全文获取类型
收费全文 | 108858篇 |
免费 | 20324篇 |
国内免费 | 11539篇 |
专业分类
化学 | 75005篇 |
晶体学 | 1096篇 |
力学 | 7086篇 |
综合类 | 637篇 |
数学 | 12749篇 |
物理学 | 44148篇 |
出版年
2024年 | 130篇 |
2023年 | 2406篇 |
2022年 | 2530篇 |
2021年 | 3571篇 |
2020年 | 4795篇 |
2019年 | 4377篇 |
2018年 | 3917篇 |
2017年 | 3493篇 |
2016年 | 5545篇 |
2015年 | 5186篇 |
2014年 | 6452篇 |
2013年 | 8248篇 |
2012年 | 10111篇 |
2011年 | 10524篇 |
2010年 | 6912篇 |
2009年 | 6722篇 |
2008年 | 7305篇 |
2007年 | 6401篇 |
2006年 | 5999篇 |
2005年 | 4850篇 |
2004年 | 3710篇 |
2003年 | 2876篇 |
2002年 | 2540篇 |
2001年 | 2219篇 |
2000年 | 1900篇 |
1999年 | 2253篇 |
1998年 | 1954篇 |
1997年 | 1919篇 |
1996年 | 1899篇 |
1995年 | 1672篇 |
1994年 | 1440篇 |
1993年 | 1214篇 |
1992年 | 1086篇 |
1991年 | 966篇 |
1990年 | 801篇 |
1989年 | 619篇 |
1988年 | 449篇 |
1987年 | 369篇 |
1986年 | 404篇 |
1985年 | 319篇 |
1984年 | 180篇 |
1983年 | 157篇 |
1982年 | 124篇 |
1981年 | 78篇 |
1980年 | 48篇 |
1979年 | 12篇 |
1974年 | 1篇 |
1957年 | 33篇 |
1923年 | 1篇 |
1922年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
Tyrosine nitration of human ERK1 introduces an intra-hydrogen bond by molecular dynamics simulations
Xu Wu Zhang Yuanya Achi Oliver Y. Knierim Kathleen D. Hanks Justin G. Wang Yingchun 《Structural chemistry》2019,30(4):1459-1470
Structural Chemistry - ERK1 is an important kinase in Ras–Raf–MEK signaling. We have recently demonstrated by mass spectrometry that Tyr210 of ERK1 can be nitrated, and the nitration... 相似文献
102.
This article proposes a global, chaos-based procedure for the discretization of functionals of Brownian motion into functionals of a Poisson process with intensity . Under this discretization we study the weak convergence, as the intensity of the underlying Poisson process goes to infinity, of Poisson functionals and their corresponding Malliavin-type derivatives to their Wiener counterparts. In addition, we derive a convergence rate of for the Poisson discretization of Wiener functionals by combining the multivariate Chen–Stein method with the Malliavin calculus. Our proposed sufficient condition for establishing the mentioned convergence rate involves the kernel functions in the Wiener chaos, yet we provide examples, especially the discretization of some common path dependent Wiener functionals, to which our results apply without committing the explicit computations of such kernels. To the best our knowledge, these are the first results in the literature on the universal convergence rate of a global discretization of general Wiener functionals. 相似文献
103.
Tian‐Jun Yue Ming‐Chao Zhang Ge‐Ge Gu Li‐Yang Wang Wei‐Min Ren Xiao‐Bing Lu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(2):628-633
The precise synthesis of poly(thioester)s with diverse structures is still a significant challenge in the polymeric materials field. Herein, we report a novel approach to the synthesis of well‐defined poly(thioester)s by the controlled alternating copolymerization of cyclic thioanhydrides and episulfides induced by simple organic ammonium salts. Both the cation and anion have strong effects on the copolymerization. [PPN]OAc ([PPN]=bis(triphenylphosphine)iminium) with a bulky cation was proven to be efficient in initiating this polymerization, yielding poly(thioester)s with a completely alternating structure, controlled molecular weight, and narrow polydispersity. The poly(thioester) obtained from succinic thioanhydride and propylene sulfide is a typical semicrystalline material, possessing a high refractive index of up to 1.78. Because it uses readily available monomers, this method is expected to open up a new route to poly(thioester)s with diverse structures and properties. 相似文献
104.
Zhi‐Chao Jiang Yao‐Yu Xiao Xia Tong Yue Zhao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(16):5386-5391
The ability to optically reconfigure an existing actuator of a liquid crystal polymer network (LCN) so that it can display a new actuation behavior or function is highly desired in developing materials for soft robotics applications. Demonstrated here is a powerful approach relying on selective polymer chain decrosslinking in a LCN actuator with uniaxial LC alignment. Using an anthracene‐containing LCN, spatially controlled optical decrosslinking can be realized through photocleavage of anthracene dimers under 254 nm UV light, which alters the distribution of actuation (crosslinked) and non‐actuation (decrosslinked) domains and thus determines the actuation behavior upon order‐disorder phase transitions. Based on this mechanism, a single actuator having a flat shape can be reconfigured in an on‐demand manner to exhibit reversible shape transformation such as self‐folding into origami three‐dimensional structures. Moreover, using a dye‐doped LCN actuator, a light‐fueled microwalker can be optically reconfigured to adopt different locomotion behaviors, changing from moving in the laser scanning direction to moving in the opposite direction. 相似文献
105.
Feng Sheng Ni Ziqiu Feng Shanshan Zhang Zhihui Liu Shuguang Wang Runbai Hu Jiawei 《Journal of Radioanalytical and Nuclear Chemistry》2019,319(3):737-748
Journal of Radioanalytical and Nuclear Chemistry - In this study, the UiO-66/Fe3O4/GO composite was prepared by one step method for removal of cesium ions (Cs+) in water and exhibited excellent... 相似文献
106.
Jiaxin Fu Yingxiong Wang Kaizhi Shen Qiang Fu Jie Zhang 《Journal of Polymer Science.Polymer Physics》2019,57(10):598-606
Many experimental results have revealed that the re‐entanglement kinetics of disentangled polymers is much slower than that predicted by tube theory. This retarded recovery of fully entangled state is of practical significance that shear‐induced modification may offer a way to improve processability for a polymer by reducing viscosity. This work tried to figure out the shear‐rate dependence variation of viscosity in the view of evolution of entanglement state through disentanglement and re‐entanglement, aiming to provide fundamental insights into application prospect of shear‐induced modification in preparing “in‐pellet” disentangled polymers prior to final processing. High‐density polyethylene was sheared on a parallel‐plate rotational rheometer with a linearly increased shear rate. Results showed that higher shear rate could induce further disentanglement, resulting in a lower viscosity with a reduction rate up to 93.7%, larger molecular weight between entanglements Me , and longer re‐entanglement time. Additionally, less entanglement would give a larger lamellar thickness of sheared samples after nonisothermal crystallization. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 598–606 相似文献
107.
Hongtao Yao Jianhua Zhou Hong Li Jiaojiao Zhao 《Journal of polymer science. Part A, Polymer chemistry》2019,57(12):1305-1314
A simple method for nanocrystalline cellulose (NCC)/fluorinated polyacrylate was developed by RAFT‐mediated surfactant‐free emulsion polymerization, in which the nanocomposites formed a core‐shell spherical morphology. The influence of the content of NCC‐g‐(PAA‐b‐PHFBA) (AA was acrylic acid, HFBA was hexafluorobutyl acrylate) on the properties of latex and film were systematically studied. The monomer conversion, the tensile strength, and water–oil repellency of film increased first and then decreased, the latex particle size decreased first and then decreased, when the content of NCC‐g‐(PAA‐b‐PHFBA) increased from 1 to 6 wt %. Elongation at break and thermal stability distinctly decreased when the content of NCC‐g‐(PAA‐b‐PHFBA) gradually increased. XPS showed that the fluorine‐containing groups well concentrated at the film–air interfaces during the annealing process. SEM analysis revealed that the treated fiber had a rugged surface, and the treated fabric had an excellent water repellency. In addition, this green grafting method in water offered a new perspective for the fabrication of exceptional NCC‐based nanocomposites with NCC as the core and also helped to promote the potential applicability of NCC in a range of multipurpose applications. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1305–1314 相似文献
108.
Yining Zhao Zhangyao Xu Tianming Wang Yuanyuan Li Li Yang Shaoyong Liu Rong Shi Yueming Ma 《Biomedical chromatography : BMC》2019,33(7)
Tanreqing capsule (TRQC) is a formulation frequently used in traditional Chinese medicine to treat pyrexia, cough, expectoration and pharyngalgia. Since the pharmacological action of traditional Chinese medicines is closely related to their complex and diverse constituents, understanding the exact composition of TRQC is important to elucidate its clinical effectiveness and mechanism of action as well as to establish quality control methods and resolve safety issues. Herein, we employed high‐performance liquid chromatography coupled with electrospray ionization tandem mass spectrometry for the simultaneous quantitation of 23 bioactive compounds in five batches of TRQC; the analytes could be categorized into five types: organic acids (seven compounds), flavonoids (10 compounds), iridoids (two compounds), phenylethanoid glycosides (two compounds) and bile acids (two compounds). The calibration curves for all analytes showed good linearity (r > 0.9953), and the inter‐ and intra‐day precisions did not exceed 4.94 and 4.97%, respectively. The recoveries varied from 90.47% to 109.80%; the corresponding relative standard deviations (RSDs) did not exceed 4.94%; and the repeatability (RSD < 4.72%) and stability (RSD < 4.88%) were also within acceptable limits. Thus, this study can be viewed as a fundamental reference for setting comprehensive TRQC quality standards. 相似文献
109.
Yongxing Tang Yajun Yu Xinyu Wei Jin Yang Yeting Zhu Yun-Hui Zhao Zilong Tang Zhihua Zhou Xiaofang Li Xianyong Yu 《Tetrahedron letters》2019,60(43):151187
A novel 6-endo-dig cyclization followed by oxidation/elimination of o-alkynylarylaldimines with 4-hydroxybenzylamine was developed for preparation of isoquinolines. The intermediates of this tandem reaction were monitored by mass spectroscopy (MS) to confirm the reaction pathway. This methodology was further applied to the design and synthesis of a novel ratiometric chemosensor for determination of fluoride. 相似文献
110.
Swinhoeisterol A is a novel steroid with unusual 6/6/5/7 tetracyclic skeleton. The model compound with BCD rings is constructed by Friedel–Crafts acylation and an oxidative dearomatization as key steps. 相似文献