全文获取类型
收费全文 | 36606篇 |
免费 | 1348篇 |
国内免费 | 1358篇 |
专业分类
化学 | 9966篇 |
晶体学 | 213篇 |
力学 | 568篇 |
综合类 | 74篇 |
数学 | 24074篇 |
物理学 | 4417篇 |
出版年
2024年 | 38篇 |
2023年 | 382篇 |
2022年 | 300篇 |
2021年 | 314篇 |
2020年 | 505篇 |
2019年 | 976篇 |
2018年 | 971篇 |
2017年 | 640篇 |
2016年 | 653篇 |
2015年 | 715篇 |
2014年 | 1192篇 |
2013年 | 2211篇 |
2012年 | 1364篇 |
2011年 | 2461篇 |
2010年 | 1992篇 |
2009年 | 2614篇 |
2008年 | 2854篇 |
2007年 | 2664篇 |
2006年 | 2035篇 |
2005年 | 1448篇 |
2004年 | 1348篇 |
2003年 | 1219篇 |
2002年 | 1353篇 |
2001年 | 788篇 |
2000年 | 755篇 |
1999年 | 834篇 |
1998年 | 688篇 |
1997年 | 545篇 |
1996年 | 689篇 |
1995年 | 665篇 |
1994年 | 605篇 |
1993年 | 468篇 |
1992年 | 385篇 |
1991年 | 273篇 |
1990年 | 232篇 |
1989年 | 263篇 |
1988年 | 171篇 |
1987年 | 179篇 |
1986年 | 163篇 |
1985年 | 224篇 |
1984年 | 164篇 |
1983年 | 119篇 |
1982年 | 172篇 |
1981年 | 158篇 |
1980年 | 106篇 |
1979年 | 73篇 |
1978年 | 82篇 |
1977年 | 79篇 |
1976年 | 73篇 |
1974年 | 25篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
11.
Valentin A. Semenov Dmitry O. Samultsev Leonid B. Krivdin 《Magnetic resonance in chemistry : MRC》2020,58(6):532-539
The density functional theory calculation of 1H and 13C NMR chemical shifts in a series of ten 10 classically known Strychnos alkaloids with a strychnine skeleton was performed at the PBE0/pcSseg-2//pcseg-2 level. It was found that calculated 1H and 13C NMR chemical shifts provided a markedly good correlation with experiment characterized by a mean absolute error of 0.08 ppm in the range of 7 ppm for protons and 1.67 ppm in the range of 150 ppm for carbons, so that a mean absolute percentage error was as small as ~1% in both cases. 相似文献
12.
Pu Duan Bo Zhi Luke Coburn Christy L. Haynes Klaus Schmidt-Rohr 《Magnetic resonance in chemistry : MRC》2020,58(11):1130-1138
The composition of fluorescent polymer nanoparticles, commonly referred to as carbon dots, synthesized by microwave-assisted reaction of citric acid and ethylenediamine was investigated by 13C, 13C{1H}, 1H─13C, 13C{14N}, and 15N solid-state nuclear magnetic resonance (NMR) experiments. 13C NMR with spectral editing provided no evidence for significant condensed aromatic or diamondoid carbon phases. 15N NMR showed that the nanoparticle matrix has been polymerized by amide and some imide formation. Five small, resolved 13C NMR peaks, including an unusual ═CH signal at 84 ppm (1H chemical shift of 5.8 ppm) and ═CN2 at 155 ppm, and two distinctive 15N NMR resonances near 80 and 160 ppm proved the presence of 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-carboxylic acid (IPCA) or its derivatives. This molecular fluorophore with conjugated double bonds, formed by a double cyclization reaction of citric acid and ethylenediamine as first shown by Y. Song, B. Yang, and coworkers in 2015, accounts for the fluorescence of the carbon dots. Cross-peaks in a 1H─13C HETCOR spectrum with brief 1H spin diffusion proved that IPCA is finely dispersed in the polyamide matrix. From quantitative 13C and 15N NMR spectra, a high concentration (18 ± 2 wt%) of IPCA in the carbon dots was determined. A pronounced gradient in 13C chemical-shift perturbations and peak widths, with the broadest lines near the COO group of IPCA, indicated at least partial transformation of the carboxylic acid of IPCA by amide or ester formation. 相似文献
13.
The structure and rotational barrier for the mesityl-silicon bond of 2,2-dimesityl-1,1,1,3,3,3-hexamethyltrisilane have been investigated by 1H- and 13C-variable temperature nuclear magnetic resonance (NMR) as well as by density functional theory structural calculations. The calculations show that the lowest energy structure has C2 symmetry with nonequivalent ortho methyl groups, consistent with the crystal structure and solution NMR. The nonequivalent ortho methyl groups exchange through a Cs transition state with a calculated relative free energy of 11.0 kcal mol−1. The barrier for this rotation found by dynamic NMR is 13.4 ± 0.2 kcal mol−1 at 298 K. 相似文献
14.
Sameerah Jamal 《Journal of Differential Equations》2019,266(7):4018-4026
A manifold that contains small perturbations will induce a perturbed partial differential equation. The partial differential equation that we select is the Poisson equation – in order to explore the interplay between the geometry of the manifold and the perturbations. Specifically, we show how the problem of symmetry determination, for higher-order perturbations, can be elegantly expressed via geometric conditions. 相似文献
15.
Alessandro Morando Paola Trebeschi Tao Wang 《Journal of Differential Equations》2019,266(9):5397-5430
We show the short-time existence and nonlinear stability of vortex sheets for the nonisentropic compressible Euler equations in two spatial dimensions, based on the weakly linear stability result of Morando and Trebeschi (2008) [20]. The missing normal derivatives are compensated through the equations of the linearized vorticity and entropy when deriving higher-order energy estimates. The proof of the resolution for this nonlinear problem follows from certain a priori tame estimates on the effective linear problem in the usual Sobolev spaces and a suitable Nash–Moser iteration scheme. 相似文献
16.
In this paper, we propose a sufficient and necessary condition for the boundedness of all the solutions for the equation with the critical situation that on g and p, where , is periodic and is bounded. 相似文献
17.
18.
《Physics letters. A》2019,383(17):2090-2092
In this paper, we have used Monte Carlo (MC) method to simulate and study the temperature and doping effects on the electric conductivity of fullerene (C60). The results show that the band gap has reduced by the doping and the charge carrier transport is facilitated from valence band to conduction band by the temperature where is touched a 300 K. In this case, the conductivity reached a value of . The electric conductivity of C60 can increase by the triphenylmethane dye crystal violet (CV) alkali metal to reach at 303 K. Our results of MC simulation have a good agreement with those extracted from literature [10], [33]. 相似文献
19.
This paper deals with the Cauchy–Dirichlet problem for the fractional Cahn–Hilliard equation. The main results consist of global (in time) existence of weak solutions, characterization of parabolic smoothing effects (implying under proper condition eventual boundedness of trajectories), and convergence of each solution to a (single) equilibrium. In particular, to prove the convergence result, a variant of the so-called ?ojasiewicz–Simon inequality is provided for the fractional Dirichlet Laplacian and (possibly) non-analytic (but ) nonlinearities. 相似文献
20.
Michiel Janssen Prof. Dirk E. De Vos 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(45):10724-10734
The practical application of Shilov-type Pt catalysis to the selective hydroxylation of terminal aliphatic C−H bonds remains a formidable challenge, due to difficulties in replacing PtIV with a more economically viable oxidant, particularly O2. We report the potential of employing FeCl2 as a suitable redox mediator to overcome the kinetic hurdles related to the direct use of O2 in the Pt reoxidation. For the selective conversion of butyric acid to γ-hydroxybutyric acid (GHB), a significantly enhanced catalyst activity and stability (turnover numbers (TON)>30) were achieved under 20 bar O2 in comparison to current state-of-the-art systems (TON<10). In this regard, essential reaction parameters affecting the overall activity were identified, along with specific additives to attain catalyst stability at longer reaction times. Notably, deactivation by reduction to Pt0 was prevented by the addition of monodentate pyridine derivatives, such as 2-fluoropyridine, but also by introducing varying partial pressures of N2 in the gaseous atmosphere. Finally, stability tests revealed the involvement of PtII and FeCl2 in catalyzing the non-selective overoxidation of GHB. Accordingly, in situ esterification with boric acid proved to be a suitable strategy to maintain enhanced selectivities at much higher conversions (TON>60). Altogether, a useful catalytic system for the selective hydroxylation of primary aliphatic C−H bonds with O2 is presented. 相似文献