Detection of ClSO with time-resolved Fourier-transform infrared absorption spectroscopy

ClSO was produced as an intermediate upon irradiating a flowing mixture of Cl2SO and Ar with a KrF excimer laser at 248 nm. A step-scan Fourier-transform infrared spectrometer coupled with a small multipass absorption cell was employed to detect time-resolved absorption spectrum of ClSO. A transient spectrum in the region 1120-1200 cm(-1), which diminished on prolonged reaction, is assigned to the S-O stretching (nu1) mode of ClSO. A spectrum with a resolution of 0.3 cm(-1) partially reveals rotational structure with the Q-branch at 1162.9 cm(-1). Calculations with density-functional theory (B3LYP/aug-cc-pVTZ) predict the geometry, vibrational, and rotational parameters of ClSO. An IR absorption spectrum of ClSO simulated based on predicted rotational parameters agrees satisfactorily with experimental results. ClSO produced from photolysis of Cl2SO at 248 nm is internally hot.     

A New Convenient Method for the Resolution of 1, 1''''-Binaphthalene-2, 2''''-diol Via a Phosphite Using (-)-Menthol as Resolving Agent

Optically active 1,1-binaphthalene-2, 2-diol has become a quite important chiral source in different fields of chirotechnology, especially in asymmetric synthesis1. Its synthesis and resolution has been extensively studied and various resolution methods have been reported2. Among the reported resolution methods, the following three, namely, via the formation of phosphoric acid derivatives3, boric acid derivatives4 and inclusion complexes5, are the most important. OHOH+_( )-1(-)-(S)-1(+)-(R)…     

Kinetic and thermodynamic characterization of the cobalt and manganese oxyhydroxide cores formed in horse spleen ferritin

Horse spleen ferritin (HoSF) containing 800-1500 cobalt or 250-1200 manganese atoms as Co(O)OH and Mn(O)OH mineral cores within the HoSF interior (Co-HoSF and Mn-HoSF) was synthesized, and the chemical reactivity, kinetics of reduction, and the reduction potentials were measured. Microcoulometric and chemical reduction of HoSF containing the M(O)OH mineral core (M = Co or Mn) was rapid and quantitative with a reduction stoichiometry of 1.05 +/- 0.10 e/M forming a stable M(OH)(2) mineral core. At pH 9.0, ascorbic acid (AH(2)), a two-electron reductant, effectively reduced the mineral cores; however, the reaction was incomplete and rapidly reached equilibrium. The addition of excess AH(2) shifted the reaction to completion with a M(3+)/AH(2) stoichiometry of 1.9-2.1, consistent with a single electron per metal atom reduction. The rate of reaction between M(O)OH and excess AH(2) was measured by monitoring the decrease in mineral core absorbance with time. The reaction was first order in each reactant with second-order rate constants of 0.53 and 4.74 M(-1) min(-1), respectively, for Co- and Mn-HoSF at pH 9.0. From the variation of absorbance with increasing AH(2) concentration, equilibrium constants at pH 9.0 of 5.0 +/- 1.9 for Co-HoSF and 2.9 +/- 0.9 for Mn-HoSF were calculated for 2M(O)OH + AH(2) = 2M(OH)(2) + D, where AH(2) and D are ascorbic acid and dehydroascorbic acid, respectively. Consistent with these equilibrium constants, the standard potential for the reduction of Co(III)-HoSF is 42 mV more positive than that of the ascorbic acid reaction, while the standard potential of Mn(III)-HoSF is 27 mV positive relative to AH(2). Fe(2+) in solution with Co- and Mn-HoSF under anaerobic conditions was oxidized to form Fe(O)OH within the HoSF interior, resulting in partial displacement of the Co or Mn by iron.     

A spectrophotometric study on the interaction of hemoglobin in a diazo coupling reaction of neonatal bilirubin: I. Interaction of bilirubin and hemoglobin in the Jendrassik-Grof diazo blank reagents

Studies of difference spectra have revealed a dynamic interaction of bilirubin and hemoglobin in the alkaline Jendrassik-Grof diazo blank reagent. The similarity obtained for difference spectra with respect to shape and peak maxima and peak minima of various ferriprotoporphyrin-containing biomolecules, such as hemin, methemoglobin, cyanmethemoglobin, and catalase implicated ferriprotoporphyrin in this interactive process. Further time studies of these mixtures seem to suggest an oxidation-reduction type of reaction, resulting in the formation of ferroprotoporphyrin and presumably the concomitant oxidation of bilirubin.     

Organic Reactions in Ionic Liquids： An Efficient Method for the Synthesis of Phenacyl Esters by Reaction of Carboxylic Acids with α-Bromoacetophenone Promoted by Potassium Fluoride

An efficient method is reported for the synthesis of phenacyl esters by reaction of carboxylic acids with a-bromoacetophenone promoted by potassium fluoride in ionic liquid [Bmim]PF6, the yield of the reaction is almost quantitative and the products are essentially pure.     

对甲烷氧化偶联W－Mn／SiO＿2催化剂Na＿2WO＿4的流失及其影响的考察

用ＸＲＤ、ＦＴ－ＩＲ、ＥＳＲ、Ｈ２－ＴＰＲ和ＴＰＯ等方法，对Ｎａ２ＷＯ４－Ｍｎ２Ｏ３／ＳｉＯ２催化剂和其经水煮处理的一系列样品进行了表征．实验发现该催化剂中的结晶态Ｎａ２ＷＯ４易于流失，单层分布的Ｎａ２ＷＯ４在苛刻的处理条件下也有可能流失．依此，探讨了上述流失现象与Ｎａ２ＷＯ４－Ｍｎ２Ｏ３／ＳｉＯ２催化剂的催化活性及该催化剂在长时间反应中发生的ＳｉＯ２相变之间的关系，证明了结晶态Ｎａ２ＷＯ４的流失对该催化剂甲烷氧化偶联反应的催化活性只有轻微的影响，单层分布Ｎａ２ＷＯ４的流失可造成催化剂中Ｍｎ从Ｍｎ３＋转变为Ｍｎ２＋，并使催化剂的催化活性明显降低．但在水煮条件下，无论是结晶态的还是单层分布，Ｎａ２ＷＯ４的流失都没有对ＳｉＯ２的α－方石英结构产生影响     

Synthesis of anticonvulsant activity of some 2-phenylcarbamoyl-1,2-diazabicyclo[2.2.2]octanes

A number of aryl isocyanates were adducted to 1,2-diazabicyclo[2.2.2]octane and afforded 2-phenyl-carbamoyl-1,2-diazabicyclo[2.2.2]octanes. Some of the products displayed anticonvulsant activity.     

等离子体聚合及其聚合物的应用

本文着重综述了烃,含氮、氧的有机化合物,碳氟化合物以及有机硅化合物的等离子体聚合。同时还系统地介绍了等离子体聚合物在制备反渗透膜、分离膜、材料表面的涂层等方面的国内外的最新研究成果。     

A density functional study on the formation of charge transfer complexes between alkaloids and iodine monochloride

The formation of charge-transfer (CT) complexes between N-methyl-6,7-methylenedioxy-tetrahydro-4-isoquinolone (MMDTIQ, the model molecule of alkaloids) and iodine monochloride has been studied with the density functional B3LYP method. The competition for ICl between n-donor(s) and π-donor in the same molecule has been compared for the first time. The results indicate that the electron-donating ability of various donor sites decreases in the following order: amino nitrogen>carbonyl oxygen>etheric oxygen≈aromatic ring. Complexes with a stoichiometry of 1:1 to 1:5 (MMDTIQ–ICl) might form. Among complexes with a given stoichiometry, the one in which the phenyl ring is involved in the binding is always the least stable. According to these results, in order to ensure an alkaloid iodinated, the amount of ICl should be far beyond that of alkaloids and a low polar solvent should be used, which is quite in agreement with our recent experimental results.     

A regiospecific synthesis of 1-methylamino-6-fluoro-7-(4-methylpiperazin-1-yl)-1,4-dihydro-4-oxoquinoline-3-carboxylic acid

An efficient and regiospecific synthesis of 1-methylamino-6-fluoro-7-(4-methylpiperizin-1-yl)-1,4-dihydro-4-oxoquinoline-3-carboxylic acid ( 3 ) via an intramolecular nucleophilic displacement cyclization reaction is reported.