全文获取类型
收费全文 | 144篇 |
免费 | 9篇 |
国内免费 | 1篇 |
专业分类
化学 | 127篇 |
数学 | 3篇 |
物理学 | 24篇 |
出版年
2023年 | 3篇 |
2022年 | 2篇 |
2021年 | 5篇 |
2020年 | 5篇 |
2019年 | 6篇 |
2018年 | 1篇 |
2017年 | 3篇 |
2016年 | 7篇 |
2015年 | 3篇 |
2014年 | 7篇 |
2013年 | 7篇 |
2012年 | 8篇 |
2011年 | 9篇 |
2010年 | 7篇 |
2009年 | 5篇 |
2008年 | 16篇 |
2007年 | 10篇 |
2006年 | 22篇 |
2005年 | 14篇 |
2004年 | 3篇 |
2003年 | 5篇 |
2002年 | 1篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1994年 | 1篇 |
1935年 | 1篇 |
排序方式: 共有154条查询结果,搜索用时 78 毫秒
151.
Kwiecien RA Khavrutskii IV Musaev DG Morokuma K Banerjee R Paneth P 《Journal of the American Chemical Society》2006,128(4):1287-1292
ONIOM calculations have provided novel insights into the mechanism of homolytic Co-C5' bond cleavage in the 5'-deoxyadenosylcobalamin cofactor catalyzed by methylmalonyl-CoA mutase. We have shown that it is a stepwise process in which conformational changes in the 5'-deoxyadenosine moiety precede the actual homolysis step. In the transition state structure for homolysis, the Co-C5' bond elongates by approximately 0.5 Angstroms from the value found in the substrate-bound reactant complex. The overall barrier to homolysis is approximately 10 kcal/mol, and the radical products are approximately 2.5 kcal/mol less stable than the initial ternary complex of enzyme, substrate, and cofactor. The movement of the deoxyadenosine moiety during the homolysis step positions the resulting 5'-deoxyadenosyl radical for the subsequent hydrogen atom transfer from the substrate, methylmalonyl-CoA. 相似文献
152.
Zhang L Rafferty JL Siepmann JI Chen B Schure MR 《Journal of chromatography. A》2006,1126(1-2):219-231
Many structural models for the stationary phase in reversed-phase liquid chromatography (RPLC) systems have been suggested from thermodynamic and spectroscopic measurements and theoretical considerations. To provide a molecular picture of chain conformation and solvent partitioning in a typical RPLC system, a particle-based Monte Carlo simulation study is undertaken for a dimethyl octadecyl (C(18)) bonded stationary phase on a model siliceous substrate in contact with mobile phases having different methanol/water concentrations. Following upon previous simulations for gas-liquid chromatography and liquid-liquid phase equilibria, the simulations are conducted using the configurational-bias Monte Carlo method in the Gibbs ensemble and the transferable potentials for phase equilibria force field. The simulations are performed for a chain surface density of 2.9 micromol/m(2), which is a typical bonded-phase coverage for mono-functional alkyl silanes. The solvent concentrations used here are pure water, approximately 33 and 67% mole fraction of methanol and pure methanol. The simulations show that the chain conformation depends only weakly on the solvent composition. Most chains are conformationally disordered and tilt away from the substrate normal. The interfacial width increases with increasing methanol content and, for mixtures, the solvent shows an enhancement of the methanol concentration in a 10 Angstrom region outside the Gibbs dividing surface. Residual surface silanol groups are found to provide hydrogen bonding sites that lead to the formation of substrate bound water and methanol clusters, including bridging clusters that penetrate from the solvent/chain interfacial region all the way to the silica surface. 相似文献
153.
Mixed-Valence CuI/CuIII Metal–Organic Frameworks with Non-innocent Ligand for Multielectron Transfer
Shang-Yuan Fu Cheng-Han Chang Dr. Alexander S. Ivanov Dr. Ilja Popovs Dr. Jeng-Lung Chen Dr. Yen-Fa Liao Dr. Hsin-Kuan Liu Dr. Suman Chirra Prof. Dr. Yun-Wei Chiang Jui-Chin Lee Wei-Ling Liu Prof. Dr. Watchareeya Kaveevivitchai Prof. Dr. Teng-Hao Chen 《Angewandte Chemie (International ed. in English)》2023,62(50):e202312494
We report two novel three-dimensional copper-benzoquinoid metal–organic frameworks (MOFs), [Cu4L3]n and [Cu4L3 ⋅ Cu(iq)3]n (LH4=1,4-dicyano-2,3,5,6-tetrahydroxybenzene, iq=isoquinoline). Spectroscopic techniques and computational studies reveal the unprecedented mixed valency in MOFs, formal Cu(I)/Cu(III). This is the first time that formally Cu(III) species are witnessed in metal–organic extended solids. The coordination between the mixed-valence metal and redox-non-innocent ligand L, which promotes through-bond charge transfer between Cu metal sites, allows better metal-ligand orbital overlap of the d-π conjugation, leading to strong long-range delocalization and semiconducting behavior. Our findings highlight the significance of the unique mixed valency between formal Cu(I) and highly-covalent Cu(III), non-innocent ligand, and pore environments of these bench stable Cu(III)-containing frameworks on multielectron transfer and electrochemical properties. 相似文献
154.
Jonas F. Goebel Julian Löffler Zhongyi Zeng Jens Handelmann Albert Hermann Ilja Rodstein Dr. Tobias Gensch Prof. Dr. Viktoria H. Gessner Prof. Dr. Lukas J. Gooßen 《Angewandte Chemie (International ed. in English)》2023,62(9):e202216160
Palladium-catalyzed couplings of silicon enolates with aryl electrophiles are of great synthetic utility, but often limited to expensive bromide substrates. A comparative experimental study confirmed that none of the established ligand systems allows to couple inexpensive aryl chlorides with α-trimethylsilyl alkylnitriles. In contrast, ylide functionalized phosphines (YPhos) led to encouraging results. A statistical model was developed that correlates the reaction yields with ligand features. It was employed to predict catalyst structures with superior performance. With this cheminformatics approach, YPhos ligands were tailored specifically to the demands of Hiyama couplings. The newly synthesized ligands displayed record-setting activities, enabling the elusive coupling of aryl chlorides with α-trimethylsilyl alkyl nitriles. The preparative utility of the catalyst system was demonstrated by the synthesis of pharmaceutically meaningful α-aryl alkylnitriles, α-arylcarbonyls and biaryls. 相似文献