全文获取类型
收费全文 | 2893篇 |
免费 | 181篇 |
国内免费 | 9篇 |
专业分类
化学 | 2031篇 |
晶体学 | 45篇 |
力学 | 47篇 |
数学 | 381篇 |
物理学 | 579篇 |
出版年
2023年 | 39篇 |
2022年 | 55篇 |
2021年 | 74篇 |
2020年 | 128篇 |
2019年 | 114篇 |
2018年 | 44篇 |
2017年 | 46篇 |
2016年 | 170篇 |
2015年 | 126篇 |
2014年 | 130篇 |
2013年 | 155篇 |
2012年 | 176篇 |
2011年 | 222篇 |
2010年 | 126篇 |
2009年 | 101篇 |
2008年 | 160篇 |
2007年 | 153篇 |
2006年 | 120篇 |
2005年 | 136篇 |
2004年 | 103篇 |
2003年 | 77篇 |
2002年 | 67篇 |
2001年 | 27篇 |
2000年 | 30篇 |
1999年 | 31篇 |
1998年 | 18篇 |
1997年 | 19篇 |
1996年 | 17篇 |
1995年 | 27篇 |
1994年 | 22篇 |
1993年 | 20篇 |
1992年 | 18篇 |
1991年 | 23篇 |
1990年 | 21篇 |
1988年 | 8篇 |
1987年 | 13篇 |
1986年 | 10篇 |
1985年 | 12篇 |
1984年 | 16篇 |
1983年 | 15篇 |
1982年 | 13篇 |
1981年 | 13篇 |
1980年 | 8篇 |
1979年 | 12篇 |
1978年 | 20篇 |
1977年 | 17篇 |
1976年 | 19篇 |
1975年 | 18篇 |
1974年 | 9篇 |
1967年 | 8篇 |
排序方式: 共有3083条查询结果,搜索用时 15 毫秒
51.
52.
For systems that contain slow and fast dynamics, variational multirate integration schemes are used. These schemes split the system into parts which are simulated using two time grids consisting of micro and macro nodes. This formulation can be extended for multi-body systems. The rigid multi-body system is described by the so called director formulation and constraints describing the joints connecting the bodies. With the Lagrange multiplier method, the constraints are introduced into the equations of motion. A way to implement the null space method into the variational multirate framework is shown and the influence on the number of unknowns is investigated. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
53.
Hepcidin-25 has been defined as the key biomarker in iron metabolism. This peptide binds to the iron transporter ferroportin to cause its degradation. Therefore, the need for specific, accurate and precise methods for the quantification of hepcidin-25 in biological fluids is dramatically increasing. In this regard, the use of rapid immunochemical methods that provide low limit of quantification is desired for routine clinical use. However, such fast methodologies should be first analytically evaluated and compared with alternative strategies to check for their advantages and limitations. Here we compare the use of a commercial immunochemical assay for hepcidin determination with a novel analytical approach based on Cu-labeling of the peptide followed by Cu determination using liquid chromatography (HPLC) and plasma mass spectrometry (ICP-MS). The figures of merit of both systems reveal similar analytical characteristics and both seem to be adequate for the determination of the peptide at biologically relevant concentrations in human serum samples. The analysis of a larger number of samples (n = 50) by both techniques showed a good agreement in the concentrations found. Such finding permits to address the hepcidin recovery in the sample preparation procedure necessary for the HPLC-ICP-MS analysis in human serum that turn out to be 76–85%. Additionally, limitations due to cross-reactivity issues of the ELISA method could be addressed in some of the samples by using LC-ICP-MS and were confirmed by LC-Electrospray-MS. 相似文献
54.
Romana Pajkert Tobias Böttcher Maksym Ponomarenko Matthias Bremer Gerd-Volker Röschenthaler 《Tetrahedron》2013
A series of novel push–pushI and push–pullII carbene-stabilized complexes of phosphorus(V) fluorides bearing substituents with liquid-crystalline properties were synthesized by the oxidative addition of difluoroamines to phosphorus(III) halides. These octahedral complexes were characterized by NMR spectroscopy and X-ray analysis. 相似文献
55.
56.
57.
Dr. Sandra Ast Tobias Fischer Holger Müller Dr. Wulfhard Mickler Mathias Schwichtenberg Dr. Knut Rurack Prof. Dr. Hans‐Jürgen Holdt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(9):2990-3005
In a systematic approach we synthesized a new series of fluorescent probes incorporating donor–acceptor (D‐A) substituted 1,2,3‐triazoles as conjugative π‐linkers between the alkali metal ion receptor N‐phenylaza‐[18]crown‐6 and different fluorophoric groups with different electron‐acceptor properties (4‐naphthalimide, meso‐phenyl‐BODIPY and 9‐anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge‐transfer (CT) type probes 1 , 2 and 7 , the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge‐separated states. In the presence of Na+ and K+ ICT is interrupted, which resulted in a lighting‐up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7 , which contains a 9‐anthracenyl moiety as the electron‐accepting fluorophore, is the only probe which retains light‐up features in water and works as a highly K+/Na+‐selective probe under simulated physiological conditions. Virtually decoupled BODIPY‐based 6 and photoinduced electron transfer (PET) type probes 3 – 5 , where the 10‐substituted anthracen‐9‐yl fluorophores are connected to the 1,2,3‐triazole through a methylene spacer, show strong ion‐induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3‐triazole fluoroionophores. 相似文献
58.
Tao Wang Shuai Shi Dr. Mie Højer Vilhelmsen Tuo Zhang Dr. Matthias Rudolph Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(37):12512-12516
New and chemoselective gold(I)‐catalyzed transformations of 1‐(arylethynyl)‐7‐oxabicyclo[4.1.0]‐ heptan‐2‐ones were developed. Two completely different products—6,7‐dihydrobenzofuran‐4(5H)‐ones and benzofurans—could be obtained from the same starting material. The selectivity is determined by the ligand of the gold catalyst: triphenylphosphine delivers 6,7‐dihydrobenzofuran‐4(5H)‐ones, and 1,3‐bis(diisopropylphenyl)imidazol‐2‐ylidene leads to benzofurans. Eleven examples of each case are provided. The mechanistic suggestions for the pathways to both product types are supported by isotope labeling experiments. 相似文献
59.
Dr. Awal Noor Tobias Bauer Dr. Tanya K. Todorova Prof. Dr. Birgit Weber Prof. Dr. Laura Gagliardi Prof. Dr. Rhett Kempe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(30):9825-9832
Herein, the ligand‐based concept of shortening quintuple bonds and some of its limitations are reported. In dichromium–diguanidinato complexes, the length of the quintuple bond can be influenced by the substituent at the central carbon atom of the used ligand. The guanidinato ligand with a 2,6‐dimethylpiperidine backbone was found to be the optimal ligand. The reduction of its chromium(II) chloride–ate complex gave a quintuply bonded bimetallic complex with a Cr? Cr distance of 1.7056 (12) Å. Its metal–metal distance, the shortest observed in any stable compound yet, is of essentially the same length as that of the longest alkane C? C bond (1.704 (4) Å). Both molecules, the alkane and the Cr complex, are of remarkable stability. Furthermore, an unsupported CrI dimer with an effective bond order (EBO) of 1.25 between the two metal atoms, indicated by CASSCF/CASPT2 calculations, was isolated as a by‐product. The formation of this by‐product indicates that with a certain bulk of the guanidinato ligand, other coordination isomers become relevant. Over‐reduction takes place, and a chromium–arene sandwich complex structurally related to the classic dibenzene chromium complex was observed, even when bulkier substituents are introduced at the central carbon atom of the used guanidinato ligand. 相似文献
60.
Prof. Dr. A. Stephen K. Hashmi Tobias Lauterbach Dipl.‐Chem. Pascal Nösel Dr. Mie Højer Vilhelmsen Dr. Matthias Rudolph Dr. Frank Rominger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):1058-1065
A series of dinuclear gold σ,π‐propyne acetylide complexes were prepared and tested for their catalytic ability in dual gold catalysis that was based on the reaction of an electrophilic π‐complex of gold with a gold acetylide. The air‐stable and storable catalysts can be isolated as silver‐free catalysts in their activated form. These dual catalysts allow a fast initiation phase for the dual catalytic cycles without the need for additional additives for acetylide formation. Because propyne serves as a throw‐away ligand, no traces of the precatalyst are generated. Based on the fast initiation process, side products are minimized and reaction rates are higher for these catalysts. A series of test reactions were used to demonstrate the general applicability of these catalysts. Lower catalyst loadings, faster reaction rates, and better selectivity, combined with the practicability of these catalysts, make them ideal catalysts for dual gold catalysis. 相似文献