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91.
Chen-Xi Zhang Zhi-Liang Liu Dai-Zheng Liao Zong-Hui Jiang Shi-Ping Yan 《Journal of Molecular Structure》2003,650(1-3):21-26
A novel complex [Cu(NIT2Py)(PDA)(H2O)]·(CH3OH)(H2O) has been synthesized and structurally characterized by X-ray diffraction methods. It crystallizes in the monoclinic space group P2(1)/c. The structure consists of [Cu(NIT2Py)(PDA)(H2O)] moiety, one solvent methanol molecule and one water molecule. The copper(II) ion is in a distorted octahedral environment: one nitrogen atom and one oxygen atom from the NIT2Py, one nitrogen atom from the PDA (2,6-pyridine dicarboxylic acid) and one oxygen atom from the aqueous in the basal plane; two oxygen atoms from the PDA in the axial position. The units of [Cu(NIT2Py)(PDA)(H2O)] were connected as one dimension chain by the intermolecular hydrogen bonds. The complex exhibits intramolecular antiferromagnetic interactions between the Cu(II) ion and the NIT2Py. 相似文献
92.
Mets motifs, which refer to methionine-rich sequences found in the high-affinity copper transporter Ctr1, also appear in other proteins involved in copper trafficking and homeostasis, including other Ctrs as well as Pco and Cop proteins isolated from copper-resistant bacteria. To understand the coordination chemistry utilized by these proteins, we studied the copper binding properties of a peptide labeled Mets7-PcoC with the sequence Met-Thr-Gly-Met-Lys-Gly-Met-Ser. By comparing this sequence to a series of mutants containing noncoordinating norleucine in place of methionine, we confirm that all three methionine residues are involved in a thioether-only binding site that is selective for Cu(I). Two independent methods, one based on mass spectrometry and one based on rate differences for the copper-catalyzed oxidation of ascorbic acid, provide an effective K(D) of approximately 2.5 microM at pH 4.5 for the 1:1 complex of Mets7-PcoC with Cu(I). These results establish that a relatively simple peptide containing an MX(2)MX(2)M motif is sufficient to bind Cu(I) with an affinity that corresponds well with its proposed biological function of extracellular copper acquisition. 相似文献
93.
A method has been developed for the speciation of trace dissolved Fe(II) and Fe(III) in water by coupling gallic acid (GA) modified nanometer-sized alumina micro-column separation with inductively coupled plasma mass spectrometry (ICP-MS). The separation of Fe(II) and Fe(III) was achieved based on the obvious difference in reaction kinetics between Fe(II) and Fe(III) with GA. Fe(III) was selectively retained on the micro-column at pH 5.5-6.5, while Fe(II) could not be retained by the micro-column at the whole tested pH range of 1.0-6.5, and passed through the micro-column. The Fe(II) can be determined by ICP-MS directly without preconcentration/separation procedure, while Fe(III) retained on the micro-column was then eluted with 1.0 mL of 1 mol L(-1) HCl and determined by ICP-MS. The parameters affecting the separation of Fe(II) and Fe(III) were investigated systematically and the optimum separation conditions were established. Under the optimized conditions, the detection limits of 0.48 microg L(-1) and 0.24 microg L(-1) with relative standard deviation of 5.6% and 4.3%(C= 5 microg L(-1), n= 7) for Fe(II) and Fe(III) were found, respectively. No obvious effect on the speciation of Fe(II) and Fe(III) was found with the change of the ratio of Fe(II) and Fe(III) from 0 ratio 10 to 10 ratio 0. The proposed method was applied for the determination of trace Fe(II) and Fe(III) in environmental water and the recoveries for spiked samples were found to be in the range of 97-105%. 相似文献
94.
Tuo Jiang Samuele Bordi Angus E. McMillan Kuang-Yen Chen Fumito Saito Paula L. Nichols Benedikt M. Wanner Jeffrey W. Bode 《Chemical science》2021,12(20):6977
The current laboratory practices of organic synthesis are labor intensive, impose safety and environmental hazards, and hamper the implementation of artificial intelligence guided drug discovery. Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions with prepacked capsules. The machine conducts coupling reactions and delivers the purified products with minimal user involvement. Two desirable reaction classes – the synthesis of saturated N-heterocycles and reductive amination – were implemented, along with multi-step sequences that provide drug-like organic molecules in a fully automated manner. We envision that this system will serve as a console for developers to provide synthetic methods as integrated, user-friendly packages for conducting organic synthesis in a safe and convenient fashion.Using a combination of reagent design, hardware engineering, and a simple operating system we provide an instrument capable of executing complex organic reactions using prepacked capsules with minimal user involvement. 相似文献
95.
Lu Y Zou J Wang H Yu Q Zhang H Jiang Y 《The journal of physical chemistry. A》2005,109(51):11956-11961
Triangular halogen trimers (RX)3, where X = Br, I and R represents H, H3C, H2FC, HF2C, F3C, CH2=CH, CH[triple bond]C, and Ph, have been investigated using the density functional theory in the Perdew, Burke, and Ernzerhof method. We report herein the optimized geometries of the stable structures, their vibrational frequencies, and binding energies with the two- and three-body terms. All trimer structures possess a cyclic array of halogen atoms in the type II approach by virtue of the nonspherical atomic charge distribution around the halogens. The Br...Br interactions in trimers are very weak, whereas the I...I interactions in trimers are relatively stronger. While all bromine trimers and most of iodine trimers are predicted to be noncooperative, three of iodine trimers show weak cooperativity. The analysis of vibration modes reveals that all halogen trimers exhibit no especially remarkable frequency shifts. It is also shown that the electrostatic contribution plays a major role in the halogen...halogen interactions in halogen trimers. In contrast to bromine trimers, the relative contribution of charge-transfer component to the halogen...halogen interactions becomes more important for iodine trimers. 相似文献
96.
Pt/钇稳定氧化锆固体电解质在高温下的电化学性质 总被引:1,自引:0,他引:1
用交流阻抗技术研究了二电极、三电极Pt/钇稳定氧化锆(简称YSZ)高温固体电化学体系.开路电位下,Pt/YSZ体系只有一个阻抗半圆,对应于电极体系的电化学活化控制过程,极化电阻随温度变化的表观活化能为171.5kJ/mol.Pt/YSZ界面的双电层电容约为300μF/cm2.阳极极化下,交流阻抗极化电阻显著减小;阴极极化下,极化电阻反而增大,并出现浓差控制现象. 相似文献
97.
An efficient Pd‐catalyzed three‐component coupling reaction of allyl carboxylates, norbornenes and diboronates is described, which allows efficient assembly of C(sp3)—C(sp3) and C(sp3)—B bonds in a single process. Moreover, this approach shows advantages of good chemo‐ and regioselectivity, as well as good substrates suitability. 相似文献
98.
聚硅氧烷涂敷的反相高效液相色谱固定相 总被引:5,自引:1,他引:5
用甲基乙烯基聚硅氧烷涂敷于硅烷化的微粒硅胶上,制备出一种新型的涂敷型反相高效液相色谱固定相。该固定相对极性、非极性和碱性化合物均有良好的分离能力,峰对称性好。对其恶性循环 了考察,连续使用三个月后,固定相的碳量和色谱性能仍保持不变。 相似文献
99.
亚临床肝性脑病患者的血清锌,铜含量的测定及临床意义 总被引:1,自引:0,他引:1
检测了30例慢性活动性肝炎患者、30例肝硬化患者、30例亚临床肝性脑病患者血清中的铜、锌含量,并与正常对照组进行比较分析,探讨了微量元素铜、锌的血清含量改变及其影响因素,分析其临床意义。结果表明体内的铜锌含量与肝脏功能有密切的关系。在慢性活动性肝炎时,虽然肝脏功能有一定的损害,但由于肝脏的代偿能力强,铜,锌含量仍可保持在正常水平,而在肝硬化、亚临床肝性脑病时,铜锌明显降低,而铜锌含量的降低又导致机 相似文献
100.
Mesylate derivatives of 3-aryl-3-hydroxy-beta-lactams and thiolactams react in DMSO-d(6) by first-order processes to give alcohol products. Substituent effect studies implicate carbocation intermediates (ion-pairs) that are captured by DMSO-d(6) to give transient oxosulfonium ions. Rapid reaction of the oxosulfonium ions with trace amounts of water leads to the alcohol product and regenerates DMSO-d(6). H(2)(17)O labeling studies show that (17)O is incorporated into the DMSO. The mesylate derivatives of endo- and exo-2-hydroxy-2-phenylbicyclo[2.2.1]heptan-3-one also react in DMSO-d(6) to give the alcohol products. Ion-pair intermediates that capture DMSO giving unstable oxosulfonium ions are again proposed. Exo-2-phenyl-endo-bicyclo[2.2.1]heptyl trifluoroacetate readily eliminates trifluoroacetic acid in DMSO-d(6) via a cationic mechanism involving loss of the endo-trifluoroacetate leaving group as well as an exo-hydrogen. The O-methyl oxime derivative of alpha-chloro-alpha,alpha-diphenylacetophenone reacts in DMSO-d(6) to give 1-methoxy-2,3-diphenylindole, a product derived from cyclization of a cationic intermediate. A common ion rate suppression provides further evidence for a cationic mechanism. The triflate derivative of pivaloin reacts by a cationic mechanism in DMSO-d(6) to give rearranged products. The rate is even faster than in highly ionizing solvents such as trifluoroethanol or trifluoroacetic acid. 1-Adamantyl mesylate reacts in DMSO-d(6) by a first-order process (Y(OMs) = -4.00) to give a long-lived oxosulfonium ion, 1-Ad-OS(CD(3))(2)(+), which can be characterized spectroscopically. This oxosulfonium ion reacts only slowly with water at elevated temperatures to give 1-adamantanol. DMSO is therefore a viable solvent for k(s), k(C), and k(Delta) cationic processes. 相似文献