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41.
Lam WH Gaspar PP Hrovat DA Trieber DA Davidson ER Borden WT 《Journal of the American Chemical Society》2005,127(27):9886-9894
CASSCF, CASPT2, CCSD(T), and (U)B3LYP electronic structure calculations have been performed in order to investigate the thermal fragmentation of P-phenylphosphirane (1) to phenylphosphinidene (PhP) and ethylene. The calculations show that generation of triplet PhP via a stepwise pathway is 21 kcal mol(-1) less endothermic and has a 12 kcal mol(-1) lower barrier height than concerted fragmentation of 1 to give singlet PhP. The formation of singlet PhP via a concerted pathway is predicted to be stereospecific, whereas formation of triplet PhP is predicted to occur with complete loss of stereochemistry. However, calculations on fragmentation of anti-cis-2,3-dimethyl-P-mesitylphosphirane (cis-1Me) to triplet mesitylphosphinidene (MesP) indicate that this reaction should be more stereospecific, in agreement with the experimental results of Li and Gaspar. Nevertheless, with a predicted free energy of activation of 42 kcal mol(-1), the formation of MesP from cis-1Me is not likely to have occurred in an uncatalyzed reaction at the temperatures at which this phosphirane has been pyrolyzed. 相似文献
42.
A Review of: “Aquatic Chemistry (An Introduction Emphasizing Chemical Equilibria in Natural Waters)”
Ernest Merian 《International journal of environmental analytical chemistry》2013,93(3-4):317-318
Abstract 2nd Edition, by Prof. Dr. Werner Stumm, Swiss Federal Institute of Technology, Zurich, and Prof. Dr. James J. Morgan, California Institute of Technology, Pasadena, 780 pages (including 97 tables, 167 figures, an appendix of 8 pages “Thermodynamic Properties of Common Chemical Species in Aquatic Systems”, an author index of 10 pages, and a subject index of 14 pages), stiff paper cover, format 234 ± 161 mm, ISBN 0-471-04831-3, John Wiley & Sons, New York (1981) 相似文献
43.
Low-angle X-ray diffraction measurements of the distance between myosin filaments comprising the smectic B1 liquid crystal found in skinned crayfish striated muscle were made. The interfilament distanceas a function of applied compressive osmotic pressure wasdetermined and the bulk modulus of this myofilament liquid crystal ascertained. Under compression the behavior of this myosin filament lattice is shown to be predicted well by the Murnaghan equation of state. The isothermal bulk modulus, B o, of this myosin filament liquid crystal is 1.51 × 105 dynes/cm2 at 2°C and at 46% actin overlap. 相似文献
44.
Dr. Xavier Just-Baringo Alejandro Yeste-Vázquez Javier Moreno-Morales Dr. Clara Ballesté-Delpierre Prof. Jordi Vila Prof. Ernest Giralt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(51):12987-12991
The introduction of a novel tetra-ortho-chloroazobenzene amino acid (CEBA) has enabled photoswitching of the antimicrobial activity of tyrocidine A analogues by using exclusively visible light, granting spatiotemporal control under benign conditions. Compounds bearing this photoswitchable amino acid become active upon irradiation with red light, but quickly turn-off upon exposure to other visible light wavelengths. Critically, sunlight quickly triggers isomerisation of the red light-activated compounds into their original trans form, offering an ideal platform for self-deactivation upon release into the environment. Linear analogues of tyrocidine A were found to provide the best photocontrol of their antimicrobial activity, leading to compounds active against Acinetobacter baumannii upon isomerisation. Exploration of their N- and C-termini has provided insights into key elements of their structure and has allowed obtaining new antimicrobials displaying excellent strain selectivity and photocontrol. 相似文献
45.
We consider various quotients of the C*-algebra of bounded operators on a nonseparable Hilbert space, and prove in some cases that, assuming some restriction of the Generalized Continuum Hypothesis, there are many outer automorphisms. 相似文献
46.
47.
The effects of quasi-periodicity on the splitting of invariant manifolds are examined. We have found that some harmonics that could be expected to be dominant in some ranges of the perturbation parameter actually are nondominant. It is proved that, under reasonable conditions, this is due to the arithmetic properties of the frequencies. 相似文献
48.
Nera Cagnoli Paolo Ceccherelli Massimo Curini Maria Carla Marcotullio Ernest Wenkert 《合成通讯》2013,43(11):1261-1271
Copper oxide-catalyzed decomposition of 1-diazoacetyl-1-methyl-3-methylenecyclohexanes produces strained tricycles whose reduction or hydrolysis affords 6-bicyclo[3.2.1]octanones. 相似文献
49.
Ernest L. Eliel 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):73-95
Abstract Earlier work concerned with a highly stereoselective asymmetric synthesis based on a 1,3-oxathiane as the ciral auxiliary reagent is reviewed and recent applications to the synthesis of the four stereoisomers of malyngolide, of (R)-(+)-γ-caprolactone (a pheromone of the Trogoderma glabrum beetle) and of (S)-(+)-mevalolactone are presented. The mechanism underlying this asymmetric synthesis is discussed briefly. 相似文献
50.
The kinetics of the noncatalyzed reaction between α, ω -dicarboxypoly-amide-11 and α, ω -dihydroxypolyoxyalkylenes is investigated by using the reactions of 11-dodecylamidoundecanoic acid with 1-dodecanol, 2-tridecanol, α-dodecyl-ω-hydroxypolyoxyethylene or α-dodecyl-ω;-hydroxypolyoxypropylene as models. Kinetic data fit a 3rd overall order (2 in acid and 1 in alcohol). Rate constants and activation parameters are determined and compared. 相似文献