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41.
Experimental data for the photoisomerization of trans-stilbene (S(1)) in thermal bath gases at pressures up to 20 bar obtained previously by Meyer, Schroeder, and Troe (J. Phys. Chem. A 1999, 103, 10528-10539) are modeled by using a full collisional-reaction master equation that includes non-RRKM (Rice-Ramsperger-Kassel-Marcus) effects due to slow intramolecular vibrational energy redistribution (IVR). The slow IVR effects are modeled by incorporating the theoretical results obtained recently by Leitner et al. (J. Phys. Chem. A 2003, 107, 10706-10716), who used the local random matrix theory. The present results show that the experimental rate constants of Meyer et al. are described to within about a factor of 2 over much of the experimental pressure range. However, a number of assumptions and areas of disagreement will require further investigation. These include a discrepancy between the calculated and experimental thermal rate constants near zero pressure, a leveling off of the experimental rate constants that is not predicted by theory and which depends on the identity of the collider gas, the need to use rate constants for collision-induced IVR that are larger than the estimated total collision rate constants, and the choice of barrier-crossing frequency. Despite these unsettled issues, the theory of Leitner et al. shows great promise for accounting for possible non-RRKM effects in an important class of reactions. 相似文献
42.
The use of redox magnetohydrodynamics (MHD) to enhance the anodic stripping voltammetry (ASV) response of heavy metals has been investigated, with respect to achieving portability: disposable electrodes consisting of screen-printed carbon (SPC) on a low temperature co-fired ceramic (LTCC) substrate, small volumes, and permanent magnets. The analytes tested (Cd(2+), Cu(2+), and Pb(2+)) were codeposited on SPC with Hg(2+) to form a Hg thin film electrode. High concentrations of Fe(3+) were used to produce a high cathodic current which generates a significant Lorentz force in the presence of a magnetic field. This Lorentz force induces solution convection during the deposition step, enhancing the mass transport of analytes to the electrode and increasing their preconcentrated quantity in the mercury thin film. Therefore, larger ASV peaks and improved sensitivities are obtained, compared to analyses performed without a magnet. The effects on ASV signal of varying Hg(2+) concentration (0.10 and 1.0 mM), deposition time (10-600 s), and electrode surface roughness were investigated. In addition, analyses were performed using a real lake water matrix. By using the disposable LTCC-SPC working electrodes in small volumes (150 microL) and with small permanent magnets (0.78 T), peak areas were increased by 75% when compared to the signal obtained in the absence of a magnetic field. A limit of detection of 25 nM for Cd(2+) was observed with only a 1 min preconcentration time. 相似文献
43.
In this report, we evaluate experimentally and through the use of simulations and calculations the possibility of using 2-beam fluorescence cross correlation spectroscopy (2BFCCS) for the multicomponent electrophoretic analysis of peptides. The concept described has potential as a high throughput, extraordinarily sensitive means of identifying proteins and accelerating proteome studies. We present Monte Carlo simulation methods and results using them that help in understanding the capabilities and limitations of 2BFCCS for protein identification. We have calculated the expected pH dependent mobility and resultant 2BFCCS fingerprint spectra for a randomly selected subset of the peptides present upon digestion of horse myoglobin by trypsin. We demonstrate experimentally the multicomponent analysis of a mixture containing a fluorescently labeled peptide and a free fluorophore. We also demonstrate experimentally the ability to measure migration rates of dilute, single-fluorophore species over more than 2 orders of magnitude in linear velocity (between 4.2 mm s(-1) and 640 mm s(-1)). 相似文献
44.
Weston M. Eldredge Pál Tóth Laurie Centauri Eric G. Eddings Kerry E. Kelly Terry A. Ring Axel Schönbucher Jeremy N. Thornock Philip J. Smith 《Flow, Turbulence and Combustion》2016,97(2):427-449
An effective approach to the model VUQ process by means of direct collaboration between computationalist and experimental data analyst is proposed. An analysis of data from a laminar helium plume experiment provides a demonstration of the proposed collaboration process. Consistency analysis serves a central role in the collaboration. It takes the data and uncertainties from both analyst and computationalist and provides an objective and quantifiable measure of agreement between the two. Despite the simplicity of the laminar helium system and the computational model, certain phenomena brought to light in the collaboration process make it difficult to find quantitative agreement in the data. These phenomena include the unsteady behavior of air flow in an open room, and the presence of helium permeation to the region near the plume. Important sources of error in the simulation include uncertainty in the room temperature (295.15 to 305.15 K), uncertainty in the helium inlet velocity (0.1215 \(\frac {m}{s}\) to 0.1415 \(\frac {m}{s}\)), and uncertainty in local helium permeation (0 % to 3 % by mass.) The collaboration process allows for a better understanding of the phenomena affecting the plume and the relative sensitivies of the system to these phenomena. 相似文献
45.
The energy of an oriented q-distribution ? in a compact oriented manifold M is defined to be the energy of the section of the Grassmannian manifold of oriented q-planes in M induced by ?. In the Grassmannian, the Sasaki metric is considered. We show here a condition for a distribution to be a critical point of the energy functional. In the spheres, we see that Hopf fibrations are critical points. Later, we prove the instability for these fibrations. 相似文献
46.
The energy of an oriented q-distribution ? in a compact oriented manifold M is defined to be the energy of the section of the Grassmannian manifold of oriented q-planes in M induced by ?. In the Grassmannian, the Sasaki metric is considered. We show here a condition for a distribution to be a critical
point of the energy functional. In the spheres, we see that Hopf fibrations are critical points. Later, we prove the instability for these fibrations.
(Received 30 December 2000; in revised form 11 April 2001) 相似文献
47.
David A. Hrovat Richard Vaughan Williams Alan C. Goren Weston Thatcher Borden 《Journal of computational chemistry》2001,22(13):1565-1573
B3LYP/6‐31G* calculations on the degenerate rearrangements of substituted semibullvalenes spuriously predict the relative enthalpies of the bishomoaromatic TSs to be lower than the experimental values. However, the calculations do make the useful and experimentally testable prediction that the two cyano and two phenyl substituents in 2,6‐dicyano‐4,8‐diphenylsemibullvalene ( 9d ) are more likely than four cyano substituents in 2,4,6,8‐tetracyanosemibullvalene ( 9f ) or the four phenyl substituents in 2,4,6,8‐tetraphenylsemibullvalene ( 9g ) to produce a semibullvalene that has a bishomoaromatic equilibrium geometry in the gas phase. The major reason for the surprising finding that 9d is more likely to be bishomoaromatic than 9g is shown to be steric interactions between the phenyl groups at C‐2 and C‐8 and at C‐4 and C‐6 in bishomoaromatic structure 10g . These interactions inhibit the conjugative stabilization of 10g ; but they are absent in bishomoaromatic structure 10d , where cyano groups replace the phenyl groups at C‐2 and C‐6 in 10g . © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1565–1573, 2001 相似文献
48.
J. D. Weston 《Mathematische Zeitschrift》1957,67(1):467-473
49.
Travelling‐wave ion mobility mass spectrometry and negative ion fragmentation of hybrid and complex N‐glycans 下载免费PDF全文
David J. Harvey Charlotte A. Scarff Matthew Edgeworth Kevin Pagel Konstantinos Thalassinos Weston B. Struwe Max Crispin James H. Scrivens 《Journal of mass spectrometry : JMS》2016,51(11):1064-1079
Nitrogen collisional cross sections (CCSs) of hybrid and complex glycans released from the glycoproteins IgG, gp120 (from human immunodeficiency virus), ovalbumin, α1‐acid glycoprotein and thyroglobulin were measured with a travelling‐wave ion mobility mass spectrometer using dextran as the calibrant. The utility of this instrument for isomer separation was also investigated. Some isomers, such as Man3GlcNAc3 from chicken ovalbumin and Man3GlcNAc3Fuc1 from thyroglobulin could be partially resolved and identified by their negative ion fragmentation spectra obtained by collision‐induced decomposition (CID). Several other larger glycans, however, although existing as isomers, produced only asymmetric rather than separated arrival time distributions (ATDs). Nevertheless, in these cases, isomers could often be detected by plotting extracted fragment ATDs of diagnostic fragment ions from the negative ion CID spectra obtained in the transfer cell of the Waters Synapt mass spectrometer. Coincidence in the drift times of all fragment ions with an asymmetric ATD profile in this work, and in the related earlier paper on high‐mannose glycans, usually suggested that separations were because of conformers or anomers, whereas symmetrical ATDs of fragments showing differences in drift times indicated isomer separation. Although some significant differences in CCSs were found for the smaller isomeric glycans, the differences found for the larger compounds were usually too small to be analytically useful. Possible correlations between CCSs and structural types were also investigated, and it was found that complex glycans tended to have slightly smaller CCSs than high‐mannose glycans of comparable molecular weight. In addition, biantennary glycans containing a core fucose and/or a bisecting GlcNAc residue fell on different mobility‐m/z trend lines to those glycans not so substituted with both of these substituents contributing to larger CCSs. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
50.