全文获取类型
收费全文 | 3693篇 |
免费 | 134篇 |
国内免费 | 34篇 |
专业分类
化学 | 2448篇 |
晶体学 | 14篇 |
力学 | 85篇 |
数学 | 509篇 |
物理学 | 805篇 |
出版年
2024年 | 6篇 |
2023年 | 27篇 |
2022年 | 109篇 |
2021年 | 142篇 |
2020年 | 99篇 |
2019年 | 151篇 |
2018年 | 127篇 |
2017年 | 115篇 |
2016年 | 170篇 |
2015年 | 129篇 |
2014年 | 160篇 |
2013年 | 214篇 |
2012年 | 299篇 |
2011年 | 321篇 |
2010年 | 168篇 |
2009年 | 174篇 |
2008年 | 262篇 |
2007年 | 234篇 |
2006年 | 208篇 |
2005年 | 187篇 |
2004年 | 148篇 |
2003年 | 98篇 |
2002年 | 98篇 |
2001年 | 35篇 |
2000年 | 29篇 |
1999年 | 30篇 |
1998年 | 29篇 |
1997年 | 28篇 |
1996年 | 22篇 |
1995年 | 11篇 |
1994年 | 5篇 |
1993年 | 6篇 |
1992年 | 6篇 |
1991年 | 6篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1981年 | 1篇 |
排序方式: 共有3861条查询结果,搜索用时 0 毫秒
51.
Eugeny Nikolaevich Zapolotsky Sergey Pavlovich Babailov Gennadiy Alexandrovich Kostin 《Molecules (Basel, Switzerland)》2022,27(14)
1H NMR measurements are reported for the CD2Cl2/CDCl3 solutions of the Co(II) calix[4]arenetetraphosphineoxide complex (I). Temperature dependences of the 1H NMR spectra of I have been analyzed using the line shape analysis, taking into account the temperature variation of paramagnetic chemical shifts, within the frame of the dynamic NMR method. Conformational dynamics of the 2:1 Co(II) calix[4]arene complexes was conditioned by the pinched cone ↔pinched cone interconversion of I (with activation Gibbs energy ΔG≠(298K) = 40 ± 3 kJ/mol. Due to substantial temperature dependence of paramagnetic shifts, complex I can be used as model compound for designing an NMR thermosensor reagent for local temperature monitoring. 相似文献
52.
53.
54.
Dr. Renata Kaczmarek Samuel Ward Dipra Debnath Taisiya Jacobs Alexander D. Stark Dariusz Korczyński Prof. Dr. Anil Kumar Prof. Dr. Michael D. Sevilla Dr. Sergey A. Denisov Dr. Viacheslav Shcherbakov Dr. Pascal Pernot Prof. Dr. Mehran Mostafavi Prof. Dr. Roman Dembinski Prof. Dr. Amitava Adhikary 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9495-9505
The directionality of the hole-transfer processes between DNA backbone and base was investigated by using phosphorodithioate [P(S−)=S] components. ESR spectroscopy in homogeneous frozen aqueous solutions and pulse radiolysis in aqueous solution at ambient temperature confirmed initial formation of G.+-P(S−)=S. The ionization potential of G-P(S−)=S was calculated to be slightly lower than that of guanine in 5′-dGMP. Subsequent thermally activated hole transfer from G.+ to P(S−)=S led to dithiyl radical (P-2S.) formation on the μs timescale. In parallel, ESR spectroscopy, pulse radiolysis, and density functional theory (DFT) calculations confirmed P-2S. formation in an abasic phosphorodithioate model compound. ESR investigations at low temperatures and higher G-P(S−)=S concentrations showed a bimolecular conversion of P-2S. to the σ2-σ*1-bonded dimer anion radical [-P-2S 2S-P-]− [ΔG (150 K, DFT)=−7.2 kcal mol−1]. However, [-P-2S 2S-P-]− formation was not observed by pulse radiolysis [ΔG° (298 K, DFT)=−1.4 kcal mol−1]. Neither P-2S. nor [-P-2S 2S-P-]− oxidized guanine base; only base-to-backbone hole transfer occurs in phosphorodithioate. 相似文献
55.
56.
57.
58.
59.
60.
Sergey L. Veber Matvey V. Fedin Sergey V. Fokin Renad Z. Sagdeev Victor I. Ovcharenko Elena G. Bagryanskaya 《Applied magnetic resonance》2010,37(1-4):693-701
We report the X-band (9 GHz) electron paramagnetic resonance (EPR) study of series of bis(o-semiquinonato)copper(II) complexes with different ligands. It was found previously, that exchange interactions in spin triads of these compounds are very sensitive to the structure of the ligand coordinated to the central copper(II) ion. Ligand moderates the copper–radical and radical–radical exchange interactions and strongly changes the magnetic properties of the compound. Depending on a ligand, ferromagnetic or antiferromagnetic character of exchange dominates in the system. The EPR study of these complexes allowed us to obtain information on zero-field splitting parameters and their distributions in the studied compounds. The EPR results compliment previously obtained spectroscopic data on these compounds and suggest the pronounced plasticity of the clusters manifested in the broad distributions of their rhombicity parameters. 相似文献