全文获取类型
收费全文 | 515209篇 |
免费 | 13657篇 |
国内免费 | 3022篇 |
专业分类
化学 | 299843篇 |
晶体学 | 7370篇 |
力学 | 20411篇 |
综合类 | 12篇 |
数学 | 58559篇 |
物理学 | 145693篇 |
出版年
2021年 | 3386篇 |
2020年 | 4820篇 |
2019年 | 6325篇 |
2018年 | 5816篇 |
2017年 | 5306篇 |
2016年 | 10561篇 |
2015年 | 8248篇 |
2014年 | 10662篇 |
2013年 | 25114篇 |
2012年 | 18656篇 |
2011年 | 21760篇 |
2010年 | 15757篇 |
2009年 | 15586篇 |
2008年 | 20751篇 |
2007年 | 20467篇 |
2006年 | 19291篇 |
2005年 | 17755篇 |
2004年 | 15931篇 |
2003年 | 14360篇 |
2002年 | 14742篇 |
2001年 | 15566篇 |
2000年 | 12243篇 |
1999年 | 8962篇 |
1998年 | 7243篇 |
1997年 | 7108篇 |
1996年 | 6951篇 |
1995年 | 6159篇 |
1994年 | 5992篇 |
1993年 | 5836篇 |
1992年 | 6376篇 |
1991年 | 6335篇 |
1990年 | 6014篇 |
1989年 | 5783篇 |
1988年 | 6010篇 |
1987年 | 5703篇 |
1986年 | 5458篇 |
1985年 | 7619篇 |
1984年 | 7828篇 |
1983年 | 6380篇 |
1982年 | 6936篇 |
1981年 | 6878篇 |
1980年 | 6504篇 |
1979年 | 6770篇 |
1978年 | 6895篇 |
1977年 | 6874篇 |
1976年 | 6846篇 |
1975年 | 6589篇 |
1974年 | 6460篇 |
1973年 | 6746篇 |
1972年 | 4136篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
81.
82.
Design and development of a two‐dimensional system based on hydrophilic and reversed‐phase liquid chromatography with on‐line sample treatment for the simultaneous separation of excreted xenobiotics and endogenous metabolites in urine 下载免费PDF全文
Diego García‐Gómez Encarnación Rodríguez‐Gonzalo Rita Carabias‐Martínez 《Biomedical chromatography : BMC》2015,29(8):1190-1196
In the present work we describe a two‐dimensional liquid chromatographic system (2D‐LC) with detection by mass spectrometry (MS) for the simultaneous separation of endogenous metabolites of clinical interest and excreted xenobiotics deriving from exposure to toxic compounds. The 2D‐LC system involves two orthogonal chromatographic modes, hydrophilic interaction liquid chromatography (HILIC) to separate polar endogenous metabolites and reversed‐phase (RP) chromatography to separate excreted xenobiotics of low and intermediate polarity. Additionally, the present proposal has the novelty of incorporating an on‐line sample treatment based on the use of restricted access materials (RAMs), which permits the direct injection of urine samples into the system. The work is focused on the instrumental coupling, studying all possible options and attempting to circumvent the problems of solvent incompatibility between the RAM device and the two chromatographic columns, HILIC and RP. The instrumental configuration developed, RAM‐HILIC‐RPLC‐MS/MS, allows the simultaneous assessment of urinary metabolites of clinical interest and excreted compounds derived from exposure to toxic agents with minimal sample manipulation. Thus, it may be of interest in areas such as occupational and environmental toxicology in order to explore the possible relationship between the two types of compounds. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
83.
Crosslinked poly(ethylene oxide) containing siloxanes fabricated through thiol‐ene photochemistry 下载免费PDF全文
Victor A. Kusuma Elliot A. Roth William P. Clafshenkel Steven S. Klara Xu Zhou Surendar R. Venna Erik Albenze David R. Luebke Meagan S. Mauter Richard R. Koepsel Alan J. Russell David Hopkinson Hunaid B. Nulwala 《Journal of polymer science. Part A, Polymer chemistry》2015,53(13):1548-1557
Homogenous amphiphilic crosslinked polymer films comprising of poly(ethylene oxide) and polysiloxane were synthesized utilizing thiol‐ene “ click ” photochemistry. A systematic variation in polymer composition was Carried out to obtain high quality films with varied amount of siloxane and poly(ethylene oxide). These films showed improved gas separation performance with high gas permeabilities with good CO2/N2 selectivity. Furthermore, the resulting films were also tested for its biocompatibility, as a carrier media which allow human adult mesenchymal stem cells to retain their capacity for osteoblastic differentiation after transplantation. The obtained crosslinked films were characterized using differential scanning calorimetry, dynamic mechanical analysis, thermogravimetric analysis, FTIR, Raman‐IR , and small angle X‐ray scattering. The synthesis ease and commercial availability of the starting materials suggests that these new crosslinked polymer networks could find applications in wide range of applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1548–1557 相似文献
84.
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
85.
86.
87.
88.
DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex 下载免费PDF全文
Cheng‐Gen Zhang Shu‐Yuan Yu Liaoyun Zhang Huayi Li Zhi‐Xiang Wang 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):576-585
DFT computations have been performed to investigate the mechanism of H2‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H2 can react with the deactivated [Zr]?pMS?PPn facilely, which displace functionalized pMS?PPn chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585 相似文献
89.
90.
A model is developed for the formation and propagation of cracks in a material sample that is heated at its top surface, pyrolyses, and then thermally degrades to form char. In this work the sample is heated uniformly over its entire top surface by a hypothetical flame (a heat source). The pyrolysis mechanism is described by a one-step overall reaction that is dependent nonlinearly on the temperature (Arrhenius form). Stresses develop in response to the thermal degradation of the material by means of a shrinkage strain caused by local mass loss during pyrolysis. When the principal stress exceeds a prescribed threshold value, the material forms a local crack. Cracks are found to generally originate at the surface in response to heating, but occasionally they form in the bulk, away from ever-changing material boundaries. The resulting cracks evolve and form patterns whose characteristics are described. Quantities examined in detail are: the crack spacing in the pyrolysis zone; the crack length evolution; the formation and nature of crack loops which are defined as individual cracks that have joined to form loops that are disconnected from the remaining material; the formation of enhanced pyrolysis area; and the impact of all of the former quantities on mass flux. It is determined that the mass flux from the sample can be greatly enhanced over its nominal (non-cracking) counterpart. The mass efflux profile qualitatively resembles those observed in Cone Calorimeter tests. 相似文献