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151.
Rafael Almeida 《Journal of Molecular Structure》1995,330(1-3):423-430
Here is used an expression, obtained from linear response theory, to carry out model calculations of thermal rate constants for a potential curve crossing system. An illustrative calculation is presented which employs a modified fast Fourier transform to study how the thermal rate coefficients are affected when non-adiabatic effects are considered. Finally an Arrhenius analysis is performed on the computed thermal rate coefficients. 相似文献
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Ederley Vélez Jairo Quijano Rafael Notario Elizabeth Pabón Juliana Murillo Julieth Leal Edilma Zapata Gustavo Alarcón 《Journal of Physical Organic Chemistry》2009,22(10):971-977
This paper reports a theoretical study, at the B3LYP/6–31 + G(d,p) and M05‐2X/6–31G + (d,p) levels, on the thermal decomposition of menthyl benzoate (2‐isopropyl‐5‐methylcyclohexyl benzoate). It undergoes a unimolecular first‐order elimination to give 3‐menthene (1‐isopropyl‐4‐methylcyclohexene), 2‐menthene (3‐isopropyl‐6‐methylcyclohexene), and benzoic acid. We studied two possible mechanisms trying to explain the formation of 2‐ and 3‐menthene, via six‐membered or four‐membered cyclic transition states. Rate constants were calculated at two temperatures, 587.1 and 598.6 K, and they agree well with the experimentally determined values. We verify that 3‐menthene is the product mainly formed at both temperatures. The progress of the reactions has been followed by means of the Wiberg bond indices. Intrinsic reaction coordinate (IRC) calculations have been carried out to verify that the localized transition state structures connect with the reactants and products and also to verify that the parent compound, menthyl benzoate, is taking the cis‐configuration needed in the reaction. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
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Dendronized Anionic Gold Nanoparticles: Synthesis,Characterization, and Antiviral Activity
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Cornelia E. Peña‐González Pilar García‐Broncano Prof. M. Francesca Ottaviani Dr. Michela Cangiotti Dr. Alberto Fattori Margarita Hierro‐Oliva Prof. M. Luisa González‐Martín Dr. Jorge Pérez‐Serrano Dr. Rafael Gómez Prof. M. Ángeles Muñoz‐Fernández Dr. Javier Sánchez‐Nieves Dr. F. Javier de la Mata 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(9):2987-2999
Anionic carbosilane dendrons decorated with sulfonate functions and one thiol moiety at the focal point have been used to synthesize water‐soluble gold nanoparticles (AuNPs) through the direct reaction of dendrons, gold precursor, and reducing agent in water, and also through a place‐exchange reaction. These nanoparticles have been characterized by NMR spectroscopy, TEM, thermogravimetric analysis, X‐ray photoelectron spectroscopy (XPS), UV/Vis spectroscopy, elemental analysis, and zeta‐potential measurements. The interacting ability of the anionic sulfonate functions was investigated by EPR spectroscopy with copper(II) as a probe. Different structures and conformations of the AuNPs modulate the availability of sulfonate and thiol groups for complexation by copper(II). Toxicity assays of AuNPs showed that those produced through direct reaction were less toxic than those obtained by ligand exchange. Inhibition of HIV‐1 infection was higher in the case of dendronized AuNPs than in dendrons. 相似文献
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Shalom Eliahou Rafael H. Villarreal 《Proceedings of the American Mathematical Society》2002,130(2):345-351
Let be a toric set in the affine space . Given a set of binomials in the toric ideal of , we give a criterion for deciding the equality rad( ) = . This criterion extends to arbitrary dimension, and to arbitrary fields, an earlier result which concerned only monomial curves over an algebraically closed field of characteristic zero.