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21.
Aldegunde J Alvariño JM Kendrick BK Sáez Rábanos V de Miranda MP Aoiz FJ 《Physical chemistry chemical physics : PCCP》2006,8(42):4881-4896
The effect of reactant polarisation on the dynamics of the title reaction at collision energies up to 1.6 eV is analysed in depth. The analysis takes advantage of two novel theoretical concepts: intrinsic reaction properties and stereodynamical portraits. Exact quantum methods are used to determine the polarisation moments that quantify the intrinsic reactant polarisation at various levels of detail, including or not product state and/or scattering angle resolution. The data is then examined with the aid of stereodynamical portraits, which facilitate the rationalisation of the stereochemical effects that are relevant for the reaction dynamics. This allows for detailed characterisations of the so-called direct and delayed reaction mechanisms. 相似文献
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Orera A Kendrick E Apperley DC Orera VM Slater PR 《Dalton transactions (Cambridge, England : 2003)》2008,(39):5296-5301
29Si NMR data have been recorded for the apatite series La8+xSr2-x(SiO4)6O2+x/2 (0 < or = x < or = 1.0). For x = 0, a single NMR peak is observed at a chemical shift of approximately -77 ppm, while as the La : Sr ratio and hence interstitial oxygen content is increased, a second peak at a chemical shift of approximately -80 ppm is observed, which has been attributed to silicate groups neighbouring interstitial oxide ions. An increase in the intensity of this second peak is observed with increasing x, consistent with an increase in interstitial oxide ion content, and the data are used to estimate the level of interstitial oxide ions, and hence Frenkel-type disorder in these materials. The increase in second 29Si NMR peak intensity/interstitial oxide ion content is also shown to correlate with an increase in conductivity. The effect of interstitial oxygen content can also be studied by means of Raman spectroscopy, with a new mode at 360 cm(-1) appearing for samples with x > 0 in the symmetric bending mode energy region of the SiO4 group. The intensity of this mode increases with increasing oxygen content, yielding results comparable to those from the NMR studies, showing the complementarities of the two techniques. 相似文献
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H. R. H. Ali H. G. M. Edwards J. Kendrick T. Munshi I. J. Scowen 《Journal of Raman spectroscopy : JRS》2007,38(7):903-908
The Raman spectrum of budesonide is reported for the first time, and molecular assignments are proposed on the basis of ab initio BLYP DFT calculations with a 6‐31 G* basis set and vibrational wavenumbers predicted on a quasi‐harmonic approximation. Comparison with previously published infrared data has explained several spectral features, and the relative band intensities in the CO and CC stretching regions are interpreted. The results from this study provide data that can be used for the preparative process monitoring of budesonide, an important steroidal pharmaceutical in various dosage forms, and its interaction with excipients and other components. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
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PHYTOCHROME INTERMEDIATES IN VIVO-I. EFFECTS OF TEMPERATURE, LIGHT INTENSITY, WAVELENGTH AND OXYGEN ON INTERMEDIATE ACCUMULATION 总被引:3,自引:0,他引:3
Abstract— Accumulation of weakly absorbing phytochrome intermediates has been demonstrated in Pisum epicotyl tissue under conditions of pigment cycling using a quasi-continuous measuring spectrophotometer. An action spectrum shows 690–700 nm to be the most efficient wavelength range in this process. Difference spectra for the decay of intermediates maintained by 690 nm light show that, if the experiment is done at 0°C, only Pfr is formed. At – 11°C, intermediates decaying to Pr can also be observed. At – 20°C, Pr is produced as well as a pigment with peak absorption at 710nm. Kinetic analysis of intermediate decay at – 11°C reveals that at least two intermediates are maintained by 690 nm light. The level of intermediate maintained by incandescent light at 0°C was 25% higher in air than in nitrogen. 相似文献
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Sandra E. Kendrick James Persky Marc L. Eckhauser Anthony L. Imbembo Jonathan D. Fleischmann Karl A. Koehler 《Photochemistry and photobiology》1987,46(5):669-673
Abstract Fluorescence spectroscopy was utilized to investigate the equilibrium interaction of dihem-atoporphyrin ether(s) (DHE) with binary and ternary phospholipid mixtures of defined composition in order to define the roles of net negative surface charge and lateral phase separations in DHE-membrane partitioning. Binary phospholipid mixtures employed were composed of dimyristoyl-phosphatidylcholine (DMPC) mixed with increasing weight percentages of dimyristoylphosphatidylgly-cerol (DMPG) providing controlled variation of net membrane surface charge. Two types of ternary phospholipid mixtures were utilized. Ternary acid mixtures contained various percentages of palmitoyl-lysophosphatidyl choline (LPC) + palmitic acid (PA) dispersed in DMPC. Ternary alcohol mixtures contained various percentages of LPC + hexadecanol (OL) dispersed in DMPC. The ternary phospholipid mixtures are known to be phase separated. At total DHE concentrations of 0.33 μA/ and using 100% DMPC, the DHE partition coefficient (P) is 250 000. This partition coefficient is to some extent dependent on the DHE concentration. The observed partition coefficients show little dependence on surface charge in DMPC-DMPG mixtures. However, P decreases markedly with increasing phase separation in the ternary lipid mixtures. The fluorescence of membrane-bound DHE is dependent on the composition of the ternary mixtures in a manner suggesting micropartitioning of DHE into the phospholipid bulk phase as well as into the disordered regions between laterally phase separated phospholipid domains. 相似文献
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