全文获取类型
收费全文 | 46530篇 |
免费 | 3173篇 |
国内免费 | 3298篇 |
专业分类
化学 | 18241篇 |
晶体学 | 372篇 |
力学 | 3868篇 |
综合类 | 500篇 |
数学 | 10483篇 |
物理学 | 19537篇 |
出版年
2024年 | 34篇 |
2023年 | 401篇 |
2022年 | 698篇 |
2021年 | 956篇 |
2020年 | 1040篇 |
2019年 | 1076篇 |
2018年 | 955篇 |
2017年 | 1111篇 |
2016年 | 1257篇 |
2015年 | 964篇 |
2014年 | 1567篇 |
2013年 | 2971篇 |
2012年 | 1877篇 |
2011年 | 2086篇 |
2010年 | 1679篇 |
2009年 | 2753篇 |
2008年 | 2998篇 |
2007年 | 3394篇 |
2006年 | 2847篇 |
2005年 | 2234篇 |
2004年 | 1862篇 |
2003年 | 2149篇 |
2002年 | 2117篇 |
2001年 | 1844篇 |
2000年 | 1752篇 |
1999年 | 1448篇 |
1998年 | 1423篇 |
1997年 | 792篇 |
1996年 | 750篇 |
1995年 | 692篇 |
1994年 | 753篇 |
1993年 | 549篇 |
1992年 | 623篇 |
1991年 | 416篇 |
1990年 | 396篇 |
1989年 | 292篇 |
1988年 | 261篇 |
1987年 | 262篇 |
1986年 | 233篇 |
1985年 | 207篇 |
1984年 | 217篇 |
1983年 | 126篇 |
1982年 | 173篇 |
1981年 | 169篇 |
1980年 | 105篇 |
1979年 | 133篇 |
1978年 | 100篇 |
1977年 | 85篇 |
1976年 | 39篇 |
1973年 | 34篇 |
排序方式: 共有10000条查询结果,搜索用时 93 毫秒
991.
Versatile cobalt complexes for initiating immortal ring‐opening polymerization (ROP) of lactide (LA), mediating living radical polymerization of t‐butyl acrylate (tBA) and catalyzing copolymerization of LA and tBA by combination of ROP and organometallic‐mediated radical polymerization 下载免费PDF全文
Jianing Zhang Baolong Wang Liying Wang Junmin Sun Yongfeng Zhang Zhenzhu Cao Zhenqiang Wu 《应用有机金属化学》2018,32(2)
Low‐cost, highly active and versatile amino‐bis(phenolate) cobalt complexes are developed. The cobalt complexes can control living polymerization of different categories of monomers including lactide (LA) by immortal ring‐opening polymerization in argon and even in air and acrylate via living radical polymerization (LRP). The cobalt‐based catalysts were used for copolymerization of LA and acrylate. The immortal polymerization of LA using the cobalt complexes as initiators proceeds in argon and even in air and without the requirement for extensive drying techniques or inert atmosphere whilst retaining end‐group fidelity. The cobalt complexes are used to mediate LRP of t‐butyl acrylate (tBA) in methanol. The block copolymerization of LA and tBA catalyzed by single‐site cobalt organometallic catalyst is also reported for the first time. This cobalt system offers a versatile and green way to produce homopolymers and block copolymers. 相似文献
992.
New Insight into the EC’ Mechanism of Uric Acid Regeneration in the Presence of Ascorbic Acid on a Poly(3,4‐ethylenedioxithiophene) Modified Gold Electrode 下载免费PDF全文
《Electroanalysis》2018,30(8):1653-1658
A gold electrode surface was functionalized by means of an electropolymerized conductive poly(3,4‐ethylenedioxythiophene) (PEDOT) organic layer. This modified electrode was used for the electrochemical detection of ascorbic (AA) and uric (UA) acids in an aqueous mixture with a selectivity around 340 mV. The electrochemical reactions kinetics were limited by AA diffusion and UA adsorption at the electrode surface, respectively. Following a previous study ([Electrochem Comm. 2011 , 13, 423–425]) cyclic voltammetry was used to provide a better understanding of the EC’ mechanism of regeneration of UA by AA. Experiments particularly showed that allantoin (i. e. the final product of UA oxidation) is not actually involved in the synergic mechanism but rather the oxidized UA product diimine which is adsorbed at the electrode surface. 相似文献
993.
Leonard I. Wassenaar Liang-Feng Han Thomas Schiefer Gustav Kainz Luis Araguas-Araguas Pradeep K. Aggarwal 《Isotopes in environmental and health studies》2018,54(3):274-287
Tritium (3H) is an essential tracer of the Earth's water cycle; yet widespread adoption of tritium in hydrologic studies remains a challenge because of analytical barriers to quantification and detection of 3H by electrolytic pre-concentration. Here, we propose a simple tritium electrolytic enrichment system based on the use of solid polymer electrolyte membranes (PEMs) that can be used to enrich 3H in 250–3000?mL environmental water samples to a 10-mL final volume. The IAEA PEM-3H system reported here can produce high enrichment factors (>70-fold) and, importantly, removes some of the deterrents to conventional 3H enrichments methods, including the use of toxic electrolysis and neutralization chemicals, spike standards, a complex electrolysis apparatus that requires extensive cooling and temperature controls, and improves precision by eliminating the need for tracking recovery gravimetrics. Preliminary results with varying operating conditions show 3H enrichments to 70-fold and higher are feasible, spanning a wide range of tritium activities from 5 to 150 TU with a precision of ~4.5?%. Further work is needed to quantify inter-sample memory and to establish lower 3H detection limits. The IAEA PEM-3H system is open source, with 3-D CAD and design files made freely available for adoption and improvement by others. 相似文献
994.
Based on the works of Gordon (1977) and Zhang and Zhou (2001) on the variational minimizing properties for Keplerian orbits and Lagrangian solutions of Newtonian 2-body and 3-body problems, we use the constrained variational principle of Ambrosetti and Coti Zelati (1990) to compute the Lagrangian actions on Keplerian and Lagrangian elliptical solutions with fixed energies. We also find an interesting relation between the period and the energy for Lagrangian elliptical solutions with Newtonian potentials. 相似文献
995.
996.
Computational insight into asymmetric uranyl‐salophen coordinated with α, β‐unsaturated aldehydes and ketones 下载免费PDF全文
Wen‐Bo Lan Xiao‐Feng Wang Li‐Ping He Yan‐Bin Meng Jun Li Bin Qiu Chang‐Ming Nie 《应用有机金属化学》2018,32(3)
The study of the catalytic activity and activation mechanism of asymmetric uranyl‐salophens with α, β‐unsaturated aldehydes or α, β‐unsaturated ketones, is a research hotspot. In this paper, the complexes of the uranyl–salophen(U‐S) modified by unilateral benzene, coordinated with cyclohexenone, cyclopentenone and acrolein, were investigated using density functional theory calculations at the level of B3LYP/6‐311G(d, p) basis set. The results showed that the uranyl‐salophen(U‐S) weakened the large π bond between C = C and C = O of the α, β‐unsaturated aldehydes and ketones, making the unsaturated aldehydes and ketones activated. In addition, the molecular‐recognition selectivity of the asymmetrical uranyl‐salophen for cyclohexenone and cyclopentenone were much higher than for acrolein. 相似文献
997.
Catalytic activity and oxidative stability of a series of iron and manganese porphyrins with 2‐chlorophenyl, phenyl and 4‐methoxyphenyl at the meso positions and metallosalens (Mn‐ and Fe‐salens) including N,N′‐bis(salicylidene)ethylenediamine, N,N′‐bis(5‐ chlorosalicylidene)ethylenediamine and N,N′‐bis(2,4‐dihydroxysalicylidene)ethylenediamine for the oxidation of olefins with tetra‐n‐butylammonium periodate (TBAP) and tetra‐n‐butyl‐ammonium Oxone (TBAO) have been investigated and compared. Although the metalloporphyrins showed an increased catalytic activity relative to the Schiff base complexes, the former provided no significant catalytic advantage over the latter. Also, a comparable or slightly higher oxidative stability was observed for the Schiff base complexes under the reaction conditions. Furthermore, in spite of large difference between the oxidizing ability of TBAO and TBAP, similar patterns were observed for the order of catalytic activity and oxidative stability of the used heme and non‐heme catalysts. The introduction of a methyl group at the ɑ position of styrene led to an increase in its reactivity, indicating the dominance of electronic effects over the steric ones in these catalytic systems. 相似文献
998.
Alena N. Maratkanova Rishat G. ValeevAlexander V. Syugaev 《Journal of Physics and Chemistry of Solids》2014
Surfactant-assisted ball milling of the Fe powder in paraffin has been used for fabrication of core–shell nanocrystalline particles. The local atomic structure of the bulk and surface layers of the mechanically milled particles has been studied using X-ray absorption spectroscopic techniques with synchrotron radiation from the DORIS storage ring at DESY, Hamburg. Regardless of milling environment composition, the as-prepared powders were shown to be characterized by a significant drop in the EXAFS signal intensity and coordination numbers of the Fe–Fe pairs due to the formation of nanocrystalline state in the particles. It has been shown that an addition of perfluorononanoic acid as a surfactant has a more prominent effect on the structure of the shell layers. The effect is revealed as an appearance of light element atoms (O, F, C) in the local atomic environment of the Fe atoms due to formation of oxide, carbide and adsorbed structures of different types in the particle shell. 相似文献
999.
On the accuracy of a nonlinear finite volume method for the solution of diffusion problems using different interpolations strategies 下载免费PDF全文
L.E.S. Queiroz M.R.A. Souza F.R.L. Contreras P.R.M. Lyra D.K.E. de Carvalho 《国际流体数值方法杂志》2014,74(4):270-291
In this paper, we consider a nonlinear finite volume method to solve the steady‐state diffusion equation in nonhomogeneous and non‐isotropic media. The method is nonlinear even if the original problem is linear. In its original form, the scheme is monotone, because the coefficient matrix is monotone under certain assumptions and, as a consequence, whenever the analytic operator demands, it preserves the positivity of numerical solutions. On the other hand, the scheme is unable to reproduce piecewise linear solutions exactly. In order to recover this interesting feature, we use two different interpolation strategies. In this case, even though we are unable to prove monotonicity, we show some numerical evidences that the combined method has an improved behavior, producing second order accurate solutions, even for nonhomogeneous and strongly anisotropic media. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
1000.