 mM borate buffer (pH=8.2), 40 mM SDS as background electrolyte. Under these conditions, the run time was 6.6 min and the limits of quantification were about 1.0 mg L^–1 for every component. Repeatability and reproducibility studies were achieved showing no significant differences at 95% confidence level. The MEKC method has been applied for quantifying these compounds in different commercials pharmaceuticals products, without separations steps.     

胶束薄层色谱法测定食品及药用胶囊中的合成食用色素

在聚酰胶片上以13%SDBS(十二烷基苯磺酸钠)+7%Triton X-100〔聚乙二醇-对-(1.1,3,3-四甲基)丁基苯基醚〕+(2+3)氨水(1+5+1)为展开剂,用胶束薄层色谱法分离和测定了柠檬黄、亮蓝、苋菜红、胭脂红和赤藓红。测定波长分别为440、632、535、525和528 nm,线性范围分别为0.1～2、0.05～1、0.05～1、0.05～1和0.05～1μg/斑点。方法用于测定软饮料糖果及药用胶囊中的合成色素,获得了满意的结果。此外,还对展开剂的最佳组成进行了单纯形法优化。