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971.
《Journal of Coordination Chemistry》2012,65(7):1036-1045
Neutral complexes of Cu(II), Ni(II), Co(II), and Zn(II) have been synthesized from the oxamide-based ligand derived from leucine and diethyloxalate. The structural features have been deduced from their microanalytical, IR, UV/Vis, mass, 1H and 13C NMR spectral data. The Co(II) and Ni(II) chelates have octahedral geometries and the Cu(II) chelate is a square-pyramidal geometry. The non-electrolytic and monomeric nature of the complexes is shown by their magnetic susceptibility and low conductance data. The biological activities of the ligand and its metal chelates against gram-positive and negative bacteria and fungi are also reported. All the compounds are antimicrobially active and show higher activity than the free ligand. 相似文献
972.
《Physics and Chemistry of Liquids》2012,50(1):102-112
The complex permittivity of glycine in water mixture for various temperatures and concentrations have been measured as a function of frequency between 10?MHz and 30?GHz using time domain reflectometry technique. Dielectric parameters, i.e. static dielectric constant and relaxation time were obtained from the complex permittivity spectra using nonlinear least square fit method. The dielectric relaxation parameter increases with an increase in molar concentration of glycine due to the formation of hydrogen bond groups by glycine molecule in an aqueous solution medium. The activation entropy, activation enthalpy and Kirkwood correlation factor have also been determined for glycine–water mixtures. 相似文献
973.
《Journal of Coordination Chemistry》2012,65(1):91-97
Abstract The stability constants of Zn(II) complexes with N,N″-bis-(2-hydroxybenzyl)-diethylenetri-amine(H2L) were determined by potentiometric pH titration at 25°C and at 0.1 M KNO3 ionic strength. A neutral complex ZnL was synthesized. In addition to IR, and 1H NMR spectra, its structure was established by single crystal X-ray diffraction. The crystal is orthorhombic, of space group Pbca, with cell constants a = 17.865(4), b = 20.079(4), c = 9.598(2)Å, z = 8 and Dc = 1.461 g°Cm?3. The structure was solved and refined to R = 0.049 (Rw = 0.054). The coordination geometry around the zinc ion is trigonal-bipyramidal with a large distortion, exhibiting two nonequivalent phenolates. 相似文献
974.
《Journal of Coordination Chemistry》2012,65(14):2419-2442
This review deals with modern theoretical and experimental approaches as well as structural elucidation of small peptides (SP), their protonated forms and metal complexes. Free peptide bond rotation in amino acids (AA) and peptides yielded various conformers, which may possess differing biological activities. Inter- and/or intramolecular stacking observed in aromatic SP is another phenomenon typical for both peptide salts and complexes. These phenomenological effects can be successfully studied, both theoretically and experimentally, using a combination of the theoretical approximations and physical methods, such as electronic absorption spectroscopy, vibrational spectroscopy (including IR and Raman), nuclear magnetic resonance, mass spectrometry, as well as single-crystal X-ray diffraction. The physical and chemical properties of these systems can be precisely calculated by ab initio and DFT methods, varying basis sets and the results obtained allow elucidation of their conformations as a function of the reaction conditions (pH, type of the solvent, temperature, metal to ligand molar ratio). Although the 3-D structures of many peptides have been determined over the past decades, peptide crystallization is still a major obstacle to crystallographic work and the presence of chiral center/s adds further difficulties. For this reason, a specific part of the review is focused on the study of the absolute structure of the peptides, their salts and metal complexes, discussing the conformational preferences of the peptides during these processes. The available crystallographic data for metal complexes are successfully used for the correlation between the structures and the spectroscopic properties. 相似文献
975.
《Journal of Coordination Chemistry》2012,65(20):3366-3376
Syntheses of copper(II) complexes of 20-membered and 15-membered aza macrocycles 1,3,6,8,11,13,16,18-octaaza-2,7,12,17-tetrachlorocycloeicosane (OTCE, [20]-N8) and 1,3,6,8, 11,13-hexaazacyclopentadecane (HCPD, [15]-N6) involving metal template condensation between 1,2-diaminoethane, trichloromethane and dichloromethane, respectively, are reported. Formulation of [Cu4(OTCE)(H2O)8]Cl8 and [Cu3(HCPD)(H2O)6]Cl6 · 2H2O and the ligand hydrochlorides OTCE · 8HCl and HCPD · 6HCl are supported by elemental analyses, conductivity measurements, and spectral studies. For a comparative cavity size effect on the stability constant, potentiometric measurements on the copper complexes of the generated macrocycles [15]-N6 and [20]-N8 and the structurally related larger macrocycle 1,3,6,8,11,13,16,18,21,23-decaaza-2,2,7,7,12,12,17,17,22,22-decachlorocyclopentacosane (DDCP, [25]-N10, prepared recently) have been performed in aqueous solution at 25°C (μ = 0.1 M KNO3). Very high stability constants obtained for reaction Cu2+ + A ? CuA2+ (A = ligand, log K = 20.51 and 25.87, respectively, for OTCE and DDCP systems) are a reflection on the folding of the ligand to provide a small cavity suitable for fitting of the copper ion. Further, a high equilibrium constant value for CuA2+ + Cu2+ ? Cu2A4+ (OTCE system, log K = 14.59) or Cu2A4+ + Cu2+ ? Cu3A6+ (DDCP system, log K = 16.69) is due to suitable fitting of two and three copper ions in the 20-membered and 25-membered ring cavity of OTCE and DDCP, respectively. 相似文献
976.
《Journal of Coordination Chemistry》2012,65(4):725-741
Pyrazolato endogenous bridged binuclear CoII, NiII, CuII, and ZnII complexes were prepared and characterized by spectro-analytical methods. The hexadentate N4S2 donor was synthesized by condensation of 3,5-dichloroformyl-1H-pyrazole with thiosemicarbazide in dry ethanol. All the complexes were binuclear and octahedral in nature. The ligand and complexes are screened for antimicrobial and DNA-binding/cleavage activities. The binding/cleavage activities with Escherichia coli DNA are monitored with absorption, hydrodynamic, thermal denaturation, and electrophoresis studies. The ligand possesses significant activity against microbes which is further enhanced upon complexation. The DNA-binding study reveals classical intercalation. The NiII and CuII complexes exhibit higher binding ability. 相似文献
977.
E. A. Rebrov N. A. Tebeneva A. M. Mouzafarov Yu. E. Ovchinnikov Yu. T. Struchkov T. V. Strelkova 《Russian Chemical Bulletin》1995,44(7):1286-1292
The hydrolytic condensation of methyltris(methyldichlorosiloxy)silane (1b), methyl(1a), and vinyltris(methyldiethoxysiloxy)silanes (1c) in dilute homogeneous solutions was studied. It was found by X-ray diffraction and1H NMR methods that, irrespective of reaction conditions, only octaorganooctasilsesquioxanes (T
8), namely, octamethyloctasilsesquioxane and 1,4-divinylhexamethyloctasilsesquioxane, were obtained instead of the expected tetraorganotetrasilsesquioxanes (T
4). These data suggest that the condensation processes involved in the hydrolysis of1a–c are predominantly intermolecular, and the molecules of the starting oligomers do not undergo rearrangements. Probably, the formation ofT
4, whose molecules are built of four strained six-membered organosiloxane cycles, is less favorable thermodynamically than the formation of their homologs (T
8) built of eightmembered organosiloxane cycles.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1332–1339, July, 1995. 相似文献
978.
V. V. Sharutin V. V. Zhidkov D. V. Muslin N. Sh. Liapina G. K. Fukin L. N. Zakharov A. I. Yanovsky Yu. T. Struchkov 《Russian Chemical Bulletin》1995,44(5):931-936
A series of aroxytetraphenylstiboranes, Ph4SbOAr, were obtained by the reaction of pentaphenylstiborane with phenols at 20 °C. The thermolysis of these compounds givesO- or o-C-phenylation products. The thermolysis of stiboranes, which incorporate aryl groups containing electron-withdrawing substituents (Ar=2,4-Br2, 2,4-Cl2, 2-NO2, 4-OPh) produces predominantly simple diaryl ethers of asymmetric structure in 58 %, 90 %, 32 %, and 60 % yields, respectively.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 958–963, May, 1995. 相似文献
979.
Prerna Aggarwal Virendra SinghArjun Singh U.W. SchererTejvir Singh Madan L. SinglaAlok Srivastava 《Radiation Physics and Chemistry》2012,81(3):284-289
Thin films of poly(ethyleneterephthalate) (PET) were exposed to different radiation dose brought about by 80 MeV carbon and 98 MeV silicon ion beam. The UV-vis absorption studies reveal that there is decrease in optical band gap energy to the extent of ∼29.3 and 42.1%. The X-ray diffraction analyses have shown that crystallite size decreased by ∼18.6 and 52.6%, indicating amorphization of PET. The colour of PET films change from colourless to light yellowish followed by light brown as radiation dose is increased. The colour formation has been ascribed to an increase in conjugation in the carbon chain. In the case of PET irradiated with carbon ion, the electrical conductivity increased with frequency beyond a threshold value of 1 kHz. The increase in conductivity of PET films on irradiation is due to formation of defects and carbon clusters as a result of polymer chain scission. The thermal study further confirmed the increase in amorphous nature with increase in radiation dose. The results indicate that radiation dose brings about significant physicochemical transformations in PET. 相似文献
980.
高分子铑配合物(PYBRh)催化甲醇羰基化为乙酸和乙酸酐的动力学研究 总被引:4,自引:1,他引:4
采用2-乙烯吡啶-丁烯酮共聚物为配体,与四羰基二氯二铑形成顺二羰基铑(I)配合物(PYBRh),用于催化甲醇羰基化制备乙酸和乙酸酐的反应动力学研究。结果表明,其对反应物甲醇和一氧化碳均为零级反应,在一定范围内,对高分子铑催化剂及助催化剂碘甲烷均为一级反应,极性溶剂的加入可以提高甲醇羰基化速度。通过实验结果计算了其反应活化能,活化熵和热焓研究证明其反应机理与小分子铑催化剂相似。 相似文献