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41.
Thomas Unnerstall 《Journal of statistical physics》1989,54(1-2):379-403
The irreversible macroscopic dynamics of the Josephson junction coupled to external wires acting as a current source is derived rigorously from the underlying microscopic Hamiltonian quantum mechanics. The external systems are treated in the singular coupling limit. The use of this limit is explicitly justified via an interpretation of the singular coupling limit in terms of the relative magnitudes of system, reservoir, and coupling energies. The qualitative behavior of the macroscopic dynamical equations is shown to depend sensitively and crucially on the interaction between the wires and the superconductors and on the size of the wires: the dc Josephson effect only happens when one lets Cooper pairs be driven into the junction by collective (i.e., small) reservoirs. 相似文献
42.
以碳酸锶为甲烷吸附活化的模型催化剂,用切换变应答、CH4(CO2)-TPD等技术,对甲烷的吸附、碱性对催化剂性能的影响进行了研究,结果表明,甲烷在碳酸锶上的活化显示出明显的酸碱活化机理特征,瞬变应答及TPD结果均证明,甲烷在碳酸锶表面有较强的吸附,其脱附温度约310℃,关联结果表明,甲烷转化率及C2烃收率与催化剂表面SrO碱性中心浓度有非常一致的顺变关系,因此催化剂表面的酸碱中心可能是甲烷的选择活 相似文献
43.
掺杂SrTiO3体系上甲烷氧化偶联反应的研究—活性氧物种的作用 总被引:1,自引:0,他引:1
本文采用循环氧化还原法,脉冲反应及TPD等实验手段对钙钛矿型氧化物掺杂SrTiO_3体系上甲烷氧化偶联反应中的活性氧物种的作用进行了研究.结果表明,催化剂由于掺杂产生的未被充分还原的氧物种(O~(α-)(0<α<2)是活化甲烷并促使其发生偶联反应的主要的活性中心,而表面晶格氧(O_L~(2-))则主要使甲烷深度氧化;消耗掉的未被充分还原的氧或晶格氧可以在高温下氧气氛中氧化复原.对于掺杂的SrTiO_3样品,体相中的氧在惰性气氛或还原气氛中可以向表面扩散.吸附氧可能不直接与甲烷作用而主要通过催化剂表面活性氧物种(O~(α-)或O_L~(2-))而起作用. 相似文献
44.
Yuhua Zhang 《Tetrahedron letters》2004,45(41):7581-7584
Under microwave conditions, tetrahydrofuran (THF), tetrahydropyran and 1,4-dioxane are added directly onto alkynes and generated various vinyl cycloethers. 相似文献
45.
硼酸酯偶联剂的合成与表征 总被引:11,自引:0,他引:11
通过分子结构设计,合成了一种氮一硼内配位结构的硼酸酯偶联剂,解决了硼酸酯水解稳定性差的问题,同时分子结构中含有氨基、丁氧基等活性基团。用傅立叶变换红外光谱对硼酸酯进行了结构表征,讨论了原料配比、合成工艺等对硼酸酯收率及反应速率的影响,并通过实验确定了最佳配方及工艺。对硼酸酯的物理性能、溶解性、水解稳定性及对硼酸铝晶须的表面处理效果进行了表征。结果表明:合成的硼酸酯偶联剂由于具有氮-硼内配位作用,表现出优良的水解稳定性,并且硼酸酯偶联剂对硼酸铝晶须具有良好的表面改性效果。 相似文献
46.
Frédéric Cadoret 《Tetrahedron letters》2007,48(31):5491-5495
Competition experiments were performed by adding pre-formed solutions of diisopropyloxy(η2-cyclopentene)titanium in diethyl ether to various mixtures of unsaturated compounds at low temperature, establishing the following reactivity scale: aldehyde > nitrile > ketone > terminal alkyne > internal alkyne > terminal alkene > ester, carbonate. 相似文献
47.
The self‐complementary tetrameric propargyl triols 8, 14, 18 , and 21 were synthesized to investigate the duplex formation of self‐complementary, ethynylene‐linked UUAA, AAUU, UAUA, and AUAU analogues with integrated bases and backbone (ONIBs). The linear synthesis is based on repetitive Sonogashira couplings and C‐desilylations (34–72% yield), starting from the monomeric propargyl alcohols 9 and 15 and the iodinated nucleosides 3, 7, 11 , and 13 . Strongly persistent intramolecular H‐bonds from the propargylic OH groups to N(3) of the adenosine units prevent the gg‐type orientation of the ethynyl groups at C(5′). As such, an orientation is required for the formation of cyclic duplexes, this H‐bond prevents the formation of duplexes connected by all four base pairs. However, the central units of the UAUA and AAUU analogues 18 and 14 associate in CDCl3/(D6)DMSO 10 : 1 to form a cyclic duplex characterized by reverse Hoogsteen base pairing. The UUAA tetramer 8 forms a cyclic UU homoduplex, while the AUAU tetramer 21 forms only linear associates. Duplex formation of the O‐silylated UUAA and AAUU tetramers is no longer prevented. The self‐complementary UUAA tetramer 22 forms Watson–Crick‐ and Hoogsteen‐type base‐paired cyclic duplexes more readily than the sequence‐isomeric AAUU tetramer 23 , further illustrating the sequence selectivity of duplex formation. 相似文献
48.
D. N. Dybtsev M. P. Yutkin E. V. Peresypkina A. V. Virovets Y. Hasegawa H. Nishihara V. P. Fedin 《Russian Chemical Bulletin》2007,56(9):1782-1786
The reaction of Co(NO3)2·6H2O with 1,3,5-benzenetricarboxylic acid (H3btc, trimesic acid) in DMF at 100 °C afforded the coordination polymer [Co3(dmf)6(btc)(Hbtc)(H2btc)]··9H2O (1) (dmf is N,N′-dimethylformamide, DMF). According to the X-ray diffraction study, the metal-organic coordination polymer is composed of
planar honeycomb (6,3) networks, in which the organic benzenetricarboxylate anions and the inorganic Co2+ cations play a role of three-connected nodes. Disordered water molecules are intercalated between the layers. A study of
the magnetic properties showed the presence of a weak antiferromagnetic coupling between the Co2+ ions (S = 3/2).
Dedicated to Academician G. A. Abakumov on the occasion of his 70th birthday.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1719–1723, September, 2007. 相似文献
49.
Andrzej Barszczewicz Michal Jaszuński Krystyna Kamieńska-Trela Trygve Helgaker Poul Jørgensen Olav Vahtras 《Theoretical chemistry accounts》1993,87(1-2):19-28
Summary
Ab initio calculations of parameters which characterize the NMR spectrum are presented for the cyclopropene molecule. The London orbitals CHF (or GIAO-CHF, Gauge-Independent Atomic Orbital Coupled Hartree-Fock) results for the shielding constants are in good agreement with the experimental data, accurately determined, and with otherab initio values. The calculations of the NMR spin-spin coupling constants have been performed using the Multiconfiguration Time-Dependent Hartree-Fock (MC TDHF) approach. Different basis sets and MC SCF wavefunctions were used to estimate the accuracy of the results. Good agreement is obtained with the coupling constants estimated using the available experimental data.Dedicated to Professor Werner Kutzelnigg on the occasion of his 60th birthday 相似文献
50.
Roberto Grisorio Giuseppe Romanazzi Piero Mastrorilli Domenico Acierno Giuseppe Ciccarella 《Tetrahedron》2006,62(4):627-634
A series of novel bifluorene based systems was synthesised by a convergent approach by means of a Suzuki cross-coupling between 7,7′-bis-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-9,9,9′,9′-tetraoctyl-2,2′-bifluorene and suitable aryl-bromides. All the oligomers have been characterized by 1H, 13C NMR, FT-IR, UV-vis, PL spectroscopy and mass analyses. In particular, it has been demonstrated that the presence of strong electron donor (amines) or withdrawing (carboxylic esters) groups causes a bathochromic shift of the optical properties with respect to those of unsubstituted molecules. The effects of these functional groups on the HOMO-LUMO energy levels were investigated by cyclic voltammetry. Remarkably, the LUMO energy level of 7,7′-bis-[5′-carbodecaoxy-2,2′-bithiophen-5-yl]-9,9,9′,9′-tetraoctyl-2,2′-bifluorene (−3.07 eV) is strongly influenced by the presence of the ester functional group. 相似文献