全文获取类型
收费全文 | 24904篇 |
免费 | 961篇 |
国内免费 | 128篇 |
专业分类
化学 | 16789篇 |
晶体学 | 140篇 |
力学 | 587篇 |
数学 | 4211篇 |
物理学 | 4266篇 |
出版年
2022年 | 217篇 |
2021年 | 301篇 |
2020年 | 433篇 |
2019年 | 435篇 |
2018年 | 267篇 |
2017年 | 267篇 |
2016年 | 685篇 |
2015年 | 628篇 |
2014年 | 727篇 |
2013年 | 1230篇 |
2012年 | 1292篇 |
2011年 | 1432篇 |
2010年 | 873篇 |
2009年 | 785篇 |
2008年 | 1220篇 |
2007年 | 1229篇 |
2006年 | 1120篇 |
2005年 | 1075篇 |
2004年 | 935篇 |
2003年 | 769篇 |
2002年 | 754篇 |
2001年 | 376篇 |
2000年 | 384篇 |
1999年 | 344篇 |
1998年 | 299篇 |
1997年 | 314篇 |
1996年 | 340篇 |
1995年 | 330篇 |
1994年 | 298篇 |
1993年 | 284篇 |
1992年 | 289篇 |
1991年 | 236篇 |
1990年 | 241篇 |
1989年 | 248篇 |
1988年 | 239篇 |
1987年 | 197篇 |
1986年 | 203篇 |
1985年 | 288篇 |
1984年 | 279篇 |
1983年 | 210篇 |
1982年 | 277篇 |
1981年 | 279篇 |
1980年 | 242篇 |
1979年 | 259篇 |
1978年 | 266篇 |
1977年 | 221篇 |
1976年 | 195篇 |
1975年 | 227篇 |
1974年 | 172篇 |
1973年 | 166篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
1.
Tomáš Hložek Martin Štícha Miroslava Bursová Ivan Jelínek Petr Tůma Radomír Čabala 《Electrophoresis》2020,41(18-19):1564-1567
Riociguat is novel antihypertensive drug for treatment of pulmonary hypertension. As such, it is still being tested in many clinical and pharmacokinetic trials. Existing methods that determine serum riociguat and desmethylriociguat (DMR) are based solely on liquid chromatography with mass spectrometry. Therefore, we present a novel capillary electrophoresis with mass spectrometry method (CE-MS) for their determination in human serum as alternative method for ongoing trials. Complete resolution of both analytes was achieved by means of pH optimization of ammonium formate background electrolytes that are fully compatible with ESI/MS detection. Simple liquid-liquid extraction was used as sample pretreatment. The calibration dependence of the method was linear (in the range of 10–1000 ng/mL), with adequate accuracy (90.1–114.9%) and precision (13.4%). LOD and LOQ were arbitrarily set at 10 ng/mL for both analytes. Clinical applicability was validated using serum samples from patients treated with riociguat in pharmacokinetic study and the results corresponded with reference HPLC-MS/MS values. Capillary electrophoresis proved to be sensitive and selective tool for the analysis of riociguat and DMR. 相似文献
2.
Dr. Sabin Llona‐Minguez Dr. Matthieu Desroses Artin Ghassemian Dr. Sylvain A. Jacques Dr. Lars Eriksson Rebecka Isacksson Tobias Koolmeister Dr. Pål Stenmark Dr. Martin Scobie Prof. Thomas Helleday 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(20):7394-7398
A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif. 相似文献
3.
4.
Solvent Influence on Cellulose 1,4‐β‐Glycosidic Bond Cleavage: A Molecular Dynamics and Metadynamics Study
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Claudia Loerbroks Eliot Boulanger Prof. Dr. Walter Thiel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(14):5477-5487
We explore the influence of two solvents, namely water and the ionic liquid 1‐ethyl‐3‐methylimidazolium acetate (EmimAc), on the conformations of two cellulose models (cellobiose and a chain of 40 glucose units) and the solvent impact on glycosidic bond cleavage by acid hydrolysis by using molecular dynamics and metadynamics simulations. We investigate the rotation around the glycosidic bond and ring puckering, as well as the anomeric effect and hydrogen bonds, in order to gauge the effect on the hydrolysis mechanism. We find that EmimAc eases hydrolysis through stronger solvent–cellulose interactions, which break structural and electronic barriers to hydrolysis. Our results indicate that hydrolysis in cellulose chains should start from the ends and not in the centre of the chain, which is less accessible to solvent. 相似文献
5.
6.
Gary W. Breton Lauren A. Hahn Kenneth L. Martin 《Acta Crystallographica. Section C, Structural Chemistry》2019,75(9):1208-1212
Tetrahydrotetrazoles are five‐membered‐ring heterocycles containing four contiguous saturated nitrogen atoms. Very few examples of such compounds have been reported in the literature. Our previous attempt at the synthesis of a member of this class of compound suggested that the N—N bonds may be more labile than expected. This finding raised the question as to whether the structures of any of the previously reported tetrahydrotetrazoles had been properly assigned. We have reproduced the synthesis of a reported tetrahydrotetrazole, namely 1,2‐di‐tert‐butyl 3‐phenyl‐1H,2H,3H,10bH‐[1,2,3,4]tetrazolo[5,1‐a]isoquinoline‐1,2‐dicarboxylate, C25H30N4O4, and have now confidently confirmed its structure via X‐ray crystallography. However, while sufficiently stable in the crystal phase, we discovered that it remains very labile in solution (having a half‐life of only 15 min at 20 °C in CDCl3). A tentative reaction pathway for its dissociation based on 1H NMR spectral evidence is provided. 相似文献
7.
Back Cover: Reactions of Group 4 Metallocenes with Monosubstituted Acetonitriles: Keteniminate Formation versus CC Coupling (Chem. Eur. J. 8/2015)
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
8.
Daniel L. Feldheim Del R. Lawson Charles R. Martin 《Journal of Polymer Science.Polymer Physics》1993,31(8):953-957
We report a strong dependence of the thermal stability of Nafion® perfluorosulfonate ionomer on the nature of the counterion associated with the fixed sulfonate site. These results were obtained using thermal gravimetric analysis on a series of alkali metal and alkyl ammonium cation-exchanged Nafion films. We have found that the temperature of decomposition of Nafion is inversely dependent on the size of the exchanged cation; i.e., Nafion films show improved thermal stability as the size of the counter cation decreases. We attribute this inverse relationship of thermal stability with counterion size to an initial decomposition reaction which is strongly influenced by the strength of the sulfonate-coun-terion interaction. © 1993 John Wiley & Sons, Inc. 相似文献
9.
We consider a randomized version of the greedy algorithm for finding a large matching in a graph. We assume that the next edge is always randomly chosen from those remaining. We analyze the performance of this algorithm when the input graph is fixed. We show that there are graphs for which this Randomized Greedy Algorithm (RGA) usually only obtains a matching close in size to that guaranteed by worst-case analysis (i.e., half the size of the maximum). For some classes of sparse graphs (e.g., planar graphs and forests) we show that the RGA performs significantly better than the worst-case. Our main theorem concerns forests. We prove that the ratio to maximum here is at least 0.7690…, and that this bound is tight. 相似文献
10.
Ludmila C. Fidale Sarah Köhler Martin H.G. Prechtl Thomas Heinze Omar A. El Seoud 《Cellulose (London, England)》2006,13(5):581-592
The concentrations of water, W, and electrolytes present in solutions of LiCl in N,N-dimethylacetamide, LiCl/DMAc, and of tetrabutylammonium fluoride. x-hydrate in DMSO, TBAF.xW/DMSO can be accurately and expediently determined by three independent methods, UV–vis, FTIR and EMF measurement. The first relies on the use of solvatochromic probes whose spectra are sensitive to solution composition. It is applicable to W/LiCl/DMAc solutions but not to TBAF.xW/DMSO, because the charge-transfer complex bands of the probes are suppressed by strong interactions with the latter electrolyte. Integration of νOH band of water may be employed in order to determine [W], hence [electrolyte] by weight difference. EMF measurement uses ion-selective electrodes in order to determine [electrolyte], hence [W] by weight difference. Results of the latter method were in excellent agreement with those of FTIR. The reason for the failure of Karl Fischer titration is addressed, and the relevance of the results obtained to functionalization of cellulose under homogenous solution conditions is briefly commented on. 相似文献