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931.
The 0 K dissociative ionization onsets of C2H3X --> C2H3(+) + X (X = Cl, I) are measured by threshold photoelectron-photoion coincidence spectroscopy. The heats of formation of C2H3Cl (Delta H(f,0K)(0) = 30.2 +/- 3.2 kJ mol(-1) and Delta(H f,298K)(0) = 22.6 +/- 3.2 kJ mol(-1)) and C2H3I (Delta(H f,0K)(0) = 140.2 +/- 3.2 kJ mol(-1) and Delta(H f,298K)(0) = 131.2 +/- 3.2 kJ mol(-1)) and C- X bond dissociation enthalpies as well as those of their ions are determined. The data help resolve a longstanding discrepancy among experimental values of the vinyl chloride heat of formation, which now agrees with the latest theoretical determination. The reported vinyl iodide heat of formation is the first reliable experimental determination. Additionally, the adiabatic ionization energy of C2H3I (9.32 +/- 0.01 eV) is measured by threshold photoelectron spectroscopy. 相似文献
932.
Gustafsson T Gilmour R Seeberger PH 《Chemical communications (Cambridge, England)》2008,(26):3022-3024
The DAST-mediated conversion of a range of alcohols to the corresponding fluorides in a microstructured device is described. This safe, practical fluorination method will facilitate reactions currently challenging on large scale. 相似文献
933.
Odedra A Geyer K Gustafsson T Gilmour R Seeberger PH 《Chemical communications (Cambridge, England)》2008,(26):3025-3027
A highly efficient system for tris(trimethylsilyl)silane (TTMSS) mediated deoxygenation, dehalogenation and hydrosilylation reactions is described in a microstructured device; this convenient platform enables the scale up of radical-based processes. 相似文献
934.
Shuman NS Zhao LY Boles M Baer T Sztáray B 《The journal of physical chemistry. A》2008,112(42):10533-10538
The dissociative photoionization onsets for Cl and Br loss reactions were measured for HCCl3, HCCl2Br, HCClBr2, and HCBr3 by threshold photoelectron photoion coincidence (TPEPICO) in order to establish the heats of formation of the mixed halides as well as the following fragment ions: HCCl2(+), HCClBr(+), HCBr2(+). The first zero Kelvin onsets were measured with a precision of 10 meV. The second onsets, which are in competition with the lower energy onsets, were established with a precision of 60 meV. Because both the chloroform and bromoform have relatively well established heats of formation, these measurements provide a route for establishing the heats of formation of the mixed halomethanes within uncertainties of less than 5 kJ mol(-1). 相似文献
935.
Tsimachidis D Cesla P Hájek T Theodoridis G Jandera P 《Journal of separation science》2008,31(6-7):1130-1136
A new capillary electrophoretic method for the chiral separation of four major Cinchona alkaloids (quinine/quinidine and cinchonine/cinchonidine) was developed using heptakis-(2,6-di-O-methyl)-beta-cyclodextrin as the chiral selector. The inner walls of the separation capillary were modified with a thin polyacrylamide layer, which substantially reduced the electroosmotic flow and improved the chiral resolution and the reproducibility of the migration time of the analytes. Various operation parameters were optimised, including the pH, the capillary temperature, the concentration of the background electrolyte, and the concentration of the chiral selector. Baseline separation of the two diastereomer pairs was achieved in 12 minutes in ammonium acetate background electrolyte pH 5.0 with addition of cyclodextrin in a concentration of 3 mM or higher. 相似文献
936.
Juan José Giner Casares Luis Camacho Prof. Dr. Maria Teresa Martín‐Romero Prof. Dr. José Javier López Cascales Prof. Dr. 《Chemphyschem》2008,9(17):2538-2543
Studying the effect of alkali and alkaline‐earth metal cations on Langmuir monolayers is relevant from biophysical and nanotechnological points of view. In this work, the effect of Na+ and Ca2+ on a model of an anionic Langmuir lipid monolayer of dimyristoylphosphatidate (DMPA?) is studied by molecular dynamics simulations. The influence of the type of cation on lipid structure, lipid–lipid interactions, and lipid ordering is analyzed in terms of electrostatic interactions. It is found that for a lipid monolayer in its solid phase, the effect of the cations on the properties of the lipid monolayer can be neglected. The influence of the cations is enhanced for the lipid monolayer in its gas phase, where sodium ions show a high degree of dehydration compared with calcium ions. This loss of hydration shell is partly compensated by the formation of lipid–ion–lipid bridges. This difference is ascribed to the higher charge‐to‐radius ratio q/r for Ca2+, which makes ion dehydration less favorable compared to Na+. Owing to the different dehydration behavior of sodium and calcium ions, diminished lipid–lipid coordination, lipid–ion coordination, and lipid ordering are observed for Ca2+ compared to Na+. Furthermore, for both gas and solid phases of the lipid Langmuir monolayers, lipid conformation and ion dehydration across the lipid/water interface are studied. 相似文献
937.
Mazouz M Camsonne A Camacho CM Ferdi C Gavalian G Kuchina E Amarian M Aniol KA Beaumel M Benaoum H Bertin P Brossard M Chen JP Chudakov E Craver B Cusanno F de Jager CW Deur A Feuerbach R Fieschi JM Frullani S Garçon M Garibaldi F Gayou O Gilman R Gomez J Gueye P Guichon PA Guillon B Hansen O Hayes D Higinbotham D Holmstrom T Hyde CE Ibrahim H Igarashi R Jiang X Jo HS Kaufman LJ Kelleher A Kolarkar A Kumbartzki G Laveissiere G Lerose JJ Lindgren R Liyanage N Lu HJ Margaziotis DJ Meziani ZE 《Physical review letters》2007,99(24):242501
The present experiment exploits the interference between the deeply virtual Compton scattering (DVCS) and the Bethe-Heitler processes to extract the imaginary part of DVCS amplitudes on the neutron and on the deuteron from the helicity-dependent D(e,e'gamma)X cross section measured at Q2=1.9 GeV2 and xB=0.36. We extract a linear combination of generalized parton distributions (GPDs) particularly sensitive to E_{q}, the least constrained GPD. A model dependent constraint on the contribution of the up and down quarks to the nucleon spin is deduced. 相似文献
938.
The mechanism of the Co(II) catalytic electroreduction of water insoluble CoR2 salt in the presence of cysteine was developed. CoR2 = cobalt(II) cyclohexylbutyrate is the component of a carbon paste electrode. Electrode surface consecutive reactions are:
(a) fast (equilibrium) reaction of the complex formation, (b) rate-determining reversible reaction of the promoting process of CoR(Ac+) complex formation, (c) rate-determining irreversible reaction of the electroactive complex formation with ligand-induced adsorption, and (d) fast irreversible reaction of the electroreduction. Reactions (a,b) connected with CoR2 dissolution and reactions (c,d) connected with CoR2 electroreduction are catalyzed by . Regeneration of (reactions “b,d”) and accumulation of atomic Co(0) (reaction “d”) take place. Experimental data [Sugawara et al., Bioelectrochem
Bioenergetics 26:469, 1991]: i
a vs E (i
a is anodic peak, E is cathodic accumulation potential), i
a vs , and i
a vs pH have been quantitatively explained. 相似文献
939.
Gengeliczki Z Szepes L Sztaray B Baer T 《The journal of physical chemistry. A》2007,111(31):7542-7550
A new organometallic complex, Co(CO)2NOtBuNC, was synthesized and investigated by photoelectron spectroscopy (PES) and threshold photoelectron photoion coincidence (TPEPICO) spectrometry in order to determine its ionization energy as well as the bond energies in the ionic forms. The assignment of the nine peaks in the PES was based on Kohn-Sham molecular orbital energies, and an adiabatic ionization energy of 7.30 +/- 0.05 eV was determined. In the TPEPICO experiment, the following 0 K onsets were determined for the various fragment ions: CoCONOtBuNC+ (8.17 +/- 0.05 eV); CoNOtBuNC+ (9.01 +/- 0.05 eV); and CotBuNC+ (10.42 +/- 0.05 eV). Because the photon source did not extend above 14 eV, we could not observe the bare Co+ ion in the experiment. The heat of formation of the CotBuNC+ ion was estimated by ab initio and DFT calculations of the CoL+ + tBuNC --> CotBuNC+ + L (L = CO, NO, NH3, H2O, PMe3) substitution enthalpies. 相似文献
940.
The sequential ethene (C2H4) loss channels of energy-selected ethylphosphine ions have been studied using threshold photoelectron photoion coincidence (TPEPICO) spectroscopy in which ion time-of-flight (TOF) distributions are recorded as a function of the photon energy. The ion TOF distributions and breakdown diagrams have been modeled in terms of the statistical RRKM theory for unimolecular reactions, providing 0 K dissociation onsets, E0, for the ethene loss channels. Three RRKM curves were used to model the five measurements, since two of the reactions differ only by the internal energy of the parent ion. This series of dissociations provides a detailed check of the calculation of the product energy distribution for sequential reactions. From the determined E0's, the heats of formation of several ethylphosphine neutrals and ions have been determined: Delta(f)H degrees 298K[P(C(2)H(5))3] = -152.7 +/- 2.8 kJ/mol, Delta(f)H degrees 298K[P(C(2)H(5))3+] = 571.6 +/- 4.0 kJ/mol, Delta(f)H degrees 298K[HP(C(2)H(5))2] = -89.6 +/- 2.1 kJ/mol, Delta(f)H degrees 298K[HP(C(2)H(5))2+] = 669.9 +/- 2.5 kJ/mol, Delta(f)H degrees 298K[H(2)PC(2)H(5)] = -36.5 +/- 1.5 kJ/mol, Delta(f)H degrees 298K[H(2)PC(2)H(5)+] = 784.0 +/- 1.9 kJ/mol. These values have been supported by G2 and G3 calculations using isodesmic reactions. Coupled cluster calculations have been used to show that the C2H4 loss channel, which involves a hydrogen transfer step, proceeds without a reverse energy barrier. 相似文献