全文获取类型
收费全文 | 76896篇 |
免费 | 6940篇 |
国内免费 | 11865篇 |
专业分类
化学 | 57000篇 |
晶体学 | 2079篇 |
力学 | 1043篇 |
综合类 | 510篇 |
数学 | 18108篇 |
物理学 | 16961篇 |
出版年
2024年 | 122篇 |
2023年 | 1223篇 |
2022年 | 1095篇 |
2021年 | 2062篇 |
2020年 | 2376篇 |
2019年 | 2368篇 |
2018年 | 2064篇 |
2017年 | 2213篇 |
2016年 | 2538篇 |
2015年 | 2394篇 |
2014年 | 3329篇 |
2013年 | 6539篇 |
2012年 | 4438篇 |
2011年 | 5428篇 |
2010年 | 4545篇 |
2009年 | 5391篇 |
2008年 | 5471篇 |
2007年 | 5382篇 |
2006年 | 4772篇 |
2005年 | 3967篇 |
2004年 | 3757篇 |
2003年 | 3176篇 |
2002年 | 3044篇 |
2001年 | 2174篇 |
2000年 | 2009篇 |
1999年 | 1816篇 |
1998年 | 1512篇 |
1997年 | 1249篇 |
1996年 | 1232篇 |
1995年 | 1240篇 |
1994年 | 1095篇 |
1993年 | 851篇 |
1992年 | 794篇 |
1991年 | 584篇 |
1990年 | 439篇 |
1989年 | 420篇 |
1988年 | 344篇 |
1987年 | 263篇 |
1986年 | 220篇 |
1985年 | 281篇 |
1984年 | 232篇 |
1983年 | 107篇 |
1982年 | 200篇 |
1981年 | 212篇 |
1980年 | 140篇 |
1979年 | 134篇 |
1978年 | 102篇 |
1977年 | 107篇 |
1976年 | 90篇 |
1973年 | 53篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
51.
A string of four new hetero binuclear Ru(III) complexes of ferrocenecarboxaldehyde-4(N)-substituted thiosemicarbazones were synthesized and characterized by various spectral (infrared, ultraviolet–visible, Electron Paramagnetic Resonance (EPR) and High Resolution Mass Spectrometry (HR-MS) techniques. The binding abilities of the ligands/complexes with nucleic acid (calf thymus DNA, CT-DNA) and bovine serum albumin (BSA) were analyzed by absorption and emission titration methods. The complexes exhibited better DNA binding affinity than their parent ligands. The interaction with CT-DNA was found to be intercalative and with BSA static quenching mechanism was observed. All the synthesized Ru(III) complexes were subjected to study their in vitro cytotoxicity against MCF-7 (human breast cancer) and HT-29 (human colon cancer) cell lines. Among the four complexes, complex 3 [RuCp (FF-etsc)PPh3]Cl exhibited the highest cytotoxicity in MCF-7 cells and complex 4 [RuCp (FF-ptsc)PPh3]Cl was the most active on HT-29 cells. 相似文献
52.
Ping Chen Yanhong Hao Xinxin Wang Prof. Dr. Dan Yuan Prof. Dr. Yingming Yao Prof. Dr. Lutz Ackermann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(30):7292-7297
Highly position selective alkylations of N-alkylindoles at C7-positions have been enabled by cationic zirconium complexes. The strategy provides a straightforward access to install alkyl groups at C7-positions of indoles without a complex directing group. Mechanistic studies provided support for the importance of Brønsted acids in the catalytic manifold. 相似文献
53.
Pan Huang Dawen Xu Robert M. Reich Felix Kaiser Boping Liu Fritz E. Kühn 《Tetrahedron letters》2019,60(24):1574-1577
A first example of an Et2Zn mediated silylation of 1-aklynes is reported. A series of functional groups are tolerated in this reaction. Mechanistic studies support Zn alkynilides as intermediates in the reaction. This reaction protocol provides a practical method for the preparation of alkynylsilanes and expands the application of organometallic zinc in organic synthesis. 相似文献
54.
Summary Carbon deposits on the surface ofRu/Fe2O3 catalysts used in the water-gas shift reaction have been investigated by Auger Electron Spectrometry. A correlation has been
found between the thickness of the carbon deposit and the catalytic activity in WGSR. The carbon deposit covers the metallic
active centers and blocks their contact with reagents. The dotting of the iron oxide support with sodium has been found to
reduce the amount of carbon deposit. . 相似文献
55.
Padavattan Govindaswamy Patrick J. Carroll Yurij A. Mozharivskyj Mohan Rao Kollipara 《Journal of Chemical Sciences》2006,118(4):319-326
The reaction of [{(η5-C5Me5)M(μ-Cl)Cl}2] {where M = Rh (1), Ir (2)} with functionalized phosphine viz., diphenyl-2-pyridylphosphine (PPh2Py) in dichloromethane solvent yield neutral ϰ1-P-coordinated rhodium and iridium complexes [(η5-C5Me5)RhCl2(κ1-P-PPh2Py)]3 and [(η5-C5Me5) IrCl2(ϰ1-P-PPh2Py)]4. Reaction of complexes 1 and 2 with the ligand PPh2Py in methanol under reflux give bis-substituted complexes such as [(η5-C5Me5)RhCl(ϰ1-P-PPh2Py)2]+
5 and [(η5-C5Me5)IrCl(ϰ1-P-PPh2Py)2]+
6, whereas stirring in methanol at room temperature gives P-, N-chelating complexes of the type [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+ 7 and [(η5-C5Me5)IrCl(ϰ2-P-N-PPh2Py)]+
8. Neutral ϰ1-P-coordinated complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3 and [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 easily undergo conversion to the cationic P-, N-chelating complexes [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+
7 and [(η5-C5Me5) IrCl(ϰ2-P, N-PPh2Py)]+
8 on stirring in methanol at room temperature. These complexes are characterized by FT-IR and FT-NMR spectroscopy as well as
analytical methods. The molecular structures of the representative complexes [(η5-C5Me5)RhCl2(ϰ1-P-PPh2Py)]3, [(η5-C5Me5)IrCl2(ϰ1-P-PPh2Py)]4 and hexafluorophosphate salt of complex [(η5-C5Me5)IrCl(ϰ2-P-PPh2Py)2]+
6 are established by single-crystal X-ray diffraction methods 相似文献
56.
G. Panina 《Central European Journal of Mathematics》2003,1(2):157-168
All 3-dimensional convex polytopes are known to be rigid. Still their Minkowski differences (virtual polytopes) can be flexible
with any finite freedom degree. We derive some sufficient rigidity conditions for virtual polytopes and present some examples
of flexible ones. For example, Bricard's first and second flexible octahedra can be supplied by the structure of a virtual
polytope. 相似文献
57.
Peter Imkeller 《Probability Theory and Related Fields》1996,106(1):105-135
Summary. The analytic treatment of problems related to the asymptotic behaviour of random dynamical systems generated by stochastic
differential equations suffers from the presence of non-adapted random invariant measures. Semimartingale theory becomes accessible
if the underlying Wiener filtration is enlarged by the information carried by the orthogonal projectors on the Oseledets spaces
of the (linearized) system.
We study the corresponding problem of preservation of the semimartingale property and the validity of a priori inequalities
between the norms of stochastic integrals in the enlarged filtration and norms of their quadratic variations in case the random
element F enlarging the filtration is real valued and possesses an absolutely continuous law. Applying the tools of Malliavin’s calculus,
we give smoothness conditions on F under which the semimartingale property is preserved and a priori martingale inequalities are valid.
Received: 12 April 1995 / In revised form: 7 March 1996 相似文献
58.
Levoglucosenone reacts with α-aminoazoles to yield azolo[1,5-a]pyrimidine systems fused with a carbohydrate fragment. The reaction oocurs much more smoothly than in the case of other α,β-unsaturated
ketones. The reactions of levoglucosenone with β-dicarbonyl compounds (dimedone, barbituric acid) in the presence of a base
results in the pyran ring closure, which has never been observed earlier in reactions of β-dicarbonyl compounds with α,β-unsaturated
ketones under the conditions of basic catalysis. The structures of products were established by IR and NMR spectroscopy.
For Part 3, see Ref. 1.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 553–558, March, 1997. 相似文献
59.
Double Michael additions of lithium enolaie of 1,4-dioxaspiro[4.5]dec-6-en-8-one to four acrylates afforded bicyclo[2.2.2]octan-2-ones with high regio- and stereoselectivities in moderate yields. 相似文献
60.
In circuit-switched networks call streams are characterized by their mean and peakedness (two-moment method). The GI/M/C/0 system is used to model a single link, where the GI-stream is determined by fitting moments appropriately. For the moments of the overflow traffic of a GI/M/C/0 system there are efficient numerical algorithms available. However, for the moments of the freed carried traffic, defined as the moments of a virtual link of infinite capacity to which the process of calls accepted by the link (carried arrival process) is virtually directed and where the virtual calls get fresh exponential i.i.d. holding times, only complex numerical algorithms are available. This is the reason why the concept of the freed carried traffic is not used. The main result of this paper is a numerically stable and efficient algorithm for computing the moments of freed carried traffic, in particular an explicit formula for its peakedness. This result offers a unified handling of both overflow and carried traffics in networks. Furthermore, some refined characteristics for the overflow and freed carried streams are derived. 相似文献