INTROMISSION OF WATER-REPELLENT AND HYDROSCOPIC PROPERTIES SIMULTANEOUSLY TO PP BY PLASMA DISCHARGE METHOD

Plasma-induced surface graft copolymerization of acrylic acid on polypropylene non-woven fabric (PP-g-AA) and polypropylene membrane were reported. The extents of grafting were controlled by the plasma and polymerization condition. Hexadecyltrimethyl ammonium bromide was then coupled with the carboxyl group of PP-g-AA to obtain a polyion complex (PIC). At last, CF4 plasma was used to give PICs hydrophobic property. The moisture regain and water-repellency of the processed PICs was investigated. The surfaces were characterized using ATR FT-IR and XPS. The result indicates that the products have very high ability to adsorb moisture, even better than cotton fiber. At the same time, the products show excellent hydrophobic property, which can‘t be wetted by those reagents whose surface tensions were higher than 327mN/m.     

Phosphinophosphiniden-Phosphorane tBu2P?P = P(R)tBu2 aus Li(THF)2[η2-(tBu2P)2P] und Alkylhalogeniden

The Phosphinophosphinidene-phosphoranes ^tBu₂P? P = P(R)^tBu₂ from Li(THF)₂[η²-(^tBu₂P)₂P] and Alkyl Halides We report the formation of ^tBu₂P? P = P(R)^tBu₂ a and (^tBu₂)₂PR b (with R = Me, Et, ⁿPr, ⁱPr, ⁿBu, PhCH₂, H₂C = CH? CH₂ and CF₃) reactions of Li(THF)₂[η²-(^tBu₂P)₂P] 2 with MeCl, MeI, EtCl, EtBr, ⁿPrCl, ⁿPrBr, ⁱPrCl, ⁿBuBr, PhCH₂Cl, H₂C = CH? CH₂Cl or CF₃Br. In THF solutions the ylidic compounds a predominate, whereas in pentane the corresponding triphosphanes b are preferrably formed. With ClCH₂? CH = CH₂ only b is produced; CF₃Br however yields both ^tBu₂P? P = P(Br)^tBu₂ and ^tBu₂P? P = P(CF₃)^tBu₂, but no b . The ratio of a:b is influenced by the reaction temperature, too. The compounds ^tBu₂P? P = P(Et)^tBu₂ 4a and (^tBu₂P)₂PEt 4 b , e. g., are produced in a ratio of 4:3 at ?70°C in THF, and 1:1 at 20°C; whereas 1:1 is obtained at ?70°C in pentane, and 1:2 at 20°C. Neither ^tBuCl nor H₂C = CHCl react with 2 . The compounds a decompose thermally or under UV irradiation forming ^tBu₂PR and the cyclophosphanes (^tBu₂P)_nP_n.     

Characterization of gem-difluoropropargyl synthons through HF loss from protonated molecules in methane chemical ionization mass spectra

Electron impact and methane chemical ionization mass spectra were obtained following gas chromatography/mass spectrometry for several gem-difluoropropargyl compounds, which had been synthesized as potential intermediates for synthesis of gem-difluoromethylene-containing C-3 acetylenes. EI spectra were variable with respect to the presentation of molecular ions, depending on substituent functional groups present. Methane-CI spectra were characterized by loss of 19 mass units from molecular weight with all compounds examined. These [M − 19]⁺ ions often presented as base peaks of the CI spectra, and were more reliably present and abundant than [M + 1]⁺ ions for these compounds. These ions could have been formed by elimination of HF from the protonated molecules under conditions of methane chemical ionization.     

Ab initio quantum chemical studies of the reactions of CF3CFHO2 with HO2

The potential energy surface (PES) for the CF₃CFHO₂+HO₂ reaction has been theoretically investigated using the DFT [B3LYP/6‐311G(d,p)] and B3LYP/6‐311++G(3df,3pd)//B3LYP/6‐311G(d,p) levels of theory. Both singlet and triplet PESs are investigated. The reaction mechanism on the triplet surface is simple. It is revealed that the formation of CF₃CFHOOH+³O₂ is the dominant channel on the triplet surface. On the basis of the ab initio data, the total rate constants for the reaction CF₃CFHO₂+HO₂ in the T = 210–500 K range have been computed using conventional transition state theory with Wigner's tunneling correction and have been fitted by a rate constant expression as k = 1.04 ×10^?12(cm³ molecule^?1 s^?1) exp (700.33/T). Calculated transition state rate constants with Wigner's tunneling correction for the reaction CF₃CFHO₂+HO₂ are in good agreement with the available experimental values. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

CF3O2自由基和NO反应机理的理论研究

用密度泛函理论(DFT)的B3LYP方法, 分别在6-31G、6-311G、6-311+G(d)基组水平上研究了CF3O2自由基和NO反应机理. 研究结果表明, CF3O2自由基和NO反应存在三条可行的反应通道, 优化得到了相应的中间体和过渡态. 从活化能看, 通道CH3O2+NO→IM1→TS1→IM2→TS2→CF3O+ONO的活化能最低, 仅为70.86 kJ•mol-1, 是主要反应通道, 主要产物是CF3O和NO2. 而通道CH3O2+NO→IM1→TS3→CF3ONO2和CH3O2+NO→TS4→IM3→TS5→IM4→TS6→CF3O+NOO的活化能较高, 故该反应难以进行.     

The effective ionization coefficients and electron drift velocities in gas mixtures of CF3I with N2 and CO2 obtained from Boltzmann equation analysis

The electron swarm parameters including the density-normalized effective ionization coefficients(α-η)/N and the electron drift velocities V e are calculated for a gas mixture of CF3I with N2 and CO2 by solving the Boltzmann equation in the condition of a steady-state Townsend(SST) experiment.The overall density-reduced electric field strength is from 100 Td to 1000 Td(1 Td = 10-17V·cm2),while the CF3I content k in the gas mixture can be varied over the range from 0% to 100%.From the variation of(αη)/N with the CF3I mixture ratio k,the limiting field strength(E/N) lim for each CF3I concentration is derived.It is found that for the mixtures with 70% CF3I,the values of(E/N) lim are essentially the same as that for pure SF 6.Additionally,the global warming potential(GWP) and the liquefaction temperature of the gas mixtures are also taken into account to evaluate the possibility of application in the gas insulation of power equipment.     

Exhaled breath condensate: Determination of non-volatile compounds and their potential for clinical diagnosis and monitoring. A review

Exhaled breath condensate is a promising, non-invasive, diagnostic sample obtained by condensation of exhaled breath. Starting from a historical perspective of early attempts of breath testing towards the contemporary state-of-the-art breath analysis, this review article focuses mainly on the progress in determination of non-volatile compounds in exhaled breath condensate. The mechanisms by which the aerosols/droplets of non-volatile compounds are formed in the airways are discussed with methodological consequences for sampling. Dilution of respiratory droplets is a major problem for correct clinical interpretation of the measured data and there is an urgent need for standardization of EBC. This applies also for collection instrumentation and therefore various commercial and in-house built devices are described and compared with regard to their design, function and collection parameters. The analytical techniques and methods for determination of non-volatile compounds as potential markers of oxidative stress and lung inflammation are scrutinized with an emphasis on method suitability, sensitivity and appropriateness. The relevance of clinical findings for each group of possible non-volatile markers of selected pulmonary diseases and methodological recommendations with emphasis on interdisciplinary collaboration that is essential for future development into a fully validated clinical diagnostic tool are given.     

两种含大吸电子取代基的SnR_2Cl_2化合物的合成和晶体结构

以SnCl4和2,4,6-(CF3)3C6H2Li、2,6-(CF3)2C6H3Li为原料合成了两种含大吸电子取代基的化合物Sn[2,4,6-(CF3)3C6H2]2Cl2(缩写为SnAr2Cl2)和Sn[2,6-(CF3)2C6H3]2Cl2(缩写为Sn Ar′2Cl2),利用X射线衍射仪和核磁共振谱仪(19F NMR)表征了产物SnAr2Cl2和SnAr′2Cl2的晶体结构.     

Remote regioselective organocatalytic asymmetric [3+2] cycloaddition of N-2,2,2-trifluoroethyl isatin ketimines with cyclic 2,4-dienones

An organocatalytic asymmetric [3+2] cycloaddition of trifluoromethyl-containing azomethine ylides with cyclic 2,4-dienones was developed.The process enables efficient incorporation of CF3 groups into functionalized spiro [pyrro lid in-3,2'-oxindoles] in high yields with good to excellent enantio-and diastereoselectivities.