全文获取类型
收费全文 | 185篇 |
免费 | 15篇 |
国内免费 | 3篇 |
专业分类
化学 | 145篇 |
力学 | 3篇 |
数学 | 33篇 |
物理学 | 22篇 |
出版年
2024年 | 2篇 |
2023年 | 6篇 |
2022年 | 4篇 |
2021年 | 4篇 |
2020年 | 12篇 |
2019年 | 6篇 |
2018年 | 8篇 |
2017年 | 2篇 |
2016年 | 5篇 |
2015年 | 7篇 |
2014年 | 8篇 |
2013年 | 10篇 |
2012年 | 14篇 |
2011年 | 20篇 |
2010年 | 8篇 |
2009年 | 5篇 |
2008年 | 13篇 |
2007年 | 11篇 |
2006年 | 14篇 |
2005年 | 11篇 |
2004年 | 8篇 |
2003年 | 3篇 |
2002年 | 7篇 |
2001年 | 2篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1994年 | 2篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1989年 | 1篇 |
1983年 | 1篇 |
1981年 | 1篇 |
1978年 | 1篇 |
排序方式: 共有203条查询结果,搜索用时 0 毫秒
31.
Xu M Elmatad YS Sebastianelli F Moskowitz JW Bacić Z 《The journal of physical chemistry. B》2006,110(49):24806-24811
We report quantum five-dimensional (5D) calculations of the energy levels and wave functions of the hydrogen molecule, para-H2 and ortho-H2, confined inside the small dodecahedral (H2O)20 cage of the sII clathrate hydrate. All three translational and the two rotational degrees of freedom of H2 are included explicitly, as fully coupled, while the cage is treated as rigid. The 5D potential energy surface (PES) of the H2-cage system is pairwise additive, based on the high-quality ab initio 5D (rigid monomer) PES for the H2-H2O complex. The bound state calculations involve no dynamical approximations and provide an accurate picture of the quantum 5D translation-rotation dynamics of H2 inside the cage. The energy levels are assigned with translational (Cartesian) and rotational quantum numbers, based on calculated root-mean-square displacements and probability density plots. The translational modes exhibit negative anharmonicity. It is found that j is a good rotational quantum number, while the threefold degeneracy of the j = 1 level is lifted completely. There is considerable translation-rotation coupling, particularly for excited translational states. 相似文献
32.
Shiran Aharon Dr. Shanti Gopal Patra Prof. Dr. Dan Meyerstein Dr. Eyal Tzur Dr. Dror Shamir Dr. Yael Albo Prof. Dr. Ariela Burg 《Chemphyschem》2023,24(22):e202300517
The Na3[Ru2(μ-CO3)4] complex is acting as a water oxidation catalyst in a homogeneous system. Due to the significance of heterogeneous systems and the effect of bicarbonate on the kinetic, we studied the bicarbonate effect on the heterogeneous electrocatalyst by entrapping the Na3[Ru2(μ-CO3)4] complex in a sol-gel matrix. We have developed two types of sol-gel electrodes, which differ by the precursor, and are demonstrating their stability over a minimum of 200 electrochemical cycles. The pH increases affected the currents and kcat for both types of electrodes, and their hydrophobicity, which was obtained from the precursor type, influenced the electrocatalytic process rate. The results indicate that NaHCO3 has an important role in the catalytic activity of the presented heterogeneous systems; without NaHCO3, the diffusing species is probably OH−, which undergoes diffusion via the Grotthuss mechanism. To the best of our knowledge, this is the first study to present a simple and fast one-step entrapment process for the Na3[Ru2(μ-CO3)4] complex by the sol-gel method under standard laboratory conditions. The results contribute to optimizing the WSP, ultimately helping expand the usage of hydrogen as a green and more readily available energy source. 相似文献
33.
Dr. Yaoyu Liang Dr. Irena Efremenko Dr. Yael Diskin-Posner Dr. Liat Avram Prof. Dr. David Milstein 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2024,136(21):e202401702
Bond activation and catalysis using s-block metals are of great significance. Herein, a series of calcium pincer complexes with deprotonated side arms have been prepared using pyridine-based PNP and PNN ligands. The complexes were characterized by NMR and X-ray crystal diffraction. Utilizing the obtained calcium complexes, unprecedented N2O activation by metal-ligand cooperation (MLC) involving dearomatization-aromatization of the pyridine ligand was achieved, generating aromatized calcium diazotate complexes as products. Additionally, the dearomatized calcium complexes were able to activate the N−H bond as well as reversibly activate H2, offering an opportunity for the catalytic hydrogenation of various unsaturated molecules. DFT calculations were applied to analyze the electronic structures of the synthesized complexes and explore possible reaction mechanisms. This study is an important complement to the area of MLC and main-group metal chemistry. 相似文献
34.
35.
Immunosensors are powerful analytical tools in clinical and veterinary diagnostics. This has led us to design a chemiluminescent immunosensor aimed at identifying anti-Brucella antibodies using optical fibers as the transducer. In order to develop the optimal transducer, to achieve an optimal chemical modification thereby allowing an optimal covalent binding of the protein receptor, several cleaning strategies and silane coupling agents were investigated. Brucella killed organisms were used as a model receptor for quantifying anti-Brucella IgG antibodies in a suspension compared to conventional colorimetric and chemiluminescent ELISA. A silane-benzophenone derivative was selected as the best performing silane coupling agent: the optical fiber immunosensor (OFIS) has showed the lowest limit of detection at 0.207 μg/ml, compared to 0.828 μg/ml and 0.414 μg/ml achieved by colorimetric and chemiluminescent ELISAs, respectively. These results, together with the additional advantages of rapidity, lower reagent volumes and moderate operating conditions, have set the grounds for further study in order to adapt this platform for on-site diagnostics of brucellosis disease markers. 相似文献
36.
Yael Pascal‐Levy Evgeny Shifman Dr. Manish Pal‐Chowdhury Eitan M. Hajaj Oleg Shtempluck Alexey Razin Valeri Kochetkov Prof. Yuval E. Yaish 《Chemphyschem》2012,13(18):4202-4206
Humidity plays an important role in molecular electronics. It facilitates charge movement on top of dielectric layers and modifies the device transfer characteristics. Using two different methods to probe temporal charge redistribution on the surface of dielectrics, we were able to extract the surface humidity for the first time. The first method is based on the relaxation time constants of the current through carbon nanotube field‐effect transistors (CNTFETs), and the second is based on electric force microscopy (EFM) measurements. Moreover, we found that applying external gate biases modifies the surface humidity. A theoretical model based on dielectrophoretic attraction between the water molecules and the substrate is introduced to explain this observation, and the results support our hypothesis. Furthermore, it is found that upon the adsorption of two to three layers of water the surface conductivity saturates. 相似文献
37.
38.
39.
Shmerling Efraim Hochberg Kenneth J. 《Methodology and Computing in Applied Probability》2004,6(2):203-218
The problem of finding the probability distribution of the number of zeros in some real interval of a random polynomial whose coefficients have a given continuous joint density function is considered. An algorithm which enables one to express this probability as a multiple integral is presented. Formulas for the number of zeros of random quadratic polynomials and random polynomials of higher order, some coefficients of which are non-random and equal to zero, are derived via use of the algorithm. Finally, the applicability of these formulas in numerical calculations is illustrated. 相似文献
40.
Direct Conversion of Alcohols into Alkenes by Dehydrogenative Coupling with Hydrazine/Hydrazone Catalyzed by Manganese 下载免费PDF全文
Dr. Uttam Kumar Das Dr. Subrata Chakraborty Dr. Yael Diskin‐Posner Prof. David Milstein 《Angewandte Chemie (International ed. in English)》2018,57(41):13444-13448
We have developed unprecedented methods for the direct transformation of primary alcohols to alkenes in the presence of hydrazine, and for the synthesis of mixed alkenes by the reaction of alcohols with hydrazones. The reactions are catalyzed by a manganese pincer complex and proceed in absence of added base or hydrogen acceptors, liberating dihydrogen, dinitrogen, and water as the only byproducts. The proposed mechanism, based on preparation of proposed intermediates and control experiments, suggests that the transformation occurs through metal–ligand cooperative N?H activation of a hydrazone intermediate. 相似文献