Sulfur Compounds. 183. A Derivative of Perthiocarbonic Acid H2CS4: X-ray structural analysis of bis(triphenylmethyl) perthiocarbonate (Ph3C)2CS4

The molecular structure of Ph₃CSSC(S)SCPh₃ · CS₂ has been determined by X-ray structural analysis. The substance crystallizes in the triclinic crystal system [a = 884.9(2) pm, b = 1 039.5(2) pm, c = 2 064.6(3) pm, α = 75.86(1)°, β = 79.83(2)°, γ = 77.31(5)°, Z = 2, space group P1 ]. The CS₃ group is planar; the S? S-bond (201.4 pm) forms an angle of 5.7° with the CS₃ plane. The torsional angle CSSC equals 96.3°. (Ph₃C)₂CS₄ was obtained by reaction of TosNSCl₂ (Tos = p-MeC₆H₄SO₂) with Ph₃CSH in CS₂ in the presence of triethylamine. The reaction mechanism is discussed.     

由(1S)-cis-菊酸合成(1R)-cis-二溴菊酸

拟除虫菊脂是在研究天然除虫菊脂化学的基础上发展起来的一类高效低毒,广谱杀虫剂。其中,溴氰菊脂是活性较高,光稳定性较好的一种菊脂类杀虫剂, 它是具有(IRcis.αs) 构型的单一光学异构体。 生产溴氰菊脂的关键中间体是IR-cis-)二溴菊脂。本文报道利用化学剪切法将(is)-cis-菊脂转化为(IR-cis-)二溴菊脂的新方法。     

Immobilization of endo-1,4-β-xylanase on polysulfone acrylate membranes: Synthesis and characterization

We report on a new enzyme/support system to immobilize proteins such as enzymes through a covalent bond on polysulfone membranes. In the present case the enzyme endo-1,4-β-xylanase (E.C.3.2.1.8) is attached to polysulfone previously derivatized by introducing an acrylate group. Membranes are properly prepared from this polysulfone acrylate. Afterwards the enzyme is immobilized though the amino groups of side chains of the amino acids of the enzyme and the acrylate group of the derivatized polysulfone. Such immobilization of the enzyme is confirmed by microelemental analysis as well as by amino acid analysis by HPLC. Moreover, the enzymatic activity of the membranes was evaluated and compared with that corresponding to the free enzyme. Certain physical parameters (asymmetry, irregularity, pore size and surface roughness) of the corresponding enzymatic membranes were obtained from SEM and AFM image interpretation.     

Surface modification of low density polyethylene (LDPE) film by low pressure O2 plasma treatment

In this work, low pressure glow discharge O₂ plasma has been used to increase wettability in a LDPE film in order to improve adhesion properties and make it useful for technical applications. Surface energy values have been estimated using contact angle measurements for different exposure times and different test liquids. In addition, plasma-treated samples have been subjected to an aging process to determine the durability of the plasma treatment. Characterization of the surface changes due to the plasma treatment has been carried out by means of Fourier transformed infrared spectroscopy (FTIR) to determine the presence of polar species such as carbonyl, carboxyl and hydroxyl groups. In addition to this, atomic force microscopy (AFM) analysis has been used to evaluate changes in surface morphology and roughness. Furthermore, and considering the semicrystalline nature of the LDPE film, a calorimetric study using differential scanning calorimetry (DSC) has been carried out to determine changes in crystallinity and degradation temperatures induced by the plasma treatment. The results show that low pressure O₂ plasma improves wettability in LDPE films and no significant changes can be observed at longer exposure times. Nevertheless, we can observe that short exposure times to low pressure O₂ plasma promote the formation of some polar species on the exposed surface and longer exposure times cause slight abrasion on LDPE films as observed by the little increase in surface roughness.     

Facilitated transport of Hg(II) through novel activated composite membranes

The results presented in this work deal with the prime application of activated composite membranes (ACMs) for the transport of Hg(II) ions in a continuous extraction–re-extraction system using di-(2-ethylhexyl)dithiophosphoric acid (DTPA) as carrier. The effects of variables such as the pH, the nature of the acid and the concentration of the casting solutions on the transport of Hg(II) are also investigated. When the ACM was prepared with a 0.5 M DTPA solution and when the feed solution contained 2.5×10^–4 M Hg(II) in 0.1 M HCl, the amount of mercury extracted was greater than 76%. The re-extracted mercury was subsequently recovered by means of a stripping phase comprising 0.3 M thiourea solution in 2 M H₂SO₄, yielding 54% of the initial amount of mercury after transport had taken place for 180 min.     

常见饮料中痕量铝的分光光度法研究

新试剂5-溴水杨基荧光酮可在pH5.5～6.8的六次甲基四胺缓冲溶液中,与铝,溴化十六烷基吡啶形成稳定的红色三元配合物。最大吸收波长约为568nm,摩尔吸光系数高达1.7×10~5L mol~(-1)·cm~1,常见金属离子很少干扰。据此,建立了测定微量铝的方法。其线性范围为0～6μg/25ml回收率在96％～103％之间。本文测定了常见饮茶,饮料及饮水中的微量铝。     

甲基膦酸二甲庚脂-HBr体系萃取色层法分离微量镉及其应用

本文提出了以 P350为固定相,硅胶为载体,1.0mol/L HBr 为流动相,采用水作洗脱液的萃取柱色层分离微量镉的新方法。研究了分离条件,萃取保留机理和干扰等。用制定的方法对铅锌矿和冶炼电转尘中微量镉进行了分离测定,均获得良好结果。回收率在95～102％之间。     

Photovoltaic and spectral properties of tetraphenyloporphyrin and metallotetraphenyloporphyrin dyes

Spectroscopical properties and photocurrent (or photovoltage) of tetraphenyloporphyrins and metallotetraphenyloporphyrins in nematic liquid crystal have been studied. Photoelectric response has been measured in an electrochemical cell made of the semitransparent semiconducting and golden electrodes with porphyrin dyes embedded in liquid crystal. Fluorescence, time-resolved luminescence in microsecond time scale and photoacoustic spectra have also been measured. The competition between radiative, non-radiative processes and charge transfer is discussed. It has been shown that effectivity of porphyrins for photocurrent generation depends on the presence/absence of central metal in the macrocycle of porphyrin skeleton and the kind of metal. The schematic model of the contributions of the dye molecule and semiconducting electrode in the electron transfer process is shown.     

A new stereoselective synthesis of 2-amino-4,5-dihydrothiophene-3-carbonitrile derivatives

A new stereoselective method for the synthesis of trans-isomers of 2-amino-4-aryl-5-benzoyl-4,5-dihydrothiophene-3-carbonitriles was proposed. The method involves base-catalyzed reactions of phenacyl thiocyanate with 3-(het)aryl-2-cyanoprop-2-enethioamides. (4R,5S/4S,5R)-2-Amino-5-benzoyl-4-(2-chlorophenyl)-4,5-ihydrothiophene-3-carbonitrile was structurally characterized by X-ray diffraction analysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1379–1383, July, 2007.     

Thermal degradation of vinylidene chloride/[4-(t-butoxycarbonyloxy)phenyl]methyl acrylate copolymers

Vinylidene chloride polymers containing comonomer units capable of consuming evolved hydrogen chloride to expose good radical-scavenging sites might be expected to display greater thermal stability than similar polymers containing simple alkyl acrylates as comonomer. Incorporation of a comonomer containing the phenyl t-butyl carbonate moiety into a vinylidene chloride polymer has the potential to afford a polymer with pendant groups which might interact with hydrogen chloride to expose phenolic groups. Copolymers of vinylidene chloride with [4-(t-butoxycarbonyloxy)phenyl]methyl acrylate have been prepared, characterized, and subjected to thermal degradation. The degradation has been characterized by thermal and spectroscopic techniques. The degradation of vinylidene chloride/[4-(t-butoxycarbonyloxy)phenyl]methyl acrylate copolymers is much more facile than the same process for similar copolymers containing either [4-(isobutoxycarbonyloxy)phenyl]methyl acrylate or methyl acrylate, a simple alkyl acrylate, as comonomer. During copolymer degradation, [4-(t-butoxycarbonyloxy) phenylmethyl acrylate units are apparently converted to acrylic acid units by extensive fragmentation of the sidechain. Thus, the phenyl t-butyl carbonate moiety does function as a labile acid-sensitive pendant group but its decomposition in this instance leads to the generation of a phenoxybenzyl carboxylate capable of further fragmentation.