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991.
An attempt to classify various types of avoided surface crossings originally discussed by Salem and co-workers is presented. From the present scheme, an order-of-forbiddenness criterion regarding reactivity is established from a consideration of electron and orbital counting. Since the new classification is qualitatively related to the energy gap created in the avoided crossing, the classification appears to be more systematic and informative. Energy transfer processes involved in electronically excited states may also be rationalized by such an application. Three major mechanistic types are distinguished: concerted two-electron process, concerted one-electron process, and stepwise one-electron process involving an ionic-pair intermediate. 相似文献
992.
A core-shell structure was found in AM SURE™ resin, in which most amino groups were located at the skin layer. The AM SURE™ resin revealed better synthetic efficiency, compared to the noncore-shell type resin in the synthesis of the fragment 65-74 of acyl carrier protein, the fragment 27-35 of HIV (human immunodeficiency virus) fusion inhibitor (T-20) and the Jung-Redemann 10-mer. 相似文献
993.
[formula: see text] S-Nitrosoglutathione oxidized 4-substituted Hantzsch 1,4-dihydropyridines in CH3CN/H2O or CH3CN/phosphate aqueous buffer solution to give aromatic products in various yields. 相似文献
994.
[formula: see text] The synthesis of all four diastereomers of bis(propionates), 3,5-dialkoxy-2,4-dimethylalkanals, by non-aldol aldol chemistry is described. The epoxy alcohols (3, 4) were converted into the mesylates (9, 11) which were cleanly rearranged to the desired 3,5-bis(oxygenated)-2,4-dimethylalkanals (10, 12) in high yield. The epoxy mesylates (13, 16) gave the desired products (14, 17) in good yield on treatment with TMSOTf and a hindered base. 相似文献
995.
The photoelectron spectrum of HCP has been obtained, Ionization potentials are found at 10.79 ± 0.01 eV (X2 Π) and 12.86 ± 0.01 eV (A 2 Σ). By comparison with HCP, a new interpretation of the first photoelectron band of HCN has been proposed which involves a Renner-Teller interaction in the Σ+ vibronic states of the molecular ion. 相似文献
996.
997.
We study rate processes in general Gaussian fluctuating environments using a path integral formalism. We derive a variational equation for the dominant survival path when the fluctuations relax exponentially or according to a stretched exponential law. In the case of a slowly varying barrier, the equilibrium regression approximation which is used by Frauenfelder and coworkers emerges. In this approximation, the survival path follows the ordinary law of relaxation to equilibrium. If the rate coefficients vary rapidly with environmental variables, however, the dominant survival paths exhibit more complex behaviour. Many phenomena analogous to geometrical optics occur. These include reflection off of rapid variations in rate constant, as well as refraction, giving paths very different from the equilibrium relaxation properties. A model with a piece-wise linear rate exhibits the basic phenomena, and the survival path equation is exactly solved for the general stretched exponential relaxing environment. 相似文献
998.
Hwang JY Choi HS Seo JS La HJ Kim DS Jeon HS Jeon MK Lee DH Gong YD 《The Journal of organic chemistry》2005,70(24):10151-10154
[reaction: see text] A library containing 1200 analogues of 2,6-difunctionalized 2-methyl-2H-1-benzopyran was constructed by using a solid-phase synthesis protocol. Polymer-bound 6-amido-, 6-sulfonamido-, and 6-uredo-functionalized 2-hydroxymethyl-2-methylbenzopyrans 10 were prepared as part of a first-generation diversification step by employing reactions of respective acid halides, sulfonyl chlorides, and isocyanates with the amine precursor 7. Transformations of the resin-bound intermediates 10 by reactions with alkyl and acid halides were then used to produce a diverse series of 2,6-difunctionalized 2-methyl-2H-1-benzopyran analogues 12 and 14. 相似文献
999.
Liping Heng Jin Zhai Yong Zhao Jinjie Xu Xianliang Sheng Lei Jiang 《Chemphyschem》2006,7(12):2520-2525
A light-emitting poly (distyryldimethylbenzene-co-triethylene glycol) rod-coil block copolymer was used to fabricate films with three-dimensionally ordered honeycomb structures by the breath-figure method. Photocurrent generation and photovoltaic performance are studied, and the dependence of photocurrent on applied electric field is investigated. Introducing the ordered porous structure significantly improves the photoelectric conversion behavior, because porous structures not only enhance the light-harvesting efficiency but also benefit charge separation and charge transfer. This phenomenon may have great prospects for enhancing the photovoltaic behavior of organic thin-film devices. 相似文献
1000.
Berry JF Cotton FA Daniels LM Murillo CA 《Journal of the American Chemical Society》2002,124(13):3212-3213
The molecule Ni(3)(dpa)(4)Cl(2) (1) can be oxidized by AgPF(6) to give crystalline Ni(3)(dpa)(4)(PF(6))(3) (2) (dpa is the anion of di(2-pyridyl)amine). This reversible oxidation occurs at a potential of 0.908 V vs Ag/AgCl electrochemically. The X-ray structure of 2 shows that the oxidation causes a major structural change (even though it is reversible), namely, a contraction of the Ni-Ni distances from ca. 2.43 A to 2.284[1] A. In addition, the electronic structure changes so that from four unpaired electrons in 1 there is only one in 2. From these remarkable results, it is inferred that while 1, and all higher homologues with 5, 7, 9,... nickel atoms are poor electronic conductors, the cations obtainable from them may be much better ones. This in turn means that by controlling the oxidation state electrochemically, these molecules may be able to function as nanoscale diodes. 相似文献