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991.
Aullón G Bernhardt PV Bozoglian F Font-Bardía M Macpherson BP Martínez M Rodríguez C Solans X 《Inorganic chemistry》2006,45(21):8551-8562
We have investigated the isomeric distribution and rearrangement of complexes of the type [CoXLn]2+,3+ (where X = Cl-, OH-, H2O, and Ln represents a pentadentate 13-, 14-, and 15-membered tetra-aza or diaza-dithia (N4 or N2S2) macrocycle bearing a pendant primary amine). The preparative procedures for chloro complexes produced almost exclusively kinetically preferred cis isomers (where the pendant primary amine is cis to the chloro ligand) that can be separated by careful cation-exchange chromatography. For L13 and L14 the so-called cis-V isomer is isolated as the kinetic product, and for L15 the cis-VI form (an N-based diastereomer) is the preferred, while for the L14(S) complex both cis-V and trans-I forms are obtained. All these complexes rearrange to form stable trans isomers in which the pendent primary amine is trans to the monodentate aqua or hydroxo ligand, depending on pH and the workup procedure. In total 11 different complexes have been studied. From these, two different trans isomers of [CoClL14(S)]2+ have been characterized crystallographically for the first time in addition to a new structure of cis-V-[CoClL14(S)]2+; all were isolated as their chloride perchlorate salts. Two additional isomers have been identified and characterized by NMR as reaction intermediates. The remaining seven forms correspond to the complexes already known, produced in preparative procedures. The kinetic, thermal, and baric activation parameters for all the isomerization reactions have been determined and involve large activation enthalpies and positive volumes of activation. Activation entropies indicate a very important degree of hydrogen bonding in the reactivity of the complexes, confirmed by density functional theory studies on the stability of the different isomeric forms. The isomerization processes are not simple and even some unstable intermediates have been detected and characterized as part of the above-mentioned 11 forms of the complexes. A common reaction mechanism for the isomerization reactions has been proposed for all the complexes derived from the observed kinetic and solution behavior. 相似文献
992.
993.
Bond dissociation enthalpies (BDEs) of a large series of aliphatic amines (21) were measured by means of photoacoustic calorimetry. Despite the different structures studied in the primary, secondary, and tertiary amine series, the alpha(C-H) BDEs were found to be very similar for unconstrained amines with values very close to 91 kcal/mol. alphaC- and N-alkylation or introduction of an hydroxy group only slightly affect the BDEs, a fact in perfect agreement with calculations performed at different CBS levels. This demonstrates the predominance of the two-orbital-three-electron interaction involving the N and alphaC(*) orbitals. On the other hand, the N-H BDE decreases when going from primary to secondary amines. This result is interpreted in term of a hyperconjugation in sigmaC-C bonds, which leads to a stabilization of the aminyl radical. For cyclized amines, the BDEs depend on the relative geometry of the singly occupied alphaC(*) orbital with respect to that of the N atom, disfavoring the two-orbital-three-electron interaction. However, such structures can exhibit through-bond interaction. For a crowded structure such as triisopropylamine, for which the alphaC(*) orbital is not coplanar with the nitrogen one, the relaxation of a strain energy allows the BDE to be comparable to flexible structures. 相似文献
994.
R. Peyton Thorn Walter A. Payne Xavier D. F. Chillier Louis J. Stief Fred L. Nesbitt D. C. Tardy 《国际化学动力学杂志》2000,32(5):304-316
The total rate constant k1 has been determined at P = 1 Torr nominal pressure (He) and at T = 298 K for the vinyl‐methyl cross‐radical reaction: (1) CH3 + C2H3 → Products. The measurements were performed in a discharge flow system coupled with collision‐free sampling to a mass spectrometer operated at low electron energies. Vinyl and methyl radicals were generated by the reactions of F with C2H4 and CH4, respectively. The kinetic studies were performed by monitoring the decay of C2H3 with methyl in excess, 6 < [CH3]0/ [C2H3]0 < 21. The overall rate coefficient was determined to be k1(298 K) = (1.02 ± 0.53) × 10−10 cm3 molecule−1 s−1 with the quoted uncertainty representing total errors. Numerical modeling was required to correct for secondary vinyl consumption by reactions such as C2H3 + H and C2H3 + C2H3. The present result for k1 at T = 298 K is compared to two previous studies at high pressure (100–300 Torr He) and to a very recent study at low pressure (0.9–3.7 Torr He). Comparison is also made with the rate constant for the similar reaction CH3 + C2H5 and with a value for k1 estimated by the geometric mean rule employing values for k(CH3 + CH3) and k(C2H3 + C2H3). Qualitative product studies at T = 298 K and 200 K indicated formation of C3H6, C2H2, and C3H5 as products of the combination‐stabilization, disproportionation, and combination‐decomposition channels, respectively, of the CH3 + C2H3 reaction. We also observed the secondary C4H8 product of the subsequent reaction of C3H5 with excess CH3; this observation provides convincing evidence for the combination‐decomposition channel yielding C3H5 + H. RRKM calculations with helium as the deactivator support the present and very recent experimental observations that allylic C‐H bond rupture is an important path in the combination reaction. The pressure and temperature dependencies of the branching fractions are also predicted. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 304–316, 2000 相似文献
995.
It is often the case that a covering map of the open annulus is semiconjugate to a map of the circle of the same degree. We investigate this possibility and its consequences on the dynamics. In particular, we address the problem of the classification up to conjugacy. However, there are examples which are not semiconjugate to a map of the circle, and this opens new questions. 相似文献
996.
997.
Xavier Calmet Basem Kamal El-Menoufi Boris Latosh Sonali Mohapatra 《The European Physical Journal C - Particles and Fields》2018,78(9):780
The effective field theory of quantum gravity generically predicts non-locality to be present in the effective action, which results from the low-energy propagation of gravitons and massless matter. Working to second order in gravitational curvature, we reconsider the effects of quantum gravity on the gravitational radiation emitted from a binary system. In particular, we calculate for the first time the leading order quantum gravitational correction to the classical quadrupole radiation formula which appears at second order in Newton’s constant. 相似文献
998.
999.
Marion Barthomeuf Xavier Castel Laurent Le Gendre Justine Louis Martine Denis Christine Pissavin 《Photochemistry and photobiology》2019,95(4):1035-1044
Structural, microstructural and bactericidal surface properties of TiO2‐coated glass substrates elaborated by reactive Radiofrequency sputtering are investigated. As pathogenic bacteria in biofilms are a major concern in food industries due to their growing resistance to cleaning and sanitizing procedures, the development of photoactive surfaces exhibiting bactericidal properties is acknowledged as an effective approach to tackle bacterial contaminations. Our principal aim concerns the study of the photoactive top‐layer thickness impact (from 80 nm to ~500 nm) on Listeria monocytogenes. Structural characterization of the TiO2 layers demonstrates that anatase and rutile phases are both present, depending on the film thickness. Photocatalytic activity of the samples has been evaluated through the degradation of aqueous methylene blue (MB) solutions under UVA light illumination for various time periods. The results show an efficiency rating increase according to TiO2 film thickness up to a threshold value close to 400 nm. Moreover, a significant decrease of the adherent bacteria number is observed after 20 min of UVA illumination. The quantitative study of the bactericidal activity associated with scanning electron microscopy observations of the postprocess bacteria damaged cells demonstrates the efficiency of the 240‐nm‐thick TiO2 coating sample. The results are correlated with the production of hydroxyl radicals during the process of photocatalysis. 相似文献
1000.
Prof. Dr. Wilfred F. van Gunsteren Prof. Dr. Xavier Daura Prof. Dr. Niels Hansen Prof. Dr. Alan E. Mark Prof. Dr. Chris Oostenbrink Prof. Dr. Sereina Riniker Prof. Dr. Lorna J. Smith 《Angewandte Chemie (International ed. in English)》2018,57(4):884-902
Computer simulation of molecular systems enables structure–energy–function relationships of molecular processes to be described at the sub‐atomic, atomic, supra‐atomic, or supra‐molecular level. To interpret results of such simulations appropriately, the quality of the calculated properties must be evaluated. This depends on the way the simulations are performed and on the way they are validated by comparison to values Qexp of experimentally observable quantities Q. One must consider 1) the accuracy of Qexp, 2) the accuracy of the function Q( r N) used to calculate a Q‐value based on a molecular configuration r N of N particles, 3) the sensitivity of the function Q( r N) to the configuration r N, 4) the relative time scales of the simulation and experiment, 5) the degree to which the calculated and experimental properties are equivalent, and 6) the degree to which the system simulated matches the experimental conditions. Experimental data is limited in scope and generally corresponds to averages over both time and space. A critical analysis of the various factors influencing the apparent degree of (dis)agreement between simulations and experiment is presented and illustrated using examples from the literature. What can be done to enhance the validation of molecular simulation is also discussed. 相似文献