全文获取类型
收费全文 | 3477篇 |
免费 | 506篇 |
国内免费 | 369篇 |
专业分类
化学 | 2593篇 |
晶体学 | 20篇 |
力学 | 175篇 |
综合类 | 34篇 |
数学 | 306篇 |
物理学 | 1224篇 |
出版年
2024年 | 7篇 |
2023年 | 82篇 |
2022年 | 74篇 |
2021年 | 82篇 |
2020年 | 133篇 |
2019年 | 135篇 |
2018年 | 105篇 |
2017年 | 100篇 |
2016年 | 149篇 |
2015年 | 142篇 |
2014年 | 188篇 |
2013年 | 258篇 |
2012年 | 334篇 |
2011年 | 355篇 |
2010年 | 234篇 |
2009年 | 197篇 |
2008年 | 250篇 |
2007年 | 214篇 |
2006年 | 187篇 |
2005年 | 149篇 |
2004年 | 113篇 |
2003年 | 87篇 |
2002年 | 86篇 |
2001年 | 82篇 |
2000年 | 57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 | 25篇 |
1992年 | 35篇 |
1991年 | 30篇 |
1990年 | 17篇 |
1989年 | 16篇 |
1988年 | 15篇 |
1987年 | 6篇 |
1986年 | 8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4352条查询结果,搜索用时 409 毫秒
101.
The reaction of Pt2Ru4(CO)18, 1 with 1,8-bis(phenylethynyl)naphthalene, 2 has yielded two metal carbonyl cluster complexes: Ru2(CO)6[-
2-C10H6C4Ph2], 3 (60% yield) and Ru2Pt(CO)6[-
2-C10H6C4Ph2]2, 4 (8% yield). Both compounds were characterized by a single crystal X-ray diffraction analysis. Both products were formed as a result of fragmentation of the Pt2Ru4 cluster of 1. Compound 3 contains two ruthenium atoms. They are bridged by a tricyclic C10H6C4Ph2 ligand formed by the coupling of the two -carbon atoms of the alkyne groups. The -carbon atoms of the alkynes are -bonded to one of the ruthenium atoms to form a metallacycle and this entire group is -bonded to the second ruthenium atom. Compound 4 contains two ruthenium atoms with a platinum atom between them. This molecule contains two tricyclic C10H6C4Ph2 ligands similar to that in 3, and two metallacycles formed by coordination of the -carbon atoms of both ligands to the platinum atom. One ligand is -bonded to each of the ruthenium atoms. 相似文献
102.
103.
104.
In this paper, Co-60γ ray was used to irradiate the ointment cold cream at room temperature (25°C). We also used FTIR, GC and thin film chromatogram to analyse various irradiated samples. It was found that the ointment cold cream can be irradiated at dose of 5–35 kGy and at dose rate from 0.2 to 0.6 kGy/h at room temperature (25°C) without evident decomposition. At dose of 5–15 kGy, the number of bacteria can be reduced to hygienic standard value. The radiation sterilization is a safe method for killing the bacteria in the ointment cold cream. 相似文献
105.
Determination of amino acids in a complex matrix without derivatization is advantageous, however, difficulties are found in both the detection and the separation of those compounds. In this study, a rapid and reliable LC-MS-MS method for the quantitation of underivatized amino acids in exocellular media was established. Injections were made directly after centrifugation of the samples, without further preparation. The separation of seven underivatized amino acids was achieved on a reversed-phase C18 column with pentadecafluorooctanoic acid as a volatile ion-pair reagent, and the specific detection of most amino acids was achieved by MS-MS of the specific transitions [M + H]+-->[M + H - 46]+. The calibration curves of all analytes were linear over the range of 1.0-1000 microg ml(-1) and the detection limits ranged from 0.1 to 5 ng ml(-1), with an injection volume of 20 microl. The inter-day and intra-day precisions ranged from 2.6 to 5.7% and 4.8 to 8.2%, respectively; the mean recoveries of the seven analytes were 81-104%, 91-107% and 93-101% respectively at the spiked level of 10, 40 and 200 microg ml(-1). A large number of fermentation samples were analysed using this method. The technique is simple, rapid, selective and sensitive, and shows potential for the high-throughput quantitation of amino acids from other biological matrices. 相似文献
106.
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
107.
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
108.
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
109.
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
110.
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