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31.
R.W. Nicholls 《Journal of Quantitative Spectroscopy & Radiative Transfer》1974,14(3):233-237
Klemsdal's recent paper on this topic (JQSRT13, 517, 1973) has stimulated the comments, (a) that molecular intensity measurements are by no means uniformly reliable and should be interpreted accordingly, (b) the mathematical basis of the r-Centroid approximation is well understood and is related to the existence (or non-existence) of a well developed uncancelled local peak on the vibrational wavefunction product. Contrary to his comments, it has been shown to hold very well for 105 bands so far studied. 相似文献
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Abstract The blue-green (B2? X2?) and orange (A2? –X2?) systems of yttrium oxide have been shock excited at temperatures of about 4000°K and photographed at high dispersion (~ 1.2Å/mm) in the first order of a 21 ft. grating spectrograph. The high dispersion shock excited spectra were recorded using multiple exposures and latensification of extremely high speed film. Over 50 new bands have been observed and assigned to specific vibrational transitions for the systems. New molecular constants have been derived from the A, B and X states. Provisional calculations have been made of Franck-Condon factors and r-centroids for the systems appropriate to new constants. 相似文献
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J. R. Nicholls 《Analytical and bioanalytical chemistry》1931,85(11-12):470-471
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The correlation of the recognition properties of a molecularly imprinted polymer (MIP) with the recognition events in pre-polymerisation mixtures is of central importance to our understanding of the molecular imprinting technique. Using the NSAID naproxen as a model template, we have applied parallel theoretical (molecular dynamics) and practical ((1)H-NMR, X-ray crystallography, HPLC, radioligand binding) methods to examine the nature of template-functional monomer complexation. An effective imprint is achieved, despite the presence of only one site on the template which provides for the formation of effective electrostatic interactions with the functional monomer used, 4-vinylpyridine. This is attributed to the creation of a well-defined receptor site for the acidic terminus of the molecule and complementary van der Waals interactions, as described in preliminary simulations of the pre-polymerisation system, and as confirmed for the resultant MIP by HPLC data. Qualitative agreement is also observed between simulation and proton NMR data examining monomer self-association in the presence and absence of the template. On the basis of the data obtained, the role of a cross-linker appears to be more significant for this system than previously anticipated. 相似文献
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Sundberg M Balaz M Bunk R Rosengren-Holmberg JP Montelius L Nicholls IA Omling P Tågerud S Månsson A 《Langmuir : the ACS journal of surfaces and colloids》2006,22(17):7302-7312
We have previously described the efficient guidance and unidirectional sliding of actin filaments along nanosized tracks with adsorbed heavy meromyosin (HMM; myosin II motor fragment). In those experiments, the tracks were functionalized with trimethylchlorosilane (TMCS) by chemical vapor deposition (CVD) and surrounded by hydrophilic areas. Here we first show, using in vitro motility assays on nonpatterned and micropatterned surfaces, that the quality of HMM function on CVD-TMCS is equivalent to that on standard nitrocellulose substrates. We further examine the influences of physical properties of different surfaces (glass, SiO(2), and TMCS) and chemical properties of the buffer solution on motility. With the presence of methylcellulose in the assay solution, there was HMM-induced actin filament sliding on both glass/SiO(2) and on TMCS, but the velocity was higher on TMCS. This difference in velocity increased with decreasing contact angles of the glass and SiO(2) surfaces in the range of 20-67 degrees (advancing contact angles for water droplets). The corresponding contact angle of CVD-TMCS was 81 degrees. In the absence of methylcellulose, there was high-quality motility on TMCS but no motility on glass/SiO(2). This observation was independent of the contact angle of the glass/SiO(2) surfaces and of HMM incubation concentrations (30-150 microg mL(-)(1)) and ionic strengths of the assay solution (20-50 mM). Complete motility selectivity between TMCS and SiO(2) was observed for both nonpatterned and for micro- and nanopatterned surfaces. Spectrophotometric analysis of HMM depletion during incubation, K/EDTA ATPase measurements, and total internal reflection fluorescence spectroscopy of HMM binding showed only minor differences in HMM surface densities between TMCS and SiO(2)/glass. Thus, the motility contrast between the two surface chemistries seems to be attributable to different modes of HMM binding with the hindrance of actin binding on SiO(2)/glass. 相似文献
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We compare the near edge structure (NES) of cubic boron nitride (cBN) measured using both electron energy loss spectroscopy (EELS) and X-ray absorption spectroscopy (XAS) with that calculated using three commonly used theoretical approaches. The boron and nitrogen K-edges collected using EELS and XAS from cBN powder were found to be nearly identical. These experimental edges were compared to calculations obtained using an all-electron density functional theory code (WIEN2k), a pseudopotential density functional theory code (CASTEP) and a multiple scattering code (FEFF). All three codes were found to reproduce the major features in the NES for both ionisation edges when a core-hole was included in the calculations. A partial core hole (1/2 of a 1s electron) was found to be essential for correctly reproducing features near the edge threshold in the nitrogen K-edge and to correctly obtain the positions of all main peaks. CASTEP and WIEN2k were found to give almost identical results. These codes were also found to produce NES which most closely matched experiment based on χ2 calculations used to qualitatively compare theory and experiment. This work demonstrated that a combined experimental and theoretical approach to the study of NES is a powerful way of investigating bonding and electronic structure in boron nitride and related materials. 相似文献