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91.
Margarida S. Miranda José E. Rodríguez‐Borges Joaquim C. G. Esteves da Silva Xerardo García‐Mera 《Journal of Physical Organic Chemistry》2012,25(6):515-522
The cycloaddition between glyoxylate imines possessing two chiral auxiliaries, N‐(R)‐ or N‐(S)‐1‐phenylethyl and 8‐phenylmenthyl or 8‐phenylneomenthyl, and cyclopentadiene is described. Computational calculations using density functional theory with the Becke, three‐parameter, Lee–Yang–Parr functional and the 6‐31G(d) basis set were performed to better understand the highly diastereoselective mechanism and the exo‐selectivity observed experimentally for these ionic aza‐Diels–Alder reactions. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
92.
Luis Miguel Azofra Ibon Alkorta José Elguero 《Journal of Physical Organic Chemistry》2012,25(12):1286-1292
A theoretical study of the hemiacetal formation reaction between methanol and CX3CHO (X = H, F, Cl, Br, and I) has been carried out using density functional theory and Becke, three‐parameter, Lee–Yang–Parr/6‐311++G(d,p) computational methods. The stationary points of the reaction between the isolated molecules and the reaction catalyzed by an additional methanol molecule have been characterized. Because the final products present a stereogenic center, the potential autocatalysis of the reaction has been examined and also the possibility of spontaneous generation of chirality when the hemiacetal molecules are involved in the transition state structure. High barriers are found in the reaction between the isolated molecules that are reduced by the assistance of an additional molecule (methanol or hemiacetal product). The reactions catalyzed by the hemiacetal products show higher barriers than the one catalyzed by methanol. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
93.
The control of sound transmission through panels is an important noise control problem in the aerospace, aeronautical, and automotive industries. The trend towards using lightweight composite materials that have lower sound insulation performance is a negative factor regarding low frequency transmission loss. Double-panel partitions with the gap filled with sound absorption materials are often employed to improve the sound insulation performance with reduced added weight penalty. However, in the low frequency range, the strong coupling between the panels through the air cavity and mechanical paths may greatly reduce the sound transmission performance, making it even lower than the performance of a single panel in some frequency ranges. In this work, an experimental investigation of a new kind of hybrid (active/passive) acoustic actuator is presented. The idea consists of replacing the acoustic absorption material by a hybrid actuator aiming at improving the transmission loss at low frequencies without altering the passive attenuation. A prototype of the system is tested in a plane wave acoustic tube setup. Different kinds of SISO feedforward control implementations were used to attenuate the sound power transmitted through the hybrid active–passive panel using an error microphone or a particle velocity sensor placed downstream with respect to the sample panel. Measurement results of the transmission loss with active and hybrid attenuation are presented and discussed. 相似文献
94.
Anomalous behavior of the resistivity at or just below the Néel temperature in antiferromagnetic metals is usually attributed to the formation of superzone gaps. However, we find that RMn12-xFex alloys which have no such gaps exhibit a similarly anomalous resistivity. We show that electron scattering by substitutional spin disorder can account for such behavior of itinerant magnets. This mechanism, which has not been studied before, leads to a relaxation rate that is proportional to x(12-x)m(2), where m is the staggered magnetization. Together with spin fluctuations, phonon, and impurity scattering, it accounts well for the resistivity data we obtain for HoMn12-xFex, for 0< or =x< or =9, in the temperature range of 4 to 400 K. 相似文献
95.
Armando Herize José R. Mora Jesus Lezama Edgar Marquez Tania Córdova Gabriel Chuchani 《Journal of Physical Organic Chemistry》2009,22(2):170-176
The elimination kinetic of methyl carbazate in the gas phase was determined in a static system over the temperature range of 340–390 °C and pressure range of 47–118 Torr. The reaction is homogeneous, unimolecular, and obeys a first order rate law. The decomposition products are methyl amine, nitrous acid, and CO gas. The variation of the rate coefficients with temperatures is given by the Arrhenius expression: log k1 (s?1) = (11.56 ± 0.34) ? (180.7 ± 4.1) kJ mol?1(2.303 RT)?1. The estimated kinetics and thermodynamics parameters are in good agreement to the experimental values using B3LYP/6‐31G (d,p), and MP2/6‐31G (d,p) levels of theory. These calculations imply a molecular mechanism involving a concerted non‐synchronous quasi three‐membered ring cyclic transition state to give an unstable intermediate, 1,2‐oxaziridin‐3‐one. Bond order analysis and natural charges implies that polarization of O (alkyl)? C (alkyl) bond of the ester is rate determining in this reaction. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
96.
Human serum albumin consists of a single polypeptide of 585 amino acid residues with 1 Trp residue. In the present work, we
measured fluorescence lifetimes of the protein in both native and denatured states. The results indicate that Trp emission
occurs with three lifetimes in both states. Lifetimes values and contribution to the global emission decay differ between
the two states. Data are interpreted as the results of an emission occurring from three substructures of the tryptophan formed
in the excited state. Two of these substructures are already present for the tryptophan free in solution. The third lifetime
is the result of the interaction between the tryptophan residue and surrounding microenvironment. The populations of these
substructures characterized by the pre-exponential parameters of the fluorescence lifetimes are dependent on the fluorophore
microenvironment and on the global protein structure. 相似文献
97.
98.
This work investigates different hemp surface modifications (mercerization, maleated polyethylene (MAPE) addition in solution or in melt blending) to improve the properties of linear medium density polyethylene (LMDPE). From the composites produced, a complete morphological and tensile characterization was performed for a fixed hemp content (30% wt.). The morphological analysis showed that both the direct (melt blending) and solution modifications were able to significantly improve the composites interface quality and therefore the tensile properties (151% increase in modulus and 36% increase in strength over the neat matrix) within the range of conditions tested. 相似文献
99.
100.