全文获取类型
收费全文 | 72707篇 |
免费 | 10491篇 |
国内免费 | 2837篇 |
专业分类
化学 | 67000篇 |
晶体学 | 625篇 |
力学 | 1178篇 |
综合类 | 10篇 |
数学 | 7436篇 |
物理学 | 9786篇 |
出版年
2023年 | 307篇 |
2022年 | 517篇 |
2021年 | 828篇 |
2020年 | 1859篇 |
2019年 | 3164篇 |
2018年 | 1743篇 |
2017年 | 1379篇 |
2016年 | 4577篇 |
2015年 | 4420篇 |
2014年 | 4419篇 |
2013年 | 6450篇 |
2012年 | 5634篇 |
2011年 | 5184篇 |
2010年 | 4462篇 |
2009年 | 4484篇 |
2008年 | 4677篇 |
2007年 | 4033篇 |
2006年 | 3457篇 |
2005年 | 3526篇 |
2004年 | 3398篇 |
2003年 | 2752篇 |
2002年 | 3316篇 |
2001年 | 2185篇 |
2000年 | 1960篇 |
1999年 | 901篇 |
1998年 | 497篇 |
1997年 | 395篇 |
1996年 | 462篇 |
1995年 | 339篇 |
1994年 | 296篇 |
1993年 | 356篇 |
1992年 | 298篇 |
1991年 | 207篇 |
1990年 | 200篇 |
1989年 | 170篇 |
1988年 | 166篇 |
1987年 | 153篇 |
1986年 | 153篇 |
1985年 | 245篇 |
1984年 | 218篇 |
1983年 | 165篇 |
1982年 | 144篇 |
1981年 | 148篇 |
1980年 | 118篇 |
1979年 | 122篇 |
1978年 | 100篇 |
1977年 | 100篇 |
1976年 | 96篇 |
1975年 | 94篇 |
1973年 | 99篇 |
排序方式: 共有10000条查询结果,搜索用时 0 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.
3.
The influence of different referencing methods on the accuracy of δ13C value measurement of ethanol fuel by gas chromatography/combustion/isotope ratio mass spectrometry 下载免费PDF全文
4.
Chemical versus Electrochemical Synthesis of Carbon Nano‐onion/Polypyrrole Composites for Supercapacitor Electrodes 下载免费PDF全文
Olena Mykhailiv Monika Imierska Martyna Petelczyc Prof. Dr. Luis Echegoyen Dr. Marta E. Plonska‐Brzezinska 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5783-5793
The development of high‐surface‐area carbon electrodes with a defined pore size distribution and the incorporation of pseudo‐active materials to optimize the overall capacitance and conductivity without destroying the stability are at present important research areas. Composite electrodes of carbon nano‐onions (CNOs) and polypyrrole (Ppy) were fabricated to improve the specific capacitance of a supercapacitor. The carbon nanostructures were uniformly coated with Ppy by chemical polymerization or by electrochemical potentiostatic deposition to form homogenous composites or bilayers. The materials were characterized by transmission‐ and scanning electron microscopy, differential thermogravimetric analyses, FTIR spectroscopy, piezoelectric microgravimetry, and cyclic voltammetry. The composites show higher mechanical and electrochemical stabilities, with high specific capacitances of up to about 800 F g?1 for the CNOs/SDS/Ppy composites (chemical synthesis) and about 1300 F g?1 for the CNOs/Ppy bilayer (electrochemical deposition). 相似文献
5.
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
6.
Interactions of Pt‐ttpy with G‐Quadruplexes Originating from Promoter Region of the c‐myc Gene Deciphered by NMR and Gel Electrophoresis Analysis 下载免费PDF全文
7.
8.
9.
Dr. Antonio M. Rodríguez Dr. Pilar Prieto Prof. Antonio de la Hoz Prof. Ángel Díaz-Ortiz D. Raúl Martín Prof. José I. García 《ChemistryOpen》2015,4(3):308-317
The aim of this work was to determine the parameters that have decisive roles in microwave-assisted reactions and to develop a model, using computational chemistry, to predict a priori the type of reactions that can be improved under microwaves. For this purpose, a computational study was carried out on a variety of reactions, which have been reported to be improved under microwave irradiation. This comprises six types of reactions. The outcomes obtained in this study indicate that the most influential parameters are activation energy, enthalpy, and the polarity of all the species that participate. In addition to this, in most cases, slower reacting systems observe a much greater improvement under microwave irradiation. Furthermore, for these reactions, the presence of a polar component in the reaction (solvent, reagent, susceptor, etc.) is necessary for strong coupling with the electromagnetic radiation. We also quantified that an activation energy of 20–30 kcal mol−1 and a polarity (μ) between 7–20 D of the species involved in the process is required to obtain significant improvements under microwave irradiation. 相似文献
10.
Pd0‐Catalyzed Intramolecular α‐Arylation of Sulfones: Domino Reactions in the Synthesis of Functionalized Tetrahydroisoquinolines 下载免费PDF全文
Prof.Dr. Daniel Solé Ferran Pérez‐Janer Dr. Raffaella Mancuso 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4580-4584
A new strategy for the synthesis of tetrahydroisoquinolines based on the Pd0‐catalyzed intramolecular α‐arylation of sulfones is reported. The combination of this Pd‐catalyzed reaction with intermolecular Michael and aza‐Michael reactions allows the development of two‐ and three‐step domino processes to synthesize diversely functionalized scaffolds from readily available starting materials. 相似文献