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Parameters for the commercially available modeling package SYBYL have been developed for Gd(3+) complexes allowing these to be studied with molecular mechanics. With these parameters and a technique termed the "coordination scan", the coordination numbers of Gd(III) based complexes can be predicted, and thus the hydration number q determined. Knowledge of q has allowed the prediction of molar relaxivities based on correlations to literature values. In addition, the calculated value DeltaE(coord) was found to successfully predict the thermodynamic stability constants for polyamino carboxylate ligands with Gd(3+). Gadolinium complexes are commonly utilized as MRI contrast agents, and thus the techniques utilized in this work should aid in the development of new contrast agents. 相似文献
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Reaction of the isodicyclopentadienide anion and its dehydro congener with Fe(II) leads to a stereochemically homogeneous ferrocene derivative in each instance. Through chemical correlation and X-ray analysis, above-plane complexation is established for both halves within the two sandwich compounds. 相似文献
25.
To avoid the toxic effects of both essential and nonessential metal ions, cells elaborate a variety of metal ion trafficking proteins that regulate metal ion mobility. While structures of several trafficking proteins have been determined, kinetic characterization of metal ion transfer between cognate protein partners and the factors controlling transfer has lagged behind, in part due to a limitation on methods to monitor the rapid transfer. In this Communication we report studies on the kinetics of Hg2+ transfer between separately expressed components of the flavoenzyme mercuric ion reductase (MerA) that take advantage of the sensitivity of the flavin fluorescence to the charge state of a cysteine thiol in the Hg2+ binding pathway. The thiolate form of C558 in the Tn501 MerA partially quenches the fluorescence of the oxidized enzyme. Protonation or binding of Hg2+ to the thiolate increases the fluorescence, providing a sensitive probe for kinetic analysis of the Hg2+ binding reaction. The kinetics of Hg2+ transfer in both directions between the cysteine pair of the separately expressed N-terminal domain and the C-terminal cysteines (C558, C559) of the catalytic core are presented, along with a model describing the overall process. 相似文献
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Michael J. Beam Jeannette Schulz Anvita Sinha Pamela Collins Susan Hallenbeck Michael Kustin 《Journal of heterocyclic chemistry》1989,26(2):521-524
Notwithstanding its tendency toward air oxidation in solution, 2-hydrazinobenzothiazole I reacted with aromatic aldehydes in ethanol to give the corresponding hydrazones III-XV in high yields and analytical purity. In related examples, acylation took place under similar conditions to produce hydrazides XVI-XX . The near-infrared bands of the absorption spectra of the araldehyde hydrazones have been associated with charge transfer and appeared to correlate with structural elements of the compounds in a way suggesting that the charge transfer was intermolecular. 相似文献
28.
Koumi P Green HE Hartley S Jordan D Lahec S Livett RJ Tsang KW Ward DM 《Electrophoresis》2004,25(14):2227-2241
The demand for high-throughput DNA profiling has increased with the introduction of national DNA databases and has led to the development of automated methods of short tandem repeat (STR) profile production; however, a potential bottleneck still exists at the gel electrophoresis stage. Capillary electrophoresis sequencers capable of processing 96 samples with considerably reduced manual intervention are now available. In this paper, we compare the ABI Prism 377 slab-gel sequencer currently used by the Forensic Science Service with three leading capillary array electrophoresis instruments: the ABI Prism 3700, the Amersham MegaBACE 1000 and the 16-capillary ABI Prism 3100. We describe the experiments used to evaluate and validate these platforms for forensic use with the STR multiplex Ampf/STR SGMplus [1, 2], along with comparative data from the ABI Prism 377 sequencer. 相似文献
29.
Clark SB Turnipseed SB Nandrea GJ Madson MR Hurlbut JA Sofos JN 《Journal of AOAC International》2002,85(5):1009-1014
A confirmatory method is described for phenylbutazone (PB) residues in bovine kidney tissue. Ground kidney tissue is diluted with water, and the mixture is made basic with 25% ammonium hydroxide in water; the lipids are extracted with ethyl and petroleum ethers. The ether layer is discarded, and the tissue is acidified with 6N HCl. PB residues are extracted with tetrahydrofuranhexane (1 + 4). The extract is passed through a silica solid-phase extraction column, and the eluate is evaporated to dryness. The residue is dissolved in acidified acetonitrile-water-acetic acid (50 + 49.4 + 0.6). A single quadrupole mass spectrometer coupled to a liquid chromatograph with an electrospray interface is used to confirm the identity of the PB residues in the kidney extract. Negative-ion detection with selected-ion monitoring of 4 ions is used. Sets of control and fortified-control kidney tissues (at 50, 100, and 200 ppb PB) and several kidney tissue field samples were analyzed for method validation. The method was tested further during the course of a survey to determine the incidence of PB residues in bovine kidney samples obtained from slaughterhouses across the country. In addition, the method was tested for use with an ion-trap mass spectrometer coupled to a liquid chromatograph, which allowed confirmation of PB at lower levels (5-10 ppb) in kidney tissue. 相似文献
30.
Aided by the construction of a custom potentiostat, a series of different PAD waveforms were compared to find the optimum detector for penicillin oxidation. The waveforms included standard 3-step direct and indirect PAD in addition to reverse-PAD and 4-step PAD. Two new waveforms, the indirect reverse-PAD and the 4-step indirect PAD were examined in the study. Under the solvent conditions of the study (0.01M acetate buffer, pH 4.6) the indirect waveforms yielded the best detectability for penicillin G while the reverse-PAD waveforms yielded the worst performance. The 4-step PAD methods did not improve detectability when compared to the 3-step types, but they did provide output peak profiles with better shapes and less tailing. Although indirect waveforms gave better detectability than direct detection in the 0.01M acetate buffer solution, the limits of detection for each were found to be differing functions of ionic strength. At higher acetate concentrations, direct PAD was more favorable than indirect detection. 相似文献