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921.
Atomic populations and localization [lambda(A)] and delocalization [delta(A,B)] indices (LIs and DIs) are calculated for a large set of molecules at the Hartree-Fock (HF), MP2, MP4(SDQ), CISD, and QCISD levels with the 6-311++G(2d,2p) basis set. The HF method and the conventional correlation methods [MP2, MP4(SDQ), CISD, and QCISD] yield distinct sets of LIs and DIs. Yet, within the four conventional correlation methods the differences in atomic populations and LIs and DIs are small. Relative to HF, the conventional correlation methods [MP2, MP4(SDQ), CISD, QCISD] yield virtually the same LIs and DIs for molecules with large charge separations while LIs and DIs that differ significantly from the HF values--the LIs are increased and DIs decreased--are obtained for bonds with no or small charge separations. Such is the case in the archetypal homopolar molecules HC(triple bond)CH, H2C=CH2, CH3-CH3, and "protonated cyclopropane" C(3)H(7) (+), in which case the bonding may be atypical. Relative to HF, the typical effect of the conventional correlation methods is to decrease the DI between atoms. 相似文献
922.
Faull KF Johnson J Kim MJ To T Whitelegge JP Stevens RL Fluharty CB Fluharty AL 《Journal of mass spectrometry : JMS》2000,35(12):1416-1424
The specific sugar residues and their linkages in the oligosaccharides from pig kidney and human urine cerebroside sulfate activator proteins (saposin B), although previously hypothesized, have been unambiguously characterized. Exhaustive sequential exoglycosidase digestion of the trimethyl-p-aminophenyl derivatives, followed by either matrix-assisted laser desorption/ionization and/or mass spectrometry, was used to define the residues and their linkages. The oligosaccharides were enzymatically released from the proteins by treatment with peptidyl-N-glycosidase F and separated from the proteins by reversed-phase high-performance liquid chromatography (HPLC). Reducing termini were converted to the trimethyl-p-aminophenyl derivative and the samples were further purified by normal-phase HPLC. The derivatized carbohydrates were then treated sequentially with a series of exoglycosidases of defined specificity, and the products of each digestion were examined by mass spectrometry. The pentasaccharides from pig kidney and human urine protein were shown to be of the asparagine-linked complex type composed of mannose-alpha 1-6-mannose-beta 1-4-N-acetylglucosamine-N-acetylglucosamine(alpha 1-6-fucose). This highly degraded structure probably represents the final product of intra-lysosomal exoglycosidase digestion. Oligosaccharide sequencing by specific exoglycosidase degradation coupled with mass spectrometry is more rapid than conventional oligosaccharide sequencing. The procedures developed will be useful for sequencing other oligosaccharides including those from other members of the lipid-binding protein class to which cerebroside sulfate activator belongs. (c) 2000 John Wiley & Sons, Ltd. 相似文献
923.
F. Román S. Montserrat J. M. Hutchinson 《Journal of Thermal Analysis and Calorimetry》2007,87(1):113-118
The procedure for
the fabrication of epoxy-based polymer layered silicate nanocomposites is
important in respect of the nanostructure that is developed. To further our
understanding of this, the influence of an organically modified clay (montmorillonite,
MMT) on the curing kinetics of an epoxy resin has been studied by differential
scanning calorimetry. Clay loadings of 10 and 20 mass% are used, and isothermal
as well as dynamic cures have been investigated. For both cure schedules the
effect of the MMT is to advance the reaction. Kinetic analysis yields values
for the activation energy, but shows that the reaction cannot be described
simply by the usual autocatalytic equation. The glass transition of the cured
nanocomposites is lower than that for the cured neat resin, a result that
is attributed to homopolymerisation taking place in addition to the epoxy–amine
reaction. 相似文献
924.
G L Grunewald M A Pleiss C L Gatchell R Pazhenchevsky M F Rafferty 《Journal of chromatography. A》1984,292(2):319-331
The elution behaviour of a selection of sequence variant and modified insulins has been compared on a C18 reversed-phase column. Observed elution times were compared with those expected from the nature of the differences from bovine insulin. In some cases prediction rules established for peptides are adequate to explain the observed elution and in others detailed knowledge of the structure of the protein is of considerable importance in understanding elution behaviour. 相似文献
925.
F. Shafizadeh 《Journal of Analytical and Applied Pyrolysis》1982,3(4):283-305
The pyrolytic properties of biomass are controlled by the chemical composition of its major components, namely cellulose, hemicelluloses and lignin and their minor components including extractives and inorganic materials. Pyrolysis of these materials proceeds through a series of complex, concurrent and consecutive reactions and provides a variety of products.Pyrolysis cellulose at lower temperatures below 300° C involves reduction in molecular weight, evolution of water, carbon dioxide and carbon monoxide and formation of char. On heating at higher temperature 300–500° C, the molecule is rapidly depolymerized to anhydroglucose units that further reacts to provide a XXXX pyrolyXXXXA: still higher temperatures, the anhydrosugar compounds undergo fussion, dehydration disproportionation and decarboxylation reaction to provide a mixture of low molecular weight gaseous and volatile produces. The composition of these produces and mechanism and kinetics of their production are reported. 相似文献
926.
N. S. Prostakov Keti Sudzhi N. M. Mikhailova L. A. Murugova V. F. Zakharov 《Chemistry of Heterocyclic Compounds》1981,17(10):1038-1042
1-Methyl-1H-indeno[1,2-b]pyridine and 1-methyl-1H-5-(, -dicarbomethoxyvinyl)-(formyl, acetyl)indeno[3,2-b]pyridines were obtained by treatment of N-methyl-4-azafluorenium iodide, as well as mixtures of it with acetylenedicarboxylic ester, dimethylformamide (DMF), and phosphorus oxychloride or acetic anhydride, with bases. 4-Azafluoronenone was used to synthesize 9-(p-methoxyphenyl)-4-azafluoren-9-ol, which was reduced to 9-(p-methoxyphenyl)-4-azafluorene, and 1-methyl-1H-5-(p-methoxyphenyl)indeno[3,2-b]pyridine was obtained from the methiodide of the latter.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1382–1386, October, 1981. 相似文献
927.
A method for the determination of low levels of ammonium ion in solution by optical emission spectrometry with an inductively coupled argon plasma source operated at 27 MHz is presented. The ammonium ion is oxidized with sodium hypobromite in alkaline medium, the evolved nitrogen is passed into the argon plasma, and the NH emission intensity produced in the plasma at 336.0 nm is monitored. A practical detection limit of 0.1 μg N ml-1 for 5-ml aqueous sample solutions has been obtained. The method has been applied to the determination of the exchangeable ammonium content of soil samples. 相似文献
928.
Lichens have long been regarded as bioindicators of air pollution, and structural studies typically have indicated negative impacts in highly polluted areas. In this research, Parmelia sulcata and Platismatia glauca were collected from one clean and two polluted sites in the Pacific Northwest forests of the United States to investigate the anatomical and ultrastructural responses of relatively resistant lichens to moderate air pollution. Light microscopy of polluted materials revealed only slight increases in the algal cell proportions of the thallus, and a decrease in the fungal cells of the medulla. Using transmission electron microscopy, increased lipid droplets in the cytoplasm and an increase in the cell wall thickness of the photobionts were found in the polluted lichens. These results were compared with physiological data in which the net carbon uptake did not show any significant differences; however, the total chlorophyll content was heightened in the polluted samples. The increased total chlorophyll content and the absence of any changes in the algal cell proportions of the polluted samples suggest that the photobionts possessed a higher chlorophyll content per unit volume of the photobiont at polluted sites. The results also indicate that lichens have altered their storage allocation in different cellular compartments. This may be a result of symbiotic readjustment(s) between the photobiont and the mycobiont. In comparison with the physiological results from these two species, these changes do not represent damaging effects by low-level air pollution. 相似文献
929.
Fabrication of hexaphenylsilole nanowires and their morphology-tunable photoluminescence. 总被引:1,自引:0,他引:1
Liping Heng Jin Zhai Anjun Qin Yuqi Zhang Yongqiang Dong Ben Zhong Tang Lei Jiang 《Chemphyschem》2007,8(10):1513-1518
Immersion of nanoporous alumina membranes into saturated solutions of hexaphenylsilole with subsequent solvent evaporation affords aligned organic nanowires. The luminescent properties of the hexaphenylsilole nanowires can be manipulated by varying their morphologies, which were controlled by changing the channel sizes of the alumina templates. 相似文献
930.
A. G. Nemazanyi Yu. M. Volovenko V. V. Neshchadimenko F. S. Babichev 《Chemistry of Heterocyclic Compounds》1992,28(2):220-222
The possibility of obtaining 3-amino-1,2-benzothiazine 1,1-dioxides by nucleophilic substitution of the chlorine atom in 5-nitro-2-chlorobenzenesulfonamides by carbanions generated from substituted acetonitriles was studied.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 264–266, February, 1992. 相似文献