Synthesis of functional polymers—Vinylidene fluoride based fluorinated copolymers and terpolymers bearing bromoaromatic side‐group

The radical co‐ and terpolymerization of 4‐[(α,β,β‐trifluorovinyl)oxy]bromo benzene (TFVOBB) with 1,1‐difluoroethylene (or vinylidene fluoride, VDF, or VF₂), hexafluoropropene (HFP), perfluoromethyl vinyl ether (PMVE), and chlorotrifluroroethylene (CTFE) is presented. Although TFVOBB could be thermocyclodimerized, it could not homopolymerize under radical initiation. TFVOBB could be copolymerized in solution under a radical initiator with VDF or CTFE comonomers, while its copolymerization with HFP or PMVE were unsuccessful. The terpolymerization of TFVOBB with VDF and HFP, or VDF and PMVE, or VDF and CTFE also led to original fluorinated terpolymers bearing bromoaromatic side‐groups. The conditions of co‐ and terpolymerization were optimized in terms of the nature of the radical initiators, and of the nature of solvents (fluorinated or nonhalogenated). Various monomer concentrations in the co‐ and terpolymers were assessed by ¹⁹F and ¹H‐NMR spectroscopy. The thermal and physico chemical properties were also studied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5077–5097, 2004     

有限局部环Z/2\+kZ上斜对称矩阵标准形和伪辛群的阶

设R=Z/2\+kZ(k>1)是\{2\}[TX-]为非单位的有限局部环. 该文首先确定了R上斜对称矩阵标准形. 设G\+m\-p(R,H)={P∈GL\-m(R)|PHP′=H}是由矩阵H确定的伪辛群,其中H=[JB((][HL(2]0[]I\+\{(v)\}\=-I\+\{(v)\}[]0[HL)][JB))]Δ，Δ=[JB((][HL(2]\{2\}[TX-]\+\{k-1\}[]\{1\}[TX-]\=-\{1\}[TX-][]0[HL)][JB))]. 其次,计算了伪辛群G\+m\-P(R,H)的阶|G\+m\-P(R,H)|.     

Physical properties and phase separation structure of Antheraea pernyi/Bombyx mori silk fibroin blend films

The physical structure and compatibility of solution-cast Antheraea pernyi/Bombyx mori silk fibroin blend films were stuided by differential scanning calorimetry (DSC), thermomechanical (TMA) and thermogravimetric (TGA) analysis, dynamic viscoelastic measurement, infrared spectroscopy, and x-ray diffractometry. The DSC curves of the blend films showed independent endotherms at 280 and 358°C, corresponding to the thermal decomposition of B. mori and A. pernyi silk fibroins with random coil conformation. The intensity was roughly proportionate to the amount of each component in the blend. The thermal behavior corresponding to the conformational transitions induced by heating on A. pernyi and B. mori silk fibroins overlapped in the temperature range 190–230°C. Thermal expansion and contraction properties, as well as weight retention behavior of the blend films were intermediate between the pure components, as shown by the TMA and TGA curves. The onset temperature of the storage modulus curve decreased markedly, approaching that of B. mori silk fibroin film when the amount of this component in the blend increased. The loss modulus curve of the blend films showed two peaks at ca. 190 and 210°C, the former corresponding to B. mori, and the latter to A. pernyi silk fibroin. Infrared spectra of the blends exhibited absorption bands characteristic of the pure components overlapping in the spectral region 2000–400 cm^?1. The x-ray diffraction peaks at 23 and 21.5°, attributed to the crystalline spacings of A. pernyi and B. mori fibroins, respectively, overlapped in the diffraction curves of the blends, while the peak at 11.4°, of A. pernyi, increased as the content of this fibroin in the blend increased. The degree of crystallinity, calculated from the x-ray diffraction curves, diminished as the amount of B. mori silk fibroin decreased. A low degree of compatibility exists between the two fibroins when they are cast from aqueous solution in the experimental conditions adopted in this work. © 1994 John Wiley & Sons, Inc.     

有序分组资料的线性趋势检验的确切概率计算

有序分组资料的线性趋势检验主要用于检验几个二项总体反应率的线性趋势；在医学与生物学中最典型的用途是研究剂量和反应的关系． 如果用Ｚ检验来代替通常在本检验中所用的卡方检验，就可容易地导出本检验的确切概率计算方法，和其他２×Ｃ有序列联表有着相同的形式．本文给出了该检验的确切概率计算方法．     

19F NMR study of relative polarities and reactivities of N-H,N-Hg,and N-Au bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and Ph3PAu derivatives in intermolecular exchange

It has been shown by the¹⁹F NMR method that the relative polarities of nitrogenelement bonds in 2-(4-fluorophenyl)benzimidazole and its PhHg and PPh₃Au derivatives increase in the order N-H19F NMR. It has been found that these reactions occur by a bimolecular associative mechanism and that the N-H bond is substantially less reactive than the N-Hg and N-Au bonds, which have identical reactivities within the limits of sensitivity of the method used.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1574–1580, August, 1995.This work was carried out with financial support from the Russian Foundation for Basic Research (Project No. 93-03-5528).     

Solvent effects in the fluorination of 1,2-dichloro-1,1-difluoroethane (R-132b) to 2-chloro-1,1,1-trifluoroethane (R-133a)

Trichloroethylene has been found to act as a rate enhancing co-factor in the liquid phase, tantalum (V) halide catalyzed, fluorine-for-chlorine exchange reaction of 1,2-dichloro-1,1-difluoroethane (R-132b) to 2-chloro-1,1,1-trifluorethane (R-133a). Several trifluoromethyl substituted benzenes have also been found to be rate-enhancing solvents.     

A neutron polarization analysis study of Ce2Fe17 in its paramagnetic phase

Spin-flip (paramagnetic) scattering and neutron depolarization studies were performed on Ce₂Fe₁₇ in its paramagnetic phase on the Dhruva neutron polarization analysis spectrometer. The absence of normalQ dependence of the scattered spin flip intensity shows that Ce₂Fe₁₇ is not a normal paramagnetic and there exist superparamagnetic clusters of sufficiently large dimensions (～100Å). The observed neutron depolarization gives an indication of the dynamics of these Ce₂Fe₁₇ superparamagnetic clusters.     

CX_2(NO_2)_2(X=H,F,C1)分子旋转势和构型稳定性的ab initio研究

本文用ab initio计算方法,采用STO-3G基组,对二硝基卤代甲烷CH_2(NO_2)_3(1),CF_2(NO_2)_2(2);CCl_2(NO_2)_2(3)等分子作了单点计算,研究其旋转势能.全构型优化研究了五个具有对称性构型的结构和稳定性,并作了理论分析和探讨.     

There exist no 2-type surfaces in E 3 which are images under stereographic projection of minimal surfaces in S 3

In this paper we deal with the following particular case of a weaker conjecture by B. Y. Chen: Are there 2-type Willmore surfaces in E ³? In particular we prove that the above question has a negative answer when the surface is the image under stereographic projection of a minimal surface in S ³.     

High sensitivity CW-cavity ring down spectroscopy of water in the region of the 1.5 μm atmospheric window

The absorption spectrum of natural water vapour around 1.5 μm has been recorded with a typical sensitivity of 5 × 10⁻¹⁰ cm⁻¹ by using a CW-cavity ring down spectroscopy set up based on fibred DFB lasers. A series of 31 DFB lasers has allowed a full coverage of the 6130.8-6748.5 cm⁻¹ (1.63-1.48 μm) region corresponding to the H transparency band of the atmosphere. The line parameters (wavenumber and intensity) of a total of 5190 lines, including 4247 lines of water vapor, were derived by a one by one fit of the lines to a Voigt profile. Different isotopologues of water (H₂¹⁶O, H₂¹⁸O, H₂¹⁷O, and HD¹⁶O) present in natural abundance in the sample contribute to the spectrum. For the main isotopologue, H₂¹⁶O, 2130 lines were measured with line intensities as weak as 10⁻²⁹ cm/molecule while only 926 lines (including a proportion of 30% inaccurate calculated lines) with a minimum intensity of 3 × 10⁻²⁷ cm/molecule are provided by the HITRAN and GEISA databases. Our comparison in the whole 5750-7965 cm⁻¹ region, has also evidenced that an error in the process of conversion of the intensity units from cm⁻²/atm to cm⁻¹/(molecule × cm⁻²) at 296 K, has led to H₂¹⁶O line intensities values listed in the HITRAN-2000 database, systematically 8 % below the original FTS values. The rovibrational assignment was performed on the basis of the ab initio calculations by Schwenke and Partridge with a subsequent refinement and validation using the Ritz combination principle together with all previously measured water transitions relevant to this study. This procedure allowed determining 172, 139, 71, and 115 new energy levels for the H₂¹⁶O, H₂¹⁸O, H₂¹⁷O, and HD¹⁶O isotopologues, respectively. The results are compared with the available databases and discussed in regard of previous investigations by Fourier transform spectroscopy. The spectrum analysis has showed that most of the transitions which cannot be assigned to water are very weak and are due to impurities such as carbon dioxide and ammonia, leaving only about 3% of the observed transitions unassigned. The interest of a detailed knowledge of water absorption for trace detectors developed in the 1.5 μm range is underlined: for instance HDO contributes significantly to the considered spectrum while no HDO line parameters are provided by the HITRAN database.