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991.
The kinetics of conversion of an edge-linked double cube, in this case [{Mo(3)PdS(4)(H(2)O)(9)}(2)](8+), to the corresponding single cube [Mo(3)(PdX)S(4)(H(2)O)(9)](4+), has been studied for the first time. Reaction is induced by six reagents X = CO, two water-soluble phosphines, Cl(-), Br(-), and NCS(-), which complex at the tetrahedral Pd. The first stage of reaction is fast and is accompanied by color changes, e.g. purple to dark blue in the case of Cl(-), assigned as double to single cube conversion. With X = CO and the two phosphines, when absorbance changes are intense enough for stopped-flow monitoring with reactants at =1 mM, rate constants 10(-)(5) k/M(-)(1) s(-)(1) at 25 degrees C are as follows: CO, 1.11; PTA, 27.8; P(C(6)H(4)SO(3))(3)(3)(-), 9.6; at I = 2.00 (Li(pts)). The reactions are independent of [H(+)] in the range 0.30-2.00 M, and no substitution at the Mo's is observed. The first stages with X = Cl(-), Br(-), and NCS(-) were too fast to monitor, but equilibrium constants K(1)/M(-)(1) were determined, Cl(-) (490), Br(-) (8040), and NCS(-) (630), by UV-vis spectrophotometry. Two subsequent kinetic stages are assigned to substitution at the Mo's. Similar behavior is observed for [Mo(3)FeS(4)(H(2)O)(10)](4+), which was selected because substitution at the Fe is also fast and there is no known double-cube formation. For both Mo(3)Pd and Mo(3)Fe the latter two stages can be explained by substitution at nonidentical (two alpha and one beta) H(2)O's on each Mo or by the presence of mixed-valent Mo(III)(2)Mo(IV) forms which are sufficiently long-lived to give a kinetic discrimination. In the case of NCS(-) an additional step, 0.015 s(-)(1), independent of [NCS(-)] is assigned to the isomerization Pd-NCS --> Pd-SCN. On removal of e.g. Cl(-) by chromatography or addition of Ag(+), the double cube re-forms. 相似文献
992.
W.David Ollis Julia Stephanidou Stephanatou J.Fraser Stoddart Gulten G. Unal David J. Williams 《Tetrahedron letters》1981,22(23):2225-2228
An X-ray structure analysis shows that the 5, 18-dimethyl derivative () of the title compound () crystallises from xylene as a 1:1 inclusion compound in which the host molecules adopt propeller-like conformations ( and *) with almost perfect 2 symmetry. Dynamic 1H n.m.r. spectroscopy shows that the 5, 18-dibenzyl derivative () of () forms a 1:1 inclusion compound with ethanol in the solid state and undergoes ring inversion ( ? *) between enantiomeric propeller-like conformations in solution against a barrier of 21.1 kcal mol?1 相似文献
993.
A generic method employing ultrafast liquid chromatography with tandem mass spectrometry (LC/MS/MS) was developed and employed for routine screening of drug candidates for inhibition of five major human cytochrome p450 (CYP) isozymes, CYP3A4, CYP2D6, CYP2C9, CYP2C19, and CYP1A2. The method utilized a monolithic silica rod column to allow fast flow rates to significantly reduce chromatographic run time. The major metabolites of six CYP-specific probe substrates for the five p450 isoforms were monitored and quantified to determine IC(50) values of five drug compounds against each p450 isozyme. Human liver microsomal incubation samples at each test compound concentration were combined and analyzed simultaneously by the LC/MS/MS method. Each pooled sample containing six substrates and an internal standard was separated and detected in only 24 seconds. The combination of ultrafast chromatography and sample pooling techniques has significantly increased sample throughput and shortened assay turnaround time, allowing a large number of compounds to be screened rapidly for potential p450 inhibitory activity, to aid in compound selection and optimization in drug discovery. 相似文献
994.
Reductive radical addition of 2-iodoethanol to N-Boc 2-tosyl-7-azabicyclo[2.2.1]heptadiene gives N-Boc syn-7-(2-hydroxyethyl)-4-tosyl-2-azabicyclo[2.2.1]hept-5-ene, which is converted into the neuroexcitants 3-(carboxymethyl)pyrrolidine-2,4-dicarboxylic acid and alpha-kainic acid. [structure: see text] 相似文献
995.
Background
Endoplasmic reticulum retention of misfolded cystic fibrosis transmembrane conductance regulator (CFTR) mutants and their rapid degradation is the major cause of cystic fibrosis (CF). An important goal is to understand the mechanism of how the misfolded proteins are recognized, retained, and targeted for degradation. 相似文献996.
Small-angle static light scattering has been used to probe the evolution of aggregate size and structure in the shear-induced aggregation of latex particles. The size of aggregates obtained from the particle-sizing instrument (Coulter LS230) was compared with the size of those obtained with another approach utilizing the Guinier equation on the scattering data. Comparison of the two methods for studying the effects of mixing on the evolution of the aggregate size with time revealed similar trends. The aggregate structures were quantified in terms of their fractal dimensions on the grounds of the validity of Rayleigh-Gans-Debye scattering theory for the fractal aggregates. Analysis of the scattering patterns of aggregates verified that restructuring of the aggregates occurred as the aggregates were exposed to certain shear environments, resulting in a scale-dependent structure that could not be quantified by a fractal dimension. The effect of restructuring on aggregate size was particularly noticeable when the aggregates were exposed to average shear rates of 40 to 80 s(-1), whereas no significant restructuring occurred at lower shear rates. At 100 s(-1), the fragmentation of aggregates appeared to be more significant than aggregate compac-tion. Copyright 2001 Academic Press. 相似文献
997.
Mendoza SM Whelan CM Jalkanen JP Zerbetto F Gatti FG Kay ER Leigh DA Lubomska M Rudolf P 《The Journal of chemical physics》2005,123(24):244708
Thin films of fumaramide [2]rotaxane, a mechanically interlocked molecule composed of a macrocycle and a thread in a "bead and thread" configuration, were prepared by vapor deposition on both Ag(111) and Au(111) substrates. X-ray photoelectron spectroscopy (XPS) and high-resolution electron-energy-loss spectroscopy were used to characterize monolayer and bulklike multilayer films. XPS determination of the relative amounts of carbon, nitrogen, and oxygen indicates that the molecule adsorbs intact. On both metal surfaces, molecules in the first adsorbed layer show an additional component in the C 1s XPS line attributed to chemisorption via amide groups. Molecular-dynamics simulation indicates that the molecule orients two of its eight phenyl rings, one from the macrocycle and one from the thread, in a parallel bonding geometry with respect to the metal surfaces, leaving three amide groups very close to the substrate. In the case of fumaramide [2]rotaxane adsorption on Au(111), the presence of certain out-of-plane phenyl ring and Au-O vibrational modes points to such bonding and a preferential molecular orientation. The theoretical and experimental results imply that the three-dimensional intermolecular configuration permits chemisorption at low coverage to be driven by interactions between the three amide functions of fumaramide [2]rotaxane and the Ag(111) or Au(111) surface. 相似文献
998.
Beşli S Coles SJ Davies DB Eaton RJ Hursthouse MB Kiliç A Shaw RA Yenilmez Ciftçi G Yeşilot S 《Journal of the American Chemical Society》2003,125(16):4943-4950
A problem has arisen in using chiral shift reagents (CSR) and chiral solvating agents (CSA) to determine meso and racemic forms of diastereoisomers in which the stereogenic centers of the molecules are separated by achiral spacers. It is found that NMR signals of both meso and racemic forms of diastereoisomers may exhibit doubling on addition of CSR/CSA, which means that unequivocal assignments cannot be made without characterizing the effects for separate meso and racemic forms; this is particularly important for additions of CSR/CSA at relatively low concentrations, which always result in the splitting of some NMR signals of diastereoisomers. The phenomenon is demonstrated in the (31)P NMR spectra of meso and racemic forms of three spermine-bridged gem-disubstituted cyclotriphosphazatrienes, 1a-c, and compared with analogous achiral molecules, the per-substituted spermine-bridged cyclotriphosphazatrienes 2a-d. As expected, only one set of (31)P NMR signals was observed for the achiral compounds 2a-d, even on addition of CSA. Two sets of (31)P NMR ABX multiplets corresponding to meso and racemic diastereoisomers were observed for compounds 1a-c; on addition of CSA, the signals of at least one of the multiplets for each compound separated into more than the expected groups of three lines with an intensity distribution of 2:1:1. To understand this phenomenon, the meso and racemic forms of 1a and 1b and the meso form of 1c have been separated and characterized by X-ray crystallography. On addition of CSA to the racemic forms of 1a and 1b, the (31)P NMR spectrum shows the expected doubling of signals, but, unexpectedly, the same is observed for each of the meso forms of 1a-c. Analogous results using both CSA and CSR have been obtained for the meso and racemic forms of the diastereoisomeric piperazine-bridged macrocyclic-phosphazene compound, 3, whereas no effect was observed for the two meso forms of the doubly bridged macrocyclic-phosphazene compound 4. The phenomenon of doubling of the (31)P NMR signals of the meso form of singly bridged cyclotriphosphazatrienes, 1a-c and 3, is explained by consideration of the equilibrium in solution of independent complexation of a chiral ligand with molecules that have two chiral cyclophosphazene moieties separated by an achiral spacer group. The results show that the stereogenicity of such diastereoisomeric molecules in solution cannot be characterized unequivocally by NMR measurements on addition of either CSR or CSA. 相似文献
999.
Porous filters were fabricated inside a microchannel using emulsion photo-polymerization. The porosity of the filter is dependent on the composition of the pre-polymer mixture. The morphology and flow resistance of four filters with varying water and cross-linker concentrations was studied. The porous filter was used to separate samples, such as whole blood to cell/serum components, based on size. The efficiency of cell/serum separation by the porous filter was tested by performing a glucose-6-phosphate dehydrogenase assay and was found to be comparable to separation by centrifuge. The porous filter thus mimics the functionality of the centrifuge, with the added benefits of no power requirements and ability to handle small sample volumes. 相似文献
1000.
[structure: see text] Four deoxyxylulose phosphate (DXP) analogues were synthesized and evaluated as substrates/inhibitors for methylerythritol phosphate (MEP) synthase. In analogues CF(3)-DXP (1), CF(2)-DXP (2), and CF-DXP (3), the three methyl hydrogens at C1 of DXP were sequentially replaced by fluorine. In the fourth analogue, Et-DXP (4), the methyl group in DXP was replaced by an ethyl moiety. Analogues 1, 2, and 4 were not substrates for MEP synthase under normal catalytic conditions and were instead modest inhibitors with IC(50) values of 2.0, 3.4, and 6.2 mM, respectively. In contrast, 3 was a good substrate (k(cat) = 38 s(-)(1), K(m) = 227 muM) with a turnover rate similar to that of the natural substrate. These results are consistent with a retro-aldol/aldol mechanism rather than an alpha-ketol rearrangement for the enzyme-catalyzed conversion of DXP to MEP. 相似文献