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41.
P. Duane Walker Gustavo A. Arteca Paul G. Mezey 《Journal of computational chemistry》1991,12(2):220-230
An algorithm for a detailed 3-D characterization of the shapes of molecular charge distributions is implemented, tested and applied for a family of AB2 molecules. The characterization is performed by computing a number of topological invariants (“shape groups”) associated with a continuum of molecular surfaces: the complete family of all electronic isodensity contours for the given molecules. These shape groups (the homology groups of truncated surfaces derived from isodensity contours) depend continuously on two parameters: a density value defining the density contour, and a reference curvature value, to which the local curvatures of the isodensity contours are compared. The electronic charge distribution is modeled by means of Gaussian-type functions. The method employs an explicit form of the charge density function in order to compute the curvature properties for the molecular surfaces analytically, from which the shape groups are derived by the algorithm. No visual inspection is required for the characterization and comparison of shapes of molecular charge densities, as these are done algorithmically by the computer. However, visual inspection of the results of the shape analysis is a possible option. For a given molecule, in a given nuclear configuration, the technique provides a two-dimensional shape map, displaying the distribution of shape groups as a function of the local curvature and the level set value (the value of the charge density at the contour). The computer program GSHAPE performs the analysis of shape maps automatically. This feature makes it potentially useful in the context of computer-aided drug design, where unbiased, automated shape characterization methods are valuable tools. As examples, several two-dimensional shape maps for simple systems are discussed. The changes induced in these maps by a change in the nuclear geometry, as well as by the changes of the nuclear charge, are also analyzed. The method is applicable to large biomolecules of interest if charge density information is available. 相似文献
42.
The separation of bupropion enantiomers on an ovomucoid stationary phase was investigated. The mobile- and stationary-phase parameters that may influence the separation were identified. The parameters that were studied include: type and concentration of organic modifier, mobile phase pH, ionic strength, type of buffer, and column temperature, as well as the effect that the amount of sample injected had on the separation. The optimized chiral separation baseline-resolved the enantiomers in less than 10 min. Calibration curves for a standard were linear over a range of 0.27-53.0 microg/g (ppm) with a correlation coefficient of 0.999 for both enantiomers. A detection limit of 0.13 microg/g and a quantitation limit of 0.27 microg/g were also found. The system precision of the method was 0.2%. 相似文献
43.
Bogert D Burnstein R Fisk R Fuess S Morfin J Ohska Stutte L Walker JK Bofill J Busza W Eldridge T Friedman JI Goodman MC Kendall HW Kostoulas IG Lyons T Magahiz R Mattison T Mukherjee A Osborne L Pitt R Rosenson L Sandacz A Tartaglia M Taylor FE Verdier R Whitaker S Yeh GP Abolins M Brock R Cohen A Ernwein J Owen D Slate J Weerts H 《Physical review letters》1985,55(6):574-577
44.
45.
H.A. Anderson A. Hepburn J.D. Miller M. Stewart R.C. Ferrier T.A.B. Walker 《Analytica chimica acta》1990
Humic substances were isolated from the vegetation throughfall, soil drainage waters and adjacent stream waters at two forested sites in the Central Region of Scotland. Fractionation on XAD-8 hydrophobic resin gave three humic substance components and one hydrophilic acid fraction. Norway spruce generally gave 2–3 times more dissolved organic carbon in the litter drainage compared with Sitka spruce, although there was little qualitative difference in organic acidity between the two litterflows. The humic substances in the drainage at ca. 1 m depth (BC horizon) showed considerable differences between sites, reflecting the types of soils and sources of soil water. Phenolic acids released on hydrolysis confirm the differences between sites and may indicate the sources of subsoil water and their relationships with the stream outputs. 相似文献
46.
47.
Ni(+)(CO(2))(n), Ni(+)(CO(2))(n)Ar, Ni(+)(CO(2))(n)Ne, and Ni(+)(O(2))(CO(2))(n) complexes are generated by laser vaporization in a pulsed supersonic expansion. The complexes are mass-selected in a reflectron time-of-flight mass spectrometer and studied by infrared resonance-enhanced photodissociation (IR-REPD) spectroscopy. Photofragmentation proceeds exclusively through the loss of intact CO(2) molecules from Ni(+)(CO(2))(n) and Ni(+)(O(2))(CO(2))(n) complexes, and by elimination of the noble gas atom from Ni(+)(CO(2))(n)Ar and Ni(+)(CO(2))(n)Ne. Vibrational resonances are identified and assigned in the region of the asymmetric stretch of CO(2). Small complexes have resonances that are blueshifted from the asymmetric stretch of free CO(2), consistent with structures having linear Ni(+)-O=C=O configurations. Fragmentation of larger Ni(+)(CO(2))(n) clusters terminates at the size of n=4, and new vibrational bands assigned to external ligands are observed for n> or =5. These combined observations indicate that the coordination number for CO(2) molecules around Ni(+) is exactly four. Trends in the loss channels and spectra of Ni(+)(O(2))(CO(2))(n) clusters suggest that each oxygen atom occupies a different coordination site around a four-coordinate metal ion in these complexes. The spectra of larger Ni(+)(CO(2))(n) clusters provide evidence for an intracluster insertion reaction assisted by solvation, producing a metal oxide-carbonyl species as the reaction product. 相似文献
48.
Pill-Soon Song Edward B. Walker Richard D. Vierstra Kenneth L. Poff 《Photochemistry and photobiology》1980,32(3):393-398
Abstract— The blue light absorption band of roseoflavin is polarized along the axis roughly connecting N3 -C8 positions. A weak, second π→π* transition with a polarization angle of ca. 25° is hidden under the short wavelength side of the blue absorption band. The excited state of roseoflavin is somewhat more basic than the ground state, by a 1.5 p K a unit. The fluorescence quantum yield and lifetime of roseoflavin are substantially lower than those of other flavins, thus making it kinetically less efficient as a blue light photoreceptor. 相似文献
49.
Stephen G. Davies Isabelle M. Dordor Jonathan C. Walker Peter Warner 《Tetrahedron letters》1984,25(25):2709-2712
β-Hydroxy acyl ligands bound to (η5-C5H5)Fe(CO)(PPh3) are stereoselectively alkylated on the α-carbon to give after decomplexation erythro-β-hydroxy carboxylic acids. 相似文献
50.
In an earlier binding study conducted in our laboratory using Thermobifida fusca cellulases Cel6B, Cel9A, and Cel5A (formally Thermomonospora fusca E3, E4, and E5), it was observed that binding capacities for these three cellulases were 18–30 times higher on BMCC than on Avicel. These
results stimulated an interest in how the difference in accessibility between the two cellulosic substrates would affect synergism
observed with cellulase mixtures. To explore the impact of substrate, accessibility on the extent of conversion and synergism,
three binary T. fusca cellulase mixtures were tested over a range of cellulase ratios and total molar cellulase concentrations on Avicel and BMCC.
Higher extents of conversion were observed for BMCC due to the higher enzyme to substrate ratio resulting from the higher
binding The processive endoglucanase, Cel9A, had four times the extent of conversion of the end endocellulase Cel5A, while
the exocellulase Cel6B had three times the extent of conversion of Cel5A. Approximately 500 nmol/g of the cel9A+Cel6B mixture
was needed to obtain 80% conversion, while the Cel6B+Cel5A and Cel9A+Cel5A mixtures required 1500 and 1250 nmol/g, respectively,
to obtain 80% conversion. Thus, it appears that the more accessible structure of BMCC, as reflected by its binding capacity,
results in relative higher processive activity. 相似文献