全文获取类型
收费全文 | 4392篇 |
免费 | 293篇 |
国内免费 | 842篇 |
专业分类
化学 | 4592篇 |
晶体学 | 81篇 |
力学 | 135篇 |
综合类 | 54篇 |
数学 | 315篇 |
物理学 | 350篇 |
出版年
2024年 | 4篇 |
2023年 | 62篇 |
2022年 | 92篇 |
2021年 | 77篇 |
2020年 | 161篇 |
2019年 | 176篇 |
2018年 | 186篇 |
2017年 | 176篇 |
2016年 | 191篇 |
2015年 | 146篇 |
2014年 | 190篇 |
2013年 | 438篇 |
2012年 | 506篇 |
2011年 | 240篇 |
2010年 | 196篇 |
2009年 | 239篇 |
2008年 | 289篇 |
2007年 | 293篇 |
2006年 | 253篇 |
2005年 | 227篇 |
2004年 | 211篇 |
2003年 | 176篇 |
2002年 | 144篇 |
2001年 | 98篇 |
2000年 | 124篇 |
1999年 | 105篇 |
1998年 | 92篇 |
1997年 | 72篇 |
1996年 | 66篇 |
1995年 | 47篇 |
1994年 | 42篇 |
1993年 | 23篇 |
1992年 | 50篇 |
1991年 | 25篇 |
1990年 | 28篇 |
1989年 | 19篇 |
1988年 | 15篇 |
1987年 | 6篇 |
1986年 | 6篇 |
1985年 | 5篇 |
1984年 | 7篇 |
1983年 | 5篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 3篇 |
1973年 | 2篇 |
排序方式: 共有5527条查询结果,搜索用时 15 毫秒
141.
Synthesis and Structural Characterization of [Mn(sapn)(H2O)2]Br 总被引:1,自引:0,他引:1
1 INTRODUCTION Many of the recent advances in the coordination chemistry of manganese have been driven by the involvement of the manganese in several biological redox-active systems[1,2], of which the most important is the oxygen-evolving complex (EOC) of photosystem II (PS II) in green plants [3]. Since the preparations and structural characterizations of the complexes containing N,O-donor ligands have been studied extensively as simple active-site models for the photosystem II[4,5]… 相似文献
142.
还原气化-原子荧光光谱法快速测定绿色食品基地土壤中的砷与汞 总被引:8,自引:1,他引:8
应用还原气化-原子荧光光谱法,使待测元素与基体自动分离、富集,测定绿色食品基地土壤中的AS、HG。经对国家经土壤标准物质进行分析证明,该方法具有快速、准确、灵敏度高等优点,用于绿色食品基地的审评检测,结果令人满意。 相似文献
143.
Yu-Xi Sun Ran Zhang De-Jun Ding Shu Liu Bao-Lin Wang Yan-Li Wang Yong-Xiang Lin 《Structural chemistry》2006,17(6):655-665
The Schiff base compounds, 4-(2-hydroxy-5-nitr- obenzylideneamino)-1,2-dihydro-1,5-dimethyl-2-phenylpy- razol-3-one and 4-(3-bromo-5-chloro-2-hydroxybenz-
ylideneamino)-1,2-dihydro-1,5-dimethyl-2-phenylpyrazol-3-one, have been synthesized and characterized by elemental analysis,
IR, and X-ray single crystal determination. Density functional calculations of the structures, natural bond orbitals, and
frontier molecular orbitals and Mülliken charge analysis on the compounds were performed at B3LYP/6-31+G(d) level of theory.
Vibrational frequencies were also predicted, assigned, and compared with the experimental values, which supported each other. 相似文献
144.
Kyle Clagg Sara Hold Archana Kumar Stefan G. Koenig Remy Angelaud 《Tetrahedron letters》2019,60(1):5-7
The direct application of Knochel-Hauser derivative arylmagnesium halides in Kumada-Corriu couplings is described. By utilizing the in situ-generated Grignard reagents, the transmetalation with stoichiometric zinc salts to known Negishi coupling conditions is avoided, thereby streamlining the transformation. Several aromatic hetereocycles participate in the deprotonation and couple with a variety of phenyl iodides and bromides in isolated yields up to 81%. The parent system is demonstrated on 6?g scale with 79% yield, and monitored via ReactIR to show the stability of the Grignard and progression of the deprotonation/CC coupling reaction. 相似文献
145.
采用改进的碱液萃取方法分离杜巴原油中的酸性化合物(主要是环烷酸),通过高分辨质谱分析萃取过程中不同组分酸性化合物组成,以研究碱萃取前后酸性化合物的分布与组成特征。实验结果表明,电喷雾傅立叶变换离子回旋共振高分辨质谱(ESI-FT-ICR-MS)是分析原油中酸性化合物的强有力的手段;酸性化合物分布于碱萃取前后的各个组分中,但其组成有明显的差异,碱液萃取出的石油酸主要是相对分子质量小于500的酸性组分,增加反萃取溶剂的用量和极性有利于脱除萃取物中的非碱性氮化合物,对石油羧酸的组成影响不大。 相似文献
146.
Four new Schiff base functionalized 1,2,3-triazolylidene nickel complexes, [Ni-(L1NHC)2](PF6)2; 3, [Ni-(L2NHC)2](PF6)2; 4, [Ni-(L3NHC)](PF6)2; 7 and [Ni-(L4NHC)](PF6)2; 8, (where L1NHC = (E)-3-methyl-1-propyl-4-(2-(((2-(pyridin-2-yl)ethyl)imino)methyl)phenyl)-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 1, L2NHC = (E)-3-methyl-4-(2-((phenethylimino)methyl)phenyl)-1-propyl-1H-1,2,3-triazol-3-ium hexafluorophosphate(V), 2, L3NHC = 4,4′-(((1E)-(ethane-1,2-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 5, and L4NHC = 4,4′-(((1E)-(butane-1,4-diylbis(azanylylidene))bis(methanylylidene))bis(2,1-phenylene))bis(3-methyl-1-propyl-1H-1,2,3-triazol-3-ium) hexafluorophosphate(V), 6), were synthesised and characterised by a variety of spectroscopic methods. Square planar geometry was proposed for all the nickel complexes. The catalytic potential of the complexes was explored in the oxidation of styrene to benzaldehyde, using hydrogen peroxide as a green oxidant in the presence of acetonitrile at 80 °C. All complexes showed good catalytic activity with high selectivity to benzaldehyde. Complex 3 gave a conversion of 88% and a selectivity of 70% to benzaldehyde in 6 h. However, complexes 4 and 7–8 gave lower conversions of 48–74% but with higher (up to 90%) selectivity to benzaldehyde. Results from kinetics studies determined the activation energy for the catalytic oxidation reaction as 65 ± 3 kJ/mol, first order in catalyst and fractional order in the oxidant. Results from UV-visible and CV studies of the catalytic activity of the Ni-triazolylidene complexes on styrene oxidation did not indicate any clear possibility of generation of a Ni(II) to Ni(III) catalytic cycle. 相似文献
147.
合成了开链冠醚Schiff碱配体H2L(H2L=N,N′-双(邻羟苯亚甲基)-3,6-二氧杂-1,8-二氨基辛烷).详细研究了该配体在不同溶剂中和过渡金属离子存在下的荧光光谱,探讨了溶剂极性和不同金属离子对其荧光光谱的影响.结果表明:溶剂的极性和金属离子对其荧光性质有较大影响,随着溶剂极性的减小,配体的荧光增强,且谱峰发生蓝移.金属离子Zn2+、Cd2+对配体具有荧光增敏作用,Ni2+、Cu2+具有荧光猝灭作用.探讨了配体与金属离子结合的pH范围,结果显示最佳pH值为7—8. 相似文献
148.
149.
Theoretical study on the mechanism for the excited-state double proton transfer process of an asymmetric Schiff base ligand
下载免费PDF全文
![点击此处可从《中国物理 B》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Zhengran Wang 《中国物理 B》2022,31(4):48202-048202
Excited-state double proton transfer (ESDPT) in the 1-[(2-hydroxy-3-methoxy-benzylidene)-hydrazonomethyl]-naphthalen-2-ol (HYDRAVH2) ligand was studied by the density functional theory and time-dependent density functional theory method. The analysis of frontier molecular orbitals, infrared spectra, and non-covalent interactions have cross-validated that the asymmetric structure has an influence on the proton transfer, which makes the proton transfer ability of the two hydrogen protons different. The potential energy surfaces in both S0 and S1 states were scanned with varying O-H bond lengths. The results of potential energy surface analysis adequately proved that the HYDRAVH2 can undergo the ESDPT process in the S1 state and the double proton transfer process is a stepwise proton transfer mechanism. Our work can pave the way towards the design and synthesis of new molecules. 相似文献
150.