全文获取类型
收费全文 | 472204篇 |
免费 | 7068篇 |
国内免费 | 1244篇 |
专业分类
化学 | 257331篇 |
晶体学 | 6641篇 |
力学 | 20019篇 |
综合类 | 13篇 |
数学 | 56475篇 |
物理学 | 140037篇 |
出版年
2021年 | 4148篇 |
2020年 | 4706篇 |
2019年 | 5032篇 |
2018年 | 6671篇 |
2017年 | 6407篇 |
2016年 | 10029篇 |
2015年 | 6686篇 |
2014年 | 9634篇 |
2013年 | 22486篇 |
2012年 | 18288篇 |
2011年 | 21986篇 |
2010年 | 15077篇 |
2009年 | 14633篇 |
2008年 | 19932篇 |
2007年 | 19815篇 |
2006年 | 18267篇 |
2005年 | 16475篇 |
2004年 | 15157篇 |
2003年 | 13237篇 |
2002年 | 12863篇 |
2001年 | 13935篇 |
2000年 | 10537篇 |
1999年 | 8231篇 |
1998年 | 6837篇 |
1997年 | 6565篇 |
1996年 | 6440篇 |
1995年 | 5682篇 |
1994年 | 5650篇 |
1993年 | 5467篇 |
1992年 | 6115篇 |
1991年 | 6150篇 |
1990年 | 5881篇 |
1989年 | 5681篇 |
1988年 | 5673篇 |
1987年 | 5557篇 |
1986年 | 5241篇 |
1985年 | 6827篇 |
1984年 | 6947篇 |
1983年 | 5469篇 |
1982年 | 5633篇 |
1981年 | 5599篇 |
1980年 | 5176篇 |
1979年 | 5539篇 |
1978年 | 5681篇 |
1977年 | 5536篇 |
1976年 | 5512篇 |
1975年 | 5081篇 |
1974年 | 5073篇 |
1973年 | 5062篇 |
1972年 | 3529篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
171.
Anton M. Zeitlin 《Letters in Mathematical Physics》2015,105(2):149-167
172.
Chris H. Hill Agnete H. Viuff Samantha J. Spratley Stéphane Salamone Stig H. Christensen Randy J. Read Nigel W. Moriarty Henrik H. Jensen Janet E. Deane 《Chemical science》2015,6(5):3075-3086
Krabbe disease is a devastating neurodegenerative disorder characterized by rapid demyelination of nerve fibers. This disease is caused by defects in the lysosomal enzyme β-galactocerebrosidase (GALC), which hydrolyzes the terminal galactose from glycosphingolipids. These lipids are essential components of eukaryotic cell membranes: substrates of GALC include galactocerebroside, the primary lipid component of myelin, and psychosine, a cytotoxic metabolite. Mutations of GALC that cause misfolding of the protein may be responsive to pharmacological chaperone therapy (PCT), whereby small molecules are used to stabilize these mutant proteins, thus correcting trafficking defects and increasing residual catabolic activity in cells. Here we describe a new approach for the synthesis of galacto-configured azasugars and the characterization of their interaction with GALC using biophysical, biochemical and crystallographic methods. We identify that the global stabilization of GALC conferred by azasugar derivatives, measured by fluorescence-based thermal shift assays, is directly related to their binding affinity, measured by enzyme inhibition. X-ray crystal structures of these molecules bound in the GALC active site reveal which residues participate in stabilizing interactions, show how potency is achieved and illustrate the penalties of aza/iminosugar ring distortion. The structure–activity relationships described here identify the key physical properties required of pharmacological chaperones for Krabbe disease and highlight the potential of azasugars as stabilizing agents for future enzyme replacement therapies. This work lays the foundation for new drug-based treatments of Krabbe disease. 相似文献
173.
Ozonolysis of a Series of Methylated Alkenes: Reaction Rate Coefficients and Gas‐Phase Products 下载免费PDF全文
Tristan Braure Véronique Riffault Alexandre Tomas Romeo Iulian Olariu Cecilia Arsene Yuri Bedjanian Patrice Coddeville 《国际化学动力学杂志》2015,47(9):596-605
The gas‐phase ozonolysis of three methylated alkenes, i.e., trans‐2,2‐dimethyl‐3‐hexene (22dM3H), trans‐2,5‐dimethyl‐3‐hexene (25dM3H), and 4‐methyl‐1‐pentene (4M1P), has been investigated in the presence of sufficient hydroxyl radical scavenger in a laminar flow reactor at ambient temperature (296 ± 2 K) and P = 1 atm of dry air (RH ≤ 5%). Ozone levels in the reactor were monitored by an automatic analyzer. Alkene and gas‐phase product concentrations were determined via online sampling either on three‐bed adsorbent cartridges followed by thermodesorption and GC/FID‐MS analysis or on 2,4‐dinitrophenylhydrazine (DNPH) cartridges for subsequent HPLC/UV analysis. Reaction rate coefficients of (3.38 ± 0.12) × 10?17 for 22dM3H and (2.71 ± 0.26) × 10?17 for 25dM3H, both in cm3 molecule?1 s?1 units, have been obtained under pseudo–first‐order conditions. Primary carbonyl products have been identified for the three investigated alkenes, and branching ratios are reported. In the case of 4M1P ozonolysis, the yield of a Criegee intermediate was indirectly determined. Kinetics and product study results are compared to those of literature when available. This work represents the first investigation of reaction products in the ozonolysis of 22dM3H, 25dM3H, and 4M1P in a flow reactor. 相似文献
174.
175.
176.
177.
Natalia L. Calvo Sebastian O. SimonettiRubén M. Maggio Teodoro S. Kaufman 《Analytica chimica acta》2015
Exposure of cimetidine (CIM) to dry heat (160–180 °C) afforded, upon cooling, a glassy solid containing new and hitherto unknown products. The kinetics of this process was studied by a second order chemometrics-assisted multi-spectroscopic approach. Proton and carbon-13 nuclear magnetic resonance (NMR), as well as ultraviolet and infrared spectroscopic data were jointly used, whereas multivariate curve resolution with alternating least squares (MCR-ALS) was employed as the chemometrics method to extract process information. It was established that drug degradation follows a first order kinetics. 相似文献
178.
179.
180.
ABSTRACT A new density functional for the study of associating inhomogeneous fluids based on Wertheim's first-order thermodynamic perturbation theory is presented and compared to the most currently used associating density functionals. This functional is developed using the weighted density approximation in the range of association of hard spheres. We implement this functional within the framework of classical density functional theory together with modified fundamental measure theory to account for volume exclusion of hard spheres. This approach is tested against molecular simulations from literature of pure associating hard spheres and mixtures of non-associationg and associating hard spheres with different number of bonding sites close to a hard uniform wall. Furthermore, we compare and review our results with the performance of associating functionals from literature, one based on fundamental measure theory and the inhomogeneous version of Wertheim's perturbation theory. Results obtained with classical DFT and the three functionals show excellent agreement with molecular simulations in systems with one hard wall. For the cases of small pores where only one or two layers of fluid are allowed discrepancies between results with classical DFT and molecular simulations were found. 相似文献