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61.
在干燥氮气气氛下,以无水乙醇为溶剂,制备了低水合氯化钕与二乙氨基荒酸二乙铵(D-DDC)配合物,确定其组成为Et2NH2[Nd(S2CNEt2)4].单晶结构分析表明,配合物中4个二乙氨基荒酸根各通过2个硫原子与钕离子成键形成八配位十二面体阴离子,并与二乙铵阳离子形成缔合型分子.晶体属单斜晶系,空间群P21/n,a=1.37517(14)nm,b=2.1146(2)nm,c=1.44641(15)nm,β=102.028(2)°,Z=4.用微量热法测定了298.15K下水合氯化钕和D-DDC在无水乙醇中的溶解焓及二乙氨基荒酸钕液相生成反应焓变分别为(-17.89±0.096),(50.280±0.151)和(-10.116±0.065)kJ/mol,求得固相生成反应焓变. 相似文献
62.
Usachev N. Ya. Belanova E. P. Krukovsky I. M. Kanaev S. A. Atal"yan O. K. Kazakov A. V. 《Russian Chemical Bulletin》2003,52(9):1940-1949
Thermal transformations in systems formed by interaction of Zn and Na nitrates with Y, X, and A zeolites were studied by TG—DTA technique. Temperature regions of existence of adsorbed water, water of crystallization, and decomposition of NO3
– anion were determined. These intervals depend on the composition, structure, method of preparation, and pre-treatment conditions of zeolite systems. The extent of NO3
– decomposition depends not only on the zinc and sodium content but also on the presence of ammonia involved in NO3
– reduction. The zeolite matrix strongly stabilizes the occluded NO3
– anions. A portion of zinc oxide formed by zinc nitrate decomposition is probably localized inside the zeolite cavities as the [Zn—O—(ZnO)
n
—Zn]2+ particles. The latter compensate charges of the isolated [AlO4]– tetrahedra. 相似文献
63.
Raman spectra of intramolecular vibration mode for each guest species in the methane + tetrafluoromethane (CF4) mixed-gas hydrate crystal have been measured at 291.1 K. Both of pure guest species generate the structure-I hydrate in the present pressure ranges. Isothermal phase-equilibrium curve exhibits two discontinuous points around the equilibrium methane compositions (water-free) in the gas phase of 0.3 and 0.8. At the above points, the Raman spectra of both guest molecules have been drastically changed. One of the most important findings is that the crystal of methane + tetrafluoromethane mixed-gas hydrate shows the structural phase-transition (from the structure-I to the structure-II and back to the structure-I) caused by composition changes. 相似文献
64.
正丁烷氧化制顺酐流化床催化剂的性能 总被引:1,自引:0,他引:1
考察了前驱体制备过程中水合肼/五氧化二钒摩尔比(以下简记\r\n为n(N2H4)/n(V2O5))对催化剂性能的影响.由较高的n(N2H4)\r\n/n(V2O5)比制得的催化剂,其(VO)2P2O7相含量较多,正丁烷转化\r\n率较高.随着n(N2H4)/n(V2O5)比的减小,δ-VOPO4相的含量逐\r\n渐增多,正丁烷转化率随之升高;而顺酐选择性开始时升高,达到最大\r\n值后逐渐降低.在n(N2H4)/n(V2O5)=0.34时制备的催化剂最佳\r\n,在丁烷浓度为4.0%、空速为500h-1及反应温度为420℃的反应条件\r\n下,顺酐收率可达49.74%.本文中细粒床催化剂有较大的操作弹性. 相似文献
65.
Oxidative free radical reactions of enamino esters are described. Electrophilic carbon-centered radicals produced by the cerium(IV) ammonium nitrate (CAN) oxidation of β-dicarbonyl compounds undergo efficient addition to the C-C double bond of enamino esters. This CAN mediated free radical reaction between enamino esters and β-dicarbonyl compounds provides a novel method for the synthesis of highly substituted pyrroles. The direct CAN oxidation of β-enaminocinnamates gave the dimerization products effectively. 相似文献
66.
67.
Fan CA Hu XD Tu YQ Wang BM Song ZL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4301-4310
A novel and highly diastereoselective samarium-catalyzed tandem rearrangement/reduction of secondary alpha-hydroxy epoxides, which involves a C1 to C3 carbon migration rearrangement and a very interesting hetero-Tishchenko reduction of the intermediate aldehyde and the reductant aldehyde, has been reported. This reaction could be developed to provide a facile and stereoselective construction of 2-quarternary 1,3-diol units with an hydroxymethyl moiety attached to the diastereogenic quaternary carbon center. Detailed investigations have been carried out concerning the screening of the aldehydes as a reductant, the optimization of reaction conditions, and the substrate scope of this tandem reaction. A catalytic cycle for this reaction, the electronic and steric effects of the reductant aldehydes, and the mechanism for the acyl migration of 1,3-diol monoesters are proposed. 相似文献
68.
69.
硝酸镧对大鼠肝脏癌前病变发展的抑制作用及机制的初步探讨 总被引:2,自引:2,他引:2
研究硝酸镧对大鼠肝脏癌前病变的抑制作用及机制. 采用肝癌发生的短期动物模型, 连续用0.2, 10 mg·kg-1的La(NO3)3灌胃2个月后, 观察了不同剂量La(NO3)3对大鼠肝脏形态结构的影响, 免疫组化技术检测肝脏中细胞周期素D1和P16及PCNA的表达, 并做半定量分析. 同时取脾细胞进行淋巴细胞转化率试验. 结果表明, 0.2 mg·kg-1剂量硝酸镧组动物健康状况明显改善, 肝癌前病变程度明显减轻, cyclinD1, PCNA表达下降, P16表达上升, 淋巴细胞转化率升高. 提示低剂量硝酸镧具有一定阻抑肝癌前病变的作用. 相似文献
70.
From relative integrated intensity measurements of the symmetric stretching vibration of nitrate ion in nitric acid solutions (both HNO
3
/H
2
O and DNO
3
/D
2
O), the mass law concentration quotients, Q
were obtained as functions of concentration. By extrapolation the limiting dissociation constants were estimated to be 24.4 and 15 respectively at 25°C. It is shown that this constant refers to a process in which the ion pair H
3
O+ NO
3
–
is in equilibrium with the dispersed, solvated H
3
O+ and NO
3
–
ions. 相似文献