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41.
Jiang J Renshaw JC Sarsfield MJ Livens FR Collison D Charnock JM Eccles H 《Inorganic chemistry》2003,42(4):1233-1240
The solution chemistry of uranyl ion with iminodiacetate (IDA) and oxydiacetate (ODA) was investigated using NMR and EXAFS spectroscopies, potentiometry, and calorimetry. From the NMR and EXAFS data and depending on stoichiometry and pH, three types of metal:ligand complex were identified in solution in the pH range 3-7: 1:1 and 1:2 monomers; a 2:2 dimer. From NMR and EXAFS data for the IDA system and previous studies, we propose the three complex types are [UO(2)(IDA)(H(2)O)(2)], [UO(2)(IDA)(2)](2)(-), and [(UO(2))(2)(IDA)(2)(mu-OH)(2)](2)(-). From EXAFS spectroscopy, similar 1:1, 2:2, and 1:2 complexes are found for the ODA system, although (13)C NMR spectroscopy was not a useful probe in this system. For the 1:1 and 1:2 complexes in solution, EXAFS spectroscopy is ambiguous because the data can be fitted with either a long U-N/O(ether) value (ca. 2.9 A) suggesting 1,7-coordination of the ligand or a U-C interaction at a similar distance, consistent with terminal bidentate coordination. However, the NMR data of the IDA system suggest that 1,7-coordination is the more likely. The stability constants of the three complexes were determined by potentiometric titrations; the log beta values are 9.90 +/-, 16.42 +/-, and 10.80 +/- for the 1:1, 1:2, and 2:2 uranyl-IDA complexes, respectively, and 5.77 +/-, 7.84 +/-, and 4.29 +/- for the 1:1, 1:2, and 2:2 uranyl-ODA complexes, respectively. The thermodynamic constants for the complexes were calculated from calorimetric titrations; the enthalpy changes (kJ mol(-)(1)) and entropy changes (J K(-)(1) mol(-)(1)) of complexation for the 1:1, 1:2, and 2:2 complexes respectively are the following. IDA: 12 +/- 2, 230 +/- 8; 8 +/- 2, 151 +/- 9; -33 +/- 3, -283 +/- 11. ODA: 26 +/- 2, 198 +/- 12; 20 +/- 2, 106 +/- 8; -24 +/- 2; -219 +/- 8. 相似文献
42.
A highly effective, economical, and environmentally friendly method using of CAN as oxidant and water as solvent for oxidative coupling of N,N-dialkylarylamines was reported. 相似文献
43.
The cyclopeptide, squamtin A (1, formula: C39H60O11N8S), was found to crystallized in two pseudopolymorphisms, i.e. 1·(H2O)3.5 and 1·(H2O)3.9. The composition of the amino acids and their linkage sequences are the same. The main differences between the two kinds of crystals lie in the positions and occupancies of the water molecules, the positions of the sulfur atoms and the conformation of the side chains. The absolute configuration of 1 is established by X-ray analysis in combination with the Marfey's analysis of its hydrolysates. 相似文献
44.
Microwave-assisted synthesis of sulfide M2S3 (m = Bi, Sb) nanorods using an ionic liquid 总被引:1,自引:0,他引:1
Single-crystalline Bi(2)S(3) and Sb(2)S(3) nanorods have been successfully synthesized by the microwave-assisted ionic liquid method. The starting reagents were Bi(2)O(3) or Sb(2)O(3), HCl, Na(2)S(2)O(3), and ethylene glycol (EG) or ethanolamine, and the ionic liquid used was 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF(4)]). Our experiments showed that the ionic liquid played an important role in the morphology of M(2)S(3) (M = Bi, Sb). Single-crystalline Bi(2)S(3) nanorods could be prepared in the presence of [BMIM][BF(4)]. However, urchinlike Bi(2)S(3) structures consisting of nanorods were formed without using [BMIM][BF(4)]. Single-crystalline Sb(2)S(3) nanorods were obtained in the presence of [BMIM][BF(4)]. However, single-crystalline Sb(2)S(3) nanosheets could be prepared in the absence of [BMIM][BF(4)]. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), and electron diffraction (ED). 相似文献
45.
[structure: see text] A family of chiral metallacyclophanes has been readily assembled based on robust Pt-acetylide linkage and characterized by a variety of spectroscopic techniques and X-ray crystallography. The steric congestion around the chiral dihydroxy groups in rigid metallacyclophane 4 prevents their reactions with Ti(O(i)()Pr)(4) to form active catalysts for enantioselective diethylzinc additions to aromatic aldehydes. In contrast, chiral dihydroxy groups in more flexible unclosed metallacyclophane 5 are effective ligands for enantioselective catalytic diethylzinc additions to aromatic aldehydes. 相似文献
46.
盾构机掘进过程中,千斤顶顶进力的不均匀引起的纵向位移是管片间初始错台的主要原因之一;基于Timoshenko梁理论的隧道纵向位移计算方法,未能考虑隧道开挖后围岩卸载破坏的变形特征及围岩与衬砌结构的协同作用效应,预测误差较大。建立了考虑围岩卸载扩容效应的等效地基抗力系数计算方法,提出了能考虑螺栓个数的等效抗剪刚度计算公式,建立一种基于Timoshenko梁理论的改进管片拼装式隧道纵向位移理论计算方法。实际工程案例分析表明:考虑围岩开挖卸载过程中围岩的非线性体积相关塑性变形(即扩容效应)更合理;考虑壁后注浆液固化过程的时效性,采用改进的滑移边界条件计算的纵向位移最大值是传统的固定端边界的计算值的2.3倍,边界条件对计算结果影响较大,本文计算方法更符合实际情况,也更安全。 相似文献
47.
为了解决无线供电网(wireless powered communication network,WPCN)中用户公平性不足与系统灵活性差的问题,提出一种基于智能反射面(intelligent reflecting surface,IRS)的优化方案。该方案直接将公平指数(fairness index,FI)和系统吞吐量加权相加作为优化目标,建立了用户公平性与系统吞吐量的联合优化问题。由于所建立的优化问题是非凸问题,因此,将优化问题拆分为时隙长度和IRS反射系数优化子问题,然后交替求解。针对时隙长度优化子问题,使用逐次凸逼近(successive convex approximation,SCA)算法求解;针对IRS反射系数优化子问题,使用闭式解、SCA和半定松弛(semi definite relaxation,SDR)算法求解。仿真结果表明,所提方案在用户公平性和系统灵活性方面优于其他方案。 相似文献
48.
本文介绍乌龙茶做青环境电脑控制系统中的温、湿度测量、A/D转换卡、输出控制电路的硬件、接口设计原理以及系统软件与控制方式。该系统对乌龙茶做青生产过程的环境能进行自动巡回检测,控制温、湿度达到最佳状态,并使生产过程自动化。 相似文献
49.
50.
Integrable systems of NLS type in 2+1 dimensions are studied in three ways: their special solutions by Lie point symmetries, breaking-solutions by the ISM, as well as the non-isospectral problems.Department of Mathematics, Statistics and Computing Science, University of New England, Armidale N.S.W. 2351, Australia. E-mail: zhuhan@neumann.une.edu.au, xhe@metz.une.edu.au Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 99, No. 3, pp. 382–389, June, 1994. 相似文献