全文获取类型
收费全文 | 3586篇 |
免费 | 531篇 |
国内免费 | 381篇 |
专业分类
化学 | 2653篇 |
晶体学 | 20篇 |
力学 | 177篇 |
综合类 | 34篇 |
数学 | 306篇 |
物理学 | 1308篇 |
出版年
2024年 | 13篇 |
2023年 | 85篇 |
2022年 | 117篇 |
2021年 | 96篇 |
2020年 | 132篇 |
2019年 | 137篇 |
2018年 | 106篇 |
2017年 | 105篇 |
2016年 | 151篇 |
2015年 | 150篇 |
2014年 | 194篇 |
2013年 | 272篇 |
2012年 | 339篇 |
2011年 | 356篇 |
2010年 | 235篇 |
2009年 | 199篇 |
2008年 | 260篇 |
2007年 | 223篇 |
2006年 | 191篇 |
2005年 | 149篇 |
2004年 | 113篇 |
2003年 | 89篇 |
2002年 | 87篇 |
2001年 | 84篇 |
2000年 | 59篇 |
1999年 | 63篇 |
1998年 | 60篇 |
1997年 | 59篇 |
1996年 | 66篇 |
1995年 | 73篇 |
1994年 | 39篇 |
1993年 | 26篇 |
1992年 | 36篇 |
1991年 | 30篇 |
1990年 | 17篇 |
1989年 | 17篇 |
1988年 | 15篇 |
1987年 | 6篇 |
1986年 | 9篇 |
1985年 | 10篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 7篇 |
1980年 | 1篇 |
1979年 | 4篇 |
1974年 | 1篇 |
1940年 | 1篇 |
1902年 | 1篇 |
1898年 | 1篇 |
排序方式: 共有4498条查询结果,搜索用时 15 毫秒
91.
Based on the QM/MM optimized X-ray crystal structure of the photosynthetic reaction center (PRC) of purple bacteriaRhodopseudomonas (Rps.)viridis, quantum chemistry density functional method (DFT, B3LYP/6-31G) has been performed to study the interactions between the pigment molecules and either the surrounded amino acid residues or water molecules that are either axially coordinated or hydrogen bonded with the pigment molecules, leading to an explanation of the mechanism of the primary electron-transfer (ET) reactions in the PRC. Results show that the axial coordination of amino acid residues greatly raises theE LUMO of pigment molecules and it is important for the possibility of ET to take place. Different hydrogen bonds between amino acid residues, water molecules and pigment molecules decrease theE LUMO of the pigment molecules to different extents. It is crucial for the ET taking place from excited P along L branch and sustains that the ET is a one-step reaction without through accessory bacteriochlorophyll (ABChl b). It is insufficient to treat the whole protein surrounding as a homogeneous dielectric medium. 相似文献
92.
Mongin F Mojovic L Guillamet B Trécourt F Quéguiner G 《The Journal of organic chemistry》2002,67(25):8991-8994
The first nickel-catalyzed cross-coupling reactions between fluoroarenes and aryl organometallics using commercially available ligands are described. The nickel-catalyzed cross-coupling reactions between aryl Grignard reagents and fluoroazines and -diazines occurred in THF at room temperature using commercially available 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, or 1,1'-bis(diphenylphosphino)ferrocene as ligand. Various fluoro substrates such as pyridines, diazines (pyrazine, pyridazine), benzodiazines (quinoxaline), and quinolines were successfully involved in the reaction with phenylmagnesium halides (phenylmagnesium chloride, 2-methoxyphenylmagnesium bromide, and 4-methoxyphenylmagnesium bromide). The conditions used also allowed the cross-coupling of 4-fluorotoluene with arylmagnesium reagents. 相似文献
93.
Zhen‐Feng Zhang Dong‐Chao Wang Jian‐Ge Wang Gui‐Rong Qu 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(9):o524-o527
The molecules of 2,2,2‐trichloro‐N,N′‐diphenylethane‐1,1‐diamine, C14H13Cl3N2, are linked into (040) sheets by a combination of C—H...Cl and C—H...π(arene) hydrogen bonds. In 2,2,2‐trichloro‐N,N′‐bis(4‐methylphenyl)ethane‐1,1‐diamine, C16H17Cl3N2, the molecules are linked into C(7) chains by two independent C—H...Cl hydrogen bonds and one Cl...Cl contact. 相似文献
94.
Synthesis and Rearrangement of P‐Nitroxyl‐Substituted PIII and PV Phosphanes: A Combined Experimental and Theoretical Case Study 下载免费PDF全文
Tobias Heurich Dr. Zheng‐Wang Qu Dr. Senada Nožinović Dr. Gregor Schnakenburg Dr. Hideto Matsuoka Prof. Dr. Stefan Grimme Prof. Dr. Olav Schiemann Prof. Dr. Rainer Streubel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(29):10102-10110
Low‐temperature generation of P‐nitroxyl phosphane 2 (Ph2POTEMP), which was obtained by the reaction of Ph2PH ( 1 ) with two equivalents of TEMPO, is presented. Upon warming, phosphane 2 decomposed to give P‐nitroxyl phosphane P‐oxide 3 (Ph2P(O)OTEMP) as one of the final products. This facile synthetic protocol also enabled access to P‐sulfide and P‐borane derivatives 7 and 13 , respectively, by using Ph2P(S)H ( 6 ) or Ph2P(BH3)H ( 11 ) and TEMPO. Phosphane sulfide 7 revealed a rearrangement to phosphane oxide 8 (Ph2P(O)STEMP) in CDCl3 at ambient temperature, whereas in THF, thermal decomposition of sulfide 7 yielded salt 10 ([TEMP‐H2][Ph2P(S)O]). As well as EPR and detailed NMR kinetic studies, indepth theoretical studies provided an insight into the reaction pathways and spin‐density distributions of the reactive intermediates. 相似文献
95.
Xiao-Min Nie Bo-Yang Shao Chen-Hui Qu Ling Zhou 《International Journal of Theoretical Physics》2013,52(9):3011-3019
We generalize usual second-order effective Hamiltonian approximation into third-order. Employing the generalized method, we propose a scheme to generate three-spin interaction using coupled cavity chain. We show that the third order term not only improves two parties interaction but also induces direct three-spin interaction which has not been simulated before. By controlling the frequency of laser field, one can obtain next nearest neighbor interaction on the same order with the nearest neighbor’s or the three-spin interaction on the same order as next nearest neighbor’s. 相似文献
96.
97.
CO and formaldehyde(HCHO)oxidation reactions were investigated over mesoporous Ag/Co3O4 catalysts prepared by one-pot(OP)and impregnation(IM)methods.It was found that the one-pot method was superior to the impregnation method for synthesizing Ag/Co3O4 catalysts with high activity for both reactions.It was also found that the catalytic behavior of mesoporous Co3O4 and Ag/Co3O4 catalysts for the both reactions was different.And the addition of silver on mesoporous Co3O4 did not always enhance the catalytic activity of final catalyst for CO oxidation at room temperature(20 C),but could significantly improve the catalytic activity of final catalyst for HCHO oxidation at low temperature(90 C).The high surface area,uniform pore structure and the pretty good dispersion degree of the silver particle should be responsible for the excellent low-temperature CO oxidation activity.However,for HCHO oxidation,the addition of silver played an important role in the activity enhancement.And the silver particle size and the reducibility of Co3O4 should be indispensable for the high activity of HCHO oxidation at low temperature. 相似文献
98.
Yuying Qu Yingchun Li Xiaoli Tan Weixiang Zhai Dr. Guifang Han Dr. Jingli Hou Prof. Guoquan Liu Prof. Yuguang Song Prof. Yangping Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(33):7888-7895
Tetrathiatriarylmethyl (TAM, trityl) radicals have found wide applications as spin probes/labels for EPR spectroscopy and imaging, and as polarizing agents for dynamic nuclear polarization. The high hydrophilicity of TAM radicals is essential for their biomedical applications. However, the synthesis of hydrophilic TAM radicals (e.g., OX063) is extremely challenging and has only been reported in the patent literature, to date. Herein, an efficient synthesis of a highly water-soluble TAM radical bis(8-carboxyl-2,2,6,6-tetramethylbenzo[1,2-d:4,5-d′]bis([1,3]dithiol-4-yl)-mono-(8-carboxyl-2,2,6,6-tetrakis(2-hydroxyethyl)benzo[1,2-d:4,5-d′]bis([1,3]dithiol-4-yl)methyl (TFO), which contains four additional hydroxylethyl groups, relative to the Finland trityl radical CT-03, is reported. Similar to OX063, TFO exhibits excellent properties, including high water solubility in phosphate buffer, low log P, low pKa, long relaxation times, and negligible binding with bovine serum albumin. On the other hand, TFO has a sharper EPR line and higher O2 sensitivity than those of OX063. Therefore, in combination with its facile synthesis, TFO should find wide applications in magnetic resonance related fields and this synthetic approach would shed new light on the synthesis of other hydrophilic TAM radicals. 相似文献
99.
100.
Tie‐Qiang Huang Wen‐Yan Qu Jin‐Chang Ding Miao‐Chang Liu Hua‐Yue Wu Jiu‐Xi Chen 《Journal of heterocyclic chemistry》2013,50(2):293-297
A facile and simple catalyst‐free protocol has been developed for the condensation of 1,2‐diketones with aromatic 1,2‐diamines in polyethylene glycol (PEG), providing quinoxaline derivatives in good yields. The important features of the methodology are broad substrates scope, simple workup, catalyst free, environmentally benign, and no requirement for metal catalysts. It is noteworthy that the cyclization reaction of 1,2‐diketones with aliphatic 1,2‐diamines is also conducted smoothly to afford pyrazines in good yields under the standard conditions. In addition, PEG could be recovered easily and was reused without evident loss in activity 相似文献