全文获取类型
收费全文 | 3826篇 |
免费 | 428篇 |
国内免费 | 735篇 |
专业分类
化学 | 4711篇 |
晶体学 | 98篇 |
力学 | 2篇 |
综合类 | 10篇 |
数学 | 1篇 |
物理学 | 167篇 |
出版年
2024年 | 3篇 |
2023年 | 25篇 |
2022年 | 87篇 |
2021年 | 156篇 |
2020年 | 222篇 |
2019年 | 172篇 |
2018年 | 145篇 |
2017年 | 145篇 |
2016年 | 223篇 |
2015年 | 186篇 |
2014年 | 222篇 |
2013年 | 319篇 |
2012年 | 457篇 |
2011年 | 245篇 |
2010年 | 215篇 |
2009年 | 235篇 |
2008年 | 244篇 |
2007年 | 246篇 |
2006年 | 214篇 |
2005年 | 182篇 |
2004年 | 231篇 |
2003年 | 157篇 |
2002年 | 91篇 |
2001年 | 76篇 |
2000年 | 65篇 |
1999年 | 83篇 |
1998年 | 51篇 |
1997年 | 47篇 |
1996年 | 37篇 |
1995年 | 30篇 |
1994年 | 27篇 |
1993年 | 23篇 |
1992年 | 30篇 |
1991年 | 14篇 |
1990年 | 15篇 |
1989年 | 6篇 |
1988年 | 19篇 |
1987年 | 5篇 |
1986年 | 11篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 7篇 |
1981年 | 4篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1972年 | 2篇 |
排序方式: 共有4989条查询结果,搜索用时 937 毫秒
851.
在B3LYP/6-31G(d,P)(Rh和P采用LANL2DZ Polar)水平下,研究了有机膦羰基铑催化乙烯的氢甲酰化反应机理,优化了反应中间体、过渡态和产物的结构.结果表明,乙烯的氢甲酰化反应有两条主要的反应路径,经历了乙烯络合、乙烯插入、膦加成、羰基插入、H2的氧化加成和丙醛还原消除及催化剂的再生等过程.乙烯插入、羰基插入、H2的氧化加成和丙醛还原消除过程中三元环的形成是协同进行的.反应以顺式活性催化剂为起始物,H2的氧化加成是反应速度控制步骤,丙酰基的消除反应是不可逆的.理论结果与实验一致. 相似文献
852.
Robert J. Bubel Warthen Douglass David P. White 《Journal of computational chemistry》2000,21(3):239-246
Ligand repulsive energies, ER, have been demonstrated to provide reliable steric parameters for ligands in organometallic systems. To date, ligand repulsive energies have been computed manually using commercially available molecular mechanics code. We report a customized code, ERCODE, that calculates ligand repulsive energies. Some reported ER values differ from those in the literature due to a modified conformational search strategy presented. Updated ligand repulsive energies for 100 phosphines, 12 phosphites, 26 amines, and 54 alcohols, ethers, and sulfides are presented. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 239–246, 2000 相似文献
853.
Ingo Muegge 《Journal of computational chemistry》2001,22(4):418-425
Recently, a knowledge‐based scoring function has been introduced that estimates the protein‐binding affinity based on the 3D structure of a protein–ligand complex (J Med Chem 1999, 42, 791). A ligand volume correction factor has been proposed and applied to filter out intraligand interactions in this simplified potential approach. Here we evaluate the effect of the ligand volume correction on the predictive power of the PMF scoring function. It is found that the effect of the ligand volume correction is significant on the derived potentials and large on the overall score. However, the effect of the ligand correction on the predictive power of the scoring function appears to be smaller. For a test set containing serine proteases the predictive power of the PMF scoring function does not change with the introduction of the volume correction. For a test set of metalloprotease complexes, the predictive power of the PMF scoring function improves only slightly when the volume correction is applied. For five test sets comprising a total of 225 diverse protein ligand complexes taken from the Brookhaven Protein Data Bank it is found, however, that the introduction of the ligand volume correction consistently improves the correlation between the PMF scores and the measured binding affinities. The effect of the correction factor on docking/scoring experiments is also analyzed using a test set of 61 biphenyl inhibitor‐stromelysin complexes. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 418–425, 2001 相似文献
854.
以气相法二氧化硅为载体,链状胺和环胺为功能化试剂,制得一系列二氧化硅-胺基复合载体,通过配位反应得到二氧化硅负载胺-钯(Ⅱ)配合物,进一步还原得到二氧化硅负载胺-钯(0)配合物.采用IR、XRD、XPS、ICP技术对配合物进行表征,并研究了配合物的制备、反应条件以及配体差异对其催化碘苯与丙烯酸的Heck反应的性能.结果表明,该类催化剂在较低的温度下(70~90℃)即可较好地催化该反应,生成反式产物;还原后催化剂具有更好的催化活性和良好的重复使用性能;具有链状胺基配体的催化剂随着N原子数目的增加,催化活性呈上升趋势,而具有环状胺基配体的催化剂活性明显低于前者. 相似文献
855.
856.
Compounds with Organometallic Alkoxo–Indium Cages The reaction of InMe3 with PhCH2OH (molar ratio 1 : 2) at 20 °C in toluene gives the tetranuclear complex [In{(PhCH2O)2InMe2}3] ( 2 ) in good yield. A further reaction under reflux conditions was not observed. However, at 160 °C in PhCH2OH a reaction could be realized, which forms an O‐centred corner‐cutted rhombic dodecahedron, [(MeIn)5(OCH2Ph)8(O)] ( 3 ), under evolution of methane. This In–O skeleton can be degraded with elemental cesium to a hexa‐ and heteronuclear complex [Cs{Cs(THF)}{[MeIn(OCH2Ph)2]4O}] ( 4 ). 2 – 4 were characterized by IR, RE, NMR and MS techniques as well as by X‐ray analyses. According to them 2 can be described as In3+ ion, coordinated by three metalate units [Me2In(OCH2Ph)2]–. 3 loses one MeIn fragment during the transfer of two electrons. Two Cs+ ions complete the new rhombic dodecahedron, at which different coordination spheres were observed. One Cs+ ion possesses additional contacts to a THF ligand and four π‐electron systems from four phenyl rings, while the THF ligand is missing in the environment of the second alkali cation. 相似文献
857.
Joungmo Cho Venkata Subbaiah Sadu Yohan Han Yunsoo Bae Hwajeong Lee Kee-In Lee 《Molecules (Basel, Switzerland)》2021,26(22)
We observed an unusual formation of four-coordinate boron(III) complexes from the reaction of 1-(2-pyridinyl)-5-pyrazolone derivatives with arylboronic acids in the basic media. The exact mechanism is not clear; however, the use of unprotected boronic acid and the presence of a bidentate ligand appeared to be the key structural requirements for the transformation. The results suggest that base-promoted disproportionation of arylboronic acid with the assistance of the [N,O]-bidentate ligation of 1-(2-pyridinyl)-5-pyrazolone should take place and facilitate the formation of pyrazole diarylborinate. Experiments to obtain a deeper understanding of its mechanism are currently underway. 相似文献
858.
Jesús Martínez Laura Valencia Rufina Bastida David E. Fenton Sharon E. Spey Alejandro Macías 《无机化学与普通化学杂志》2002,628(5):1059-1067
The pendant‐armed ligands L1 and L2 were synthesized by N‐alkylation of the two secondary aminic groups of the oxaazamacrocyclic precursor L with o‐nitrobenzylbromide (L1) or p‐nitrobenzylbromide (L2). Metal complexes of L1 and L2 have been synthesized and characterized by microanalysis, MS‐FAB, conductivity measurements, IR, UV‐Vis, 1H and 13C NMR spectroscopy and magnetic studies. Crystal structures of ligands L1 and L2, as well as complexes [CdL1(NO3)2]·2CH3CN and [Ag2Br(L2)2](ClO4)·2CH3CN have been determined by single crystal X‐ray crystallography. 相似文献
859.
This article concerns the calculation of equilibria of ligand binding to multiple sites in macromolecules in the presence of conformational flexibility and conformation-dependent interaction among the sites. A formulation of this problem is presented in which global conformational changes are distinguished from conformational changes that are confined to “locally flexible regions.” The formalism is quite general in that ligands of different types, multivalent binding sites, tautomeric binding sites, and sites that bind more than one type of ligand can be accommodated. Strictly speaking, the separation of the conformational problem into global and local parts does not impose any loss of generality, although in practice it is necessary to restrict the number of global and local conformers. Because of the combinatorics of binding and conformational states, the computational complexity of a problem having only local conformational flexibility grows exponentially with the number of sites and the number of locally flexible regions. An iterative mobile clustering method for cutting off this exponential growth and obtaining approximate solutions with low computational cost is presented and tested. In this method, a binding site is selected, and a “cluster” of strongly interacting sites is set up around it; within the cluster, the binding and conformational states are fully enumerated, whereas the influences of sites outside the cluster on the sites inside are treated by a mean field approximation. The procedure then moves to the next site around which another (possibly overlapping) cluster is formed and the calculation is repeated. The procedure iterates through the list of sites in this way, using the results of previous iterations for the mean-field terms of current iterations until a convergence criterion is met. The method is tested on a large set of randomly generated problems of varying size, whose geometries are chosen to have protein-like statistical properties. It is found that the method is accurate and rapid with the computational cost scaling linearly to quadratically with the number of sites, except for a minority of cases in which large clusters occur by chance. The new method is more accurate than a Monte Carlo method, and may be faster or slower depending on the clustering criteria and details of the macromolecule. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 1091–1111, 1999 相似文献
860.
Jeffrey W. Godden Florence L. Stahura Jürgen Bajorath 《Journal of computational chemistry》1999,20(15):1634-1643
The results of 16 docking simulations with rigid receptor sites and flexible ligands (∼60,000 compounds in each case) are statistically analyzed and compared. Different combinations of binding sites, scoring functions, and compound collections are used in these calculations. The docking scores are not randomly distributed over the scoring range; they follow Gaussian distributions (regardless of the binding sites), scoring functions, or screened compounds. If the docking sites are small, the Gaussian distributions are positively skewed. Peaks of the Gaussian distributions are populated with compounds having similar scores but different sizes and binding modes. These findings have implications for compound selection via computational docking. ©1999 John Wiley & Sons, Inc. J Comput Chem 20: 1634–1643, 1999 相似文献