Search results for "Kinetic"
showing 10 items of 3064 documents
Studies in organic mass spectrometry. Part 9—mass spectra of 9,10-disubstituted 2,3,6,7-tetraalkoxy-9,10-dihydroanthracenes: A remarkable loss of rad…
1991
The electron impact-induced fragmentations of 23 9,10-disubstituted 2,3,6,7-tetraalkoxy-9,10-dihydroanthracenes, including six stereoisomeric pairs, were studied. The loss of the 9-(or 10-)substituent constitutes the main fragmentation route. The resulting ions give rise to a remarkable violation of the so-called even-electron rule as they eject the second substituent at the 10-(or 9-)position as a radical. The latter aspect was particularly investigated with the aid of low-energy (nominal value 15 eV) and mass-analysed ion kinetic energy spectra
State-to-state vibrational and rotational energy transfer in CO2 gas from time-resolved raman-infrared double resonance experiments
1998
A time-resolved Raman–infrared double resonance technique was used to study collisional relaxation rates of vibrational and rotational energy levels in CO2 gas at 295 K. A pulsed Raman excitation populated a selected rovibrational initial state. Measurements of the rates of transfer from the pumped initial state into specific final states were carried out using time-resolved laser absorption spectroscopy. First, the transfer rates were determined for the five lower vibrational energy levels. In particular, it was confirmed that the rate of transfer between the two Fermi levels (1000) and (0200) is very small [(5.3±0.2)×104 Torr-1 s-1]. The rotational structure inside the (0200) vibrational …
Effect of Experimental and Sample Factors on Dehydration Kinetics of Mildronate Dihydrate: Mechanism of Dehydration and Determination of Kinetic Para…
2014
The dehydration kinetics of mildronate dihydrate [3-(1,1,1-trimethylhydrazin-1-ium-2-yl)propionate dihydrate] was analyzed in isothermal and nonisothermal modes. The particle size, sample preparation and storage, sample weight, nitrogen flow rate, relative humidity, and sample history were varied in order to evaluate the effect of these factors and to more accurately interpret the data obtained from such analysis. It was determined that comparable kinetic parameters can be obtained in both isothermal and nonisothermal mode. However, dehydration activation energy values obtained in nonisothermal mode showed variation with conversion degree because of different rate-limiting step energy at hi…
Nanoelectron spectroscopy for chemical analysis: a novel energy filter for imaging x-ray photoemission spectroscopy
2005
An ovel instrument for imaging ESCA is described. It is based on a tandem arrangement of two hemispherical energy analysers used as an imaging energy filter. The main spherical aberration (α 2 -term) of the analyser is corrected by the antisymmetry of the tandem configuration. The kinetic energy range useable for imaging extends up to 1.6 keV; this is compatible with Mg and Al Kα laboratory x-ray sources. First experiments on the chemical surface composition of a Cu0.98Bi0.02 polycrystal, a GaAs/AlGaAs heterostructure and Ag crystallites on Si(111) have been performed using synchrotron radiation. The results reveal an energy resolutio no f190 meV and a lateral resolution (edge resolution) o…
Combined theoretical and experimental analysis of processes determining cathode performance in solid oxide fuel cells
2013
Solid oxide fuel cells (SOFC) are under intensive investigation since the 1980's as these devices open the way for ecologically clean direct conversion of the chemical energy into electricity, avoiding the efficiency limitation by Carnot's cycle for thermochemical conversion. However, the practical development of SOFC faces a number of unresolved fundamental problems, in particular concerning the kinetics of the electrode reactions, especially oxygen reduction reaction. We review recent experimental and theoretical achievements in the current understanding of the cathode performance by exploring and comparing mostly three materials: (La,Sr)MnO3 (LSM), (La,Sr)(Co,Fe)O3 (LSCF) and (Ba,Sr)(Co,…
Improved synthesis of Bn5CpRu(CO)2Cl and its application as racemization catalyst in preparative-scale metalloenzymatic dynamic kinetic resolution of…
2010
An improved gram-scale synthesis of Bn5CpRu(CO)2Cl is reported based on heating of pentabenzylcyclopentadiene with Ru3(CO)12 at 160 °C under argon atmosphere in mesitylene followed by addition of chloroform, continued heating, and evaporation of the solvents. Subsequent washing of unreacted ligand precursor with hexane provided pure title compound in 77 % yield. In combination with Candida antarctica lipase B (CAL-B) (Novozym 435), this complex forms a highly active racemization catalyst for metallo-enzymatic dynamic kinetic resolution (DKR) of secondary alcohols as demonstrated in the present work by converting 100 g of racemic 1-phenylethanol to (R)-1-phenylethanol in >99 % ee and 93 %…
Determination of relative chlorophyll binding affinities in the major light-harvesting chlorophyll a/b complex.
2002
The major light-harvesting complex (LHCIIb) of photosystem II can be reconstituted in vitro from its recombinant apoprotein in the presence of a mixture of carotenoids and chlorophylls a and b. By varying the chlorophyll a/b ratio in the reconstitution mixture, the relative amounts of chlorophyll a and chlorophyll b bound to LHCIIb can be changed. We have analyzed the chlorophyll stoichiometry in recombinant wild type and mutant LHCIIb reconstituted at different chlorophyll a/b ratios in order to assess relative affinities of the chlorophyll-binding sites. This approach reveals five sites that exclusively bind chlorophyll b. Another site exhibits a slight preference of chlorophyll b over ch…
Consecutive binding of chlorophylls a and b during the assembly in vitro of light-harvesting chlorophyll-a/b protein (LHCIIb).
2006
The apoprotein of the major light-harvesting chlorophyll a/b complex (LHCIIb) is post-translationally imported into the chloroplast, where membrane insertion, protein folding, and pigment binding take place. The sequence and molecular mechanism of the latter steps is largely unknown. The complex spontaneously self-organises in vitro to form structurally authentic LHCIIb upon reconstituting the unfolded recombinant protein with the pigments chlorophyll a, b, and carotenoids in detergent micelles. Former measurements of LHCIIb assembly had revealed two apparent kinetic phases, a faster one (tau1) in the range of 10 s to 1 min, and a slower one (tau2) in the range of several min. To unravel th…
Refinement of a structural model of a pigment-protein complex by accurate optical line shape theory and experiments.
2007
Time-local and time-nonlocal theories are used in combination with optical spectroscopy to characterize the water-soluble chlorophyll binding protein complex (WSCP) from cauliflower. The recombinant cauliflower WSCP complexes reconstituted with either chlorophyll b (Chl b) or Chl a/Chl b mixtures are characterized by absorption spectroscopy at 77 and 298 K and circular dichroism at 298 K. On the basis of the analysis of these spectra and spectra reported for recombinant WSCP reconstituted with Chl a only (Hughes, J. L.; Razeghifard, R.; Logue, M.; Oakley, A.; Wydrzynski, T.; Krausz, E. J. Am. Chem. Soc. U.S.A. 2006, 128, 3649), the "open-sandwich" model proposed for the structure of the pig…
Pigment−Pigment and Pigment−Protein Interactions in Recombinant Water-Soluble Chlorophyll Proteins (WSCP) from Cauliflower
2007
Plants contain water-soluble chlorophyll-binding proteins (WSCPs) that function neither as antennas nor as components of light-induced electron transfer of photosynthesis but are likely constituents of regulatory protective pathways in particular under stress conditions. This study presents results on the spectroscopic properties of recombinant WSCP from cauliflower reconstituted with chlorophyll b (Chl b) alone or with mixtures of Chl a and Chl b. Two types of experiments were performed: (a) measurements of stationary absorption spectra at 77 and 298 K and CD spectra at 298 K and (b) monitoring of laser flash-induced transient absorption changes with a resolution of 200 fs in the time doma…