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131.
Ab initio molecular orbital calculations employing a 4-31G basis set have been used to study the minimum energy paths for the formation of HCO+, COH+, and HCOH2+ from CO by protonation. The protonation of N2 to give NNH+ and HNNH2+ and of NO+ to form HNO2+ and NOH2+ have also been investigated. All species formed have linear equilibrium geometries and the minimum energy path for approach of the proton is along the line-of-centers of the heavy atoms. Energy barriers to the formation of the various species are given, where appropriate, and changes in geometry, ordering of molecular orbitals and orbital occupancy are discussed. 相似文献
132.
Aqueous polymerization of acrylonitrile (M) initiated by the Ce(IV)-glucose (R) redox system has been studied under nitrogen in the temperature range of 30–40 °C. The rate of polymerization (Rp) is proportional to [M]2, [R] and inversely proportional to [Ce(IV)]. The rate of ceric ion disappearance is proportional to [R] and [Ce(IV)]. The end group in the polymer is characterised by IR spectra. A suitable kinetic scheme has been proposed and explained in the light of these experimental findings. 相似文献
133.
《Electroanalysis》2006,18(11):1097-1104
Copolymerization of an osmium(II) functionalized pyrrole moiety, osmium‐bis‐N,N'‐(2,2′‐bipyridyl)‐N‐(pyridine‐4‐ylmethyl‐(8‐pyrrole‐1yl–octyl)‐amine)chloride ( I ) with 3‐methylthiophene was carried out. The resulting conducting polymer film exhibited a clear redox couple associated with the Os3+/2+ response and the familiar conducting polymer backbone signature. The effect of film thickness upon the redox properties of the copolymer was investigated in organic electrolyte solutions. Scanning electron micrographs (SEM) along with energy dispersive X‐ray (EDX) spectra of the copolymerized films were undertaken, both after formation and redox cycling in neutral buffer solution. These clearly show that electrolyte is incorporated into the polymer film upon redox cycling through the Os3+/2+ redox system. The Os3+/2+ response associated with the copolymer was seen to be significantly altered in the presence of ascorbic acid both in acidic and neutral pH buffer solutions. This pointed to an electrocatalytic reaction between the ascorbic acid and the Os3+ form of the copolymer. Under acidic conditions the copolymer film exhibited a sensitivity of 1.76 (±0.05) μA/mM with a limit of detection (LOD) of 1.45 μM for ascorbic acid. Under neutral pH conditions the copolymer exhibited a sensitivity of 19.26 (±1.05) μA/mM with a limit of detection (LOD) of 1.28 μM for ascorbic acid. 相似文献
134.
《Surface and interface analysis : SIA》2005,37(9):713-720
The surface structure of polytetrafluoroethylene (PTFE) upon α‐particle irradiation has been investigated at doses in the range of 1 × 107 to 1 × 1011 Rad and compared with the surface structure of the unirradiated polymer. Both neat and 25% fiberglass content PTFE were studied. The samples, maintained at nominal room temperature, were irradiated in vacuum by 5.5 MeV 4He2+ ions generated in a tandem accelerator beam line. Static time‐of‐flight SIMS (ToF‐SIMS) was employed to probe chemical changes at the surface as a function of the irradiation level. In general, the data are indicative of increased cross‐linking at α‐doses less than 1 × 109 Rad, followed by increased fragmentation and unsaturation at α‐doses greater than 1 × 109 Rad. Throughout the irradiation regime, scission is a constant factor promoting cross‐linking, branching, and unsaturation. However, at α‐doses greater than 1 × 1010 Rad, extreme structural degradation of the polymer becomes evident and is accompanied by conversion to oxygen‐functionalized and aliphatic compounds. Thus, for PTFE in an α‐particle field, an upper exposure limit of ~1010 Rad is essential for nominal retention of molecular structure. Finally, a quantitative relationship between α‐dose and characteristic fragment ion intensity is developed. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
135.
A. Manjon J. A. Ferragut J. C. Garcia-Borron J. L. Iborra 《Applied biochemistry and biotechnology》1984,9(2):173-185
Fluorescence spectra and soluble quenching of intrinsic protein fluorescence were used as indexes of conformational changes
suffered by frog epidermis tyrosinase. The activation process and the immobilization of the enzyme involving either free amino
groups or its carbohydrate moiety were studied. The conformational changes resulting from denaturation of each one of the
protein derivatives, as well as the effect of active center copper extraction, were followed by fluorescence studies.
The results showed that: (a) both activation and immobilization were accompanied by conformational changes of the protein
leading to more unfolded states; (b) neither enzyme nor immobilized enzyme were fully unfolded upon denaturation although
enzymic activity was lost; (c) the enzyme immobilized through its carbohydrate moiety was more unfolded upon denaturation
than the enzyme immobilized through amino groups, thus pointing to a higher conformational stabilization in the last situation;
and (d), that tryptophyl residues moved to a localization near the active site upon activation. 相似文献
136.
Alkylidynephosphanes and -arsanes. I [P ≡ C? S]?[Li(dme)3]+ – Synthesis and Structure O,O′-Diethyl thiocarbonate and bis(tetrahydrofuran)-lithium bis(trimethylsilyl)phosphanide dissolved in 1,2-dimethoxyethane, react below 0°C to give ethoxy trimethylsilane and tris(1,2-dimethoxyethane-O,O′)lithium 2λ3-phosphaethynylsulfanide – [P≡C? S]? [Li(dme)3]+ – ( 1a ). Apart from bis(trimethylsilyl)sulfane or carbon oxide sulfide, dark red concentrated solutions of λ3-phosphaalkyne 1 are also obtained from reactions of carbon disulfide with bis(tetrahydrofuran)-lithium bis(trimethylsilyl)phosphanide or with the homologous lithoxy-methylidynephosphane ( 2 ) [1]. The ir spectrum shows two absorptions at 1762 and 747 cm?1 characteristic for the P≡C and C? S stretching vibrations. The nmr parameters {δ(31P) ? 121.3; δ(13C) 190.8 ppm; 1JCP 18.2 Hz} resemble much more values of diorganylamino-2λ3-phosphaalkynes than those of bis(1,2-dimethoxyethane-O,O′)lithoxy-methylidyne-phosphane ( 2a ). As found by an X-ray structure analysis (P21/c; a = 1192.6(16); b = 1239.1(19); c = 1414.8(26) pm; β = 105.91(13)° at ?100 ± 3°C; Z = 4 formula units; wR = 0.064) of pale yellow crystals (mp. + 16°C) isolated from the reaction with O,O′-diethyl thiocarbonate, the solid is built up of separate [P≡C? S]? and [Li(dme)3]+ ions. Typical bond lengths and angles are: P≡C 155.5(11); C? S 162.0(11); Li? O 206.4(17) to 220.3(20) pm; P≡C? S 178.9(7)°. 相似文献
137.
A New Tricyclic Sulfur-rich Phosphane From the products of the reaction of P4S3 with tert-Butyliodide the compound (t-Bu(S)P)2P4S3 was isolated in low yield. The compound is stable and has a structure related to the hydrocarbon brexane. By reaction with triphenylphosphin the compounds (t-BuP)(t-Bu(S)P)P4S3 and (t-BuP)2P4S3 were obtained. The 31P-nmr spectra of all compounds were solved and used to determine the structure of the molecules. A complete set of 31P-nmr data is given. 相似文献
138.
Summary The SCF method is applied to determine the (gas phase) structure of [(CF3)2PN]2NVCl2, which agrees with the solid-state X-ray structure within typical errors of 2 pm and 2° in bond distances and angles. The electronic structure of atoms forming the ring is best described in terms of divalent N– and tetravlent P+ with appreciable declocalization of nitrogen lone pairs into low-lying empty orbitals of neighbouring atoms P and V. No evidence for aromaticity of the ring system is found. 相似文献
139.
综述了近年来利用一些新型的含氟砌块,通过它们的环加成反应来高效地合成 含氟杂环化合物的研究,其中包括以下两个部分:(1)用1,3—偶极环加成反应合 成五元含氟杂环化合物;(2)用杂原于Diels-Alder反应合成六元含氟杂环化合物. 相似文献
140.
本文提出一种用于海洋温跃层边界提取的组合算法,该算法基于调整判定阈值后的垂直梯度法和一种改进函数模型几何形态后的拟阶梯函数逼近法。为验证该算法对于温跃层边界提取的适应性、客观性,利用中国Argo实时资料中心发布的全球海洋Argo网格资料集(BOA_Argo),选取2018年夏季0°~30°N,135°E~165°E所在的太平洋区域的温度剖面数据进行处理,结果表明,该算法对低纬度海区温度剖面拟合质量较好,拟合均方根误差普遍低于1.3℃,而且提取到的温跃层上下边界在纬向更加平缓,然而对于中高纬度海区的温度剖面,组合算法的处理效果不佳,更适合直接通过垂直梯度法进行温跃层的提取。 相似文献