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Crowder KN Garcia SJ Burr RL North JM Wilson MH Conley BL Fanwick PE White PS Sienerth KD Granger RM 《Inorganic chemistry》2004,43(1):72-78
We report on the synthesis of a platinum(IV) compound containing a di-2-pyridyl ketone (dpk) ligand that is stable both in its anhydrous form [Pt(dpk)Cl(4)] (1) and in its hydrated form [Pt(dpk-O-OH)Cl(3)].H-phenCl (2). The crystal structure of the hydrated form shows that one of the hydroxide groups from the resulting gem-diol has undergone a cyclometalation/condensation reaction resulting in an oxygen atom directly coordinated to the Pt(IV) center and the formation of H-phenCl. We correlate our physical data with predictions made by molecular modeling, and we propose an explanation for the unusual activity found for this dpk ketone. Spectroscopic and solubility studies are presented here, as well. Electrochemical studies of 1 indicate that it undergoes a highly irreversible reduction at a potential of about -0.45 V vs Ag(+)/Ag in CH(3)CN and that the irreversibility is likely due to an EC mechanism, the nature of which is currently under further investigation. Another distinct redox pair, apparently reversible, appears at a potential of about -1.1 V vs Ag(+)/Ag. 相似文献
34.
ICP-AES法测定内蒙古地区六种沙生木本植物中金属元素 总被引:19,自引:5,他引:14
采用ICP-AES法分别对内蒙古地区梭梭、小叶锦鸡儿、沙冬青、红柳、沙枣和沙柳等六种沙生木本植物中金属元素进行了测定和分析。该方法的加标回收率为94.98%~120.25%,RSD<3.4%,具有良好的准确度和精密度。结果表明,常量元素Ca,K,Mg,Na,Al及植物生命活动所必需的微量元素Fe,Mn,Cu,Zn在六种沙生木本植物中表现为不同的含量顺序,且Fe,Mn,Cu,Zn四种元素的含量均低于陆生高等植物的平均含量。该测定结果为改善西部地区生态环境,选择优良防风固沙树种提供可靠的数据和理论依据。 相似文献
35.
36.
Hu Z Periyannan G Bennett B Crowder MW 《Journal of the American Chemical Society》2008,130(43):14207-14216
In an effort to probe the role of the Zn(II) sites in metallo-beta-lactamase L1, mononuclear metal ion containing and heterobimetallic analogues of the enzyme were generated and characterized using kinetic and spectroscopic studies. Mononuclear Zn(II)-containing L1, which binds Zn(II) in the consensus Zn1 site, was shown to be slightly active; however, this enzyme did not stabilize a nitrocefin-derived reaction intermediate that had been previously detected. Mononuclear Co(II)- and Fe(III)-containing L1 were essentially inactive, and NMR and EPR studies suggest that these metal ions bind to the consensus Zn2 site in L1. Heterobimetallic analogues (ZnCo and ZnFe) analogues of L1 were generated, and stopped-flow kinetic studies revealed that these enzymes rapidly hydrolyze nitrocefin and that there are large amounts of the reaction intermediate formed during the reaction. The heterobimetallic analogues were reacted with nitrocefin, and the reactions were rapidly freeze quenched. EPR studies on these samples demonstrate that Co(II) is 5-coordinate in the resting state, proceeds through a 4-coordinate species during the reaction, and is 5-coordinate in the enzyme-product complex. These studies demonstrate that the metal ion in the Zn1 site is essential for catalysis in L1 and that the metal ion in the Zn2 site is crucial for stabilization of the nitrocefin-derived reaction intermediate. 相似文献
37.
Metallo-beta-lactamases are responsible for conferring antibiotic resistance on certain pathogenic bacteria. In consequence, the search for inhibitors that may be useful in combating antibiotic resistance has fueled much study of the active sites of these enzymes. There exists circumstantial evidence that the binding of substrates and inhibitors to metallo-beta-lactamases may involve binding to the organic part of the molecule, in addition to or prior to binding to one or more active site metal ions. It has also been postulated that a conformational change may accompany this putative binding. In the present study, electron paramagnetic resonance spectrokinetic study of a spin-labeled variant of the class B2 metallo-beta-lactamase ImiS identified movement of a component residue on a conserved alpha-helix in a catalytically competent time upon formation of a transient reaction intermediate with the substrate imipenem. In a significant subpopulation of ImiS, this conformational change was not associated with substrate binding to the active site metal ion but, rather, represents a distinct step in the reaction with ImiS. This observation has implications regarding the determinants of substrate specificity in metallo-beta-lactamases and the design of potentially clinically useful inhibitors. 相似文献
38.
Abstract Infrared spectra were obtained for 1,2-dibromopropane-d6 in the liquid and in the unannealed and annealed solid states. Vibrational assignments were made for the three conformers of 1,2-dibromopropane and the three conformers of 1,2-dibromopropane-d6 with the aid of normal coordinate calculations. All three possible conformers of CD2BrCDBrCD3 were found to be present in the liquid and unannealed solid, but the PHSHH conformer was absent in the annealed solid. 相似文献
39.
G.A. Crowder 《Molecular physics》2013,111(6):971-976
Normal coordinate calculations were carried out for H-C=C-CH2Cl using a valence force field and the force constants obtained were transferred to CH3-C=C-CH2Cl. There seem to be small but significant differences in some of the force constants of the -CH2Cl group of these two molecules. The vibrational assignment of McLachland [1] is confirmed, and the calculations show that the fundamental vibrations are relatively pure except for the C-C symmetric stretch and the skeletal bends. 相似文献
40.
Alan P. Bashall John Crowder Hagen Dronia Gerhard Hgele Harry R. Hudson Rosalind J. Lee Mary McPartlin Ray W. Matthews Johannes Ollig 《Heteroatom Chemistry》2010,21(5):314-325
X‐ray structural data for α‐aminopropanephosphonic acid (APPA), together with 1H NMR spectroscopy including PANIC and WIN‐DAISY spectral simulation, and theoretical calculations using the programs VAMP 4.4 (PM3) and GAUSSIAN 92 (3–21G**), confirm an antistaggered relationship between the methyl and phosphonic acid groups in this zwitterionic compound, both in the solid state and in aqueous solution. 31P{1H} and 13C{1H}‐NMR controlled titrations provide information on pKa values, proton exchange, ion‐specific chemical shifts, and coupling constants in solution. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:314–325, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20609 相似文献