全文获取类型
收费全文 | 70629篇 |
免费 | 7238篇 |
国内免费 | 5801篇 |
专业分类
化学 | 43838篇 |
晶体学 | 1076篇 |
力学 | 3831篇 |
综合类 | 397篇 |
数学 | 7537篇 |
物理学 | 26989篇 |
出版年
2023年 | 681篇 |
2022年 | 1151篇 |
2021年 | 1490篇 |
2020年 | 1730篇 |
2019年 | 1796篇 |
2018年 | 1776篇 |
2017年 | 1748篇 |
2016年 | 2413篇 |
2015年 | 2282篇 |
2014年 | 3005篇 |
2013年 | 4454篇 |
2012年 | 4876篇 |
2011年 | 5331篇 |
2010年 | 3930篇 |
2009年 | 3981篇 |
2008年 | 4392篇 |
2007年 | 3889篇 |
2006年 | 3599篇 |
2005年 | 2977篇 |
2004年 | 2463篇 |
2003年 | 2101篇 |
2002年 | 2072篇 |
2001年 | 2249篇 |
2000年 | 1654篇 |
1999年 | 1348篇 |
1998年 | 993篇 |
1997年 | 943篇 |
1996年 | 810篇 |
1995年 | 738篇 |
1994年 | 712篇 |
1993年 | 596篇 |
1992年 | 627篇 |
1991年 | 599篇 |
1990年 | 583篇 |
1989年 | 497篇 |
1988年 | 512篇 |
1987年 | 481篇 |
1986年 | 437篇 |
1985年 | 475篇 |
1984年 | 484篇 |
1983年 | 364篇 |
1982年 | 393篇 |
1981年 | 383篇 |
1979年 | 412篇 |
1978年 | 382篇 |
1977年 | 403篇 |
1976年 | 395篇 |
1975年 | 345篇 |
1974年 | 322篇 |
1973年 | 338篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
41.
Adel Z. El‐Sonbati Mostafa A. Diab Ahmed M. Eldesoky Shaimaa M. Morgan Omnia L. Salem 《应用有机金属化学》2019,33(5)
Novel polymer complexes of 8‐hydroxyquinoline‐5‐sulfonic acid hydrate ( H 2 L ) with Cu2+, Co2+ and Ni2+ chloride were prepared and characterized. Microanalysis, magnetic susceptibility, IR spectra, electron spin resonance, mass spectra, X‐ray, molar conductance, thermal, and UV–Vis spectra studies have been used to confirm the structure of the prepared polymer complexes. The molecular and electronic structures of the hydrogen bond conformers for ligand ( H 2 L ) were optimized theoretically and the quantum chemical parameters were calculated. On the basis of elemental and IR data, the chemical structure of metal chelates commensurate that the tri‐dentate (H2L) coordinate to metal chlorides through oxygen atom of phenolic OH and oxygen atom of SO3‐H group by replacing H atoms and nitrogen of the quinoline ring. The magnetic studies suggested the octahedral geometrical structure for all produced polymer complexes with general formula {[ML (OH2)3] .xH2O}n (M = Cu2+, x = 1.; Co2+, x = 2 and Ni2+, x = 2) in molar ratio (1:1). Coats–Redfern and Horowitz–Metzger methods have been used for calculating the activation thermodynamic parameters of the thermal decomposition for H 2 L and its polymer complexes. The interaction between H 2 L and its transition metal complexes with the calf thymus DNA (CT‐DNA) was determined by UV–Vis spectra. Binding efficiency between H 2 L with the receptors of the prostate cancer (PDB code 2Q7L Hormone) and the breast cancer (PDB code 1JNX Gene regulation) was studied by molecular docking. The inhibition behaviour of H 2 L against the corrosion of carbon steel / HCl (2 M) solution was studied by weight loss, Tafel polarisation, electrochemical impedance spectroscopy (EIS) and electrochemical frequency modulation (EFM) techniques. The adsorption isotherm was found to be Friendlish isotherm. The morphology of inhibited carbon steel? s surface was studied using scanning electron microscope (SEM) and energy dispersive X‐ray spectroscopy (EDS). 相似文献
42.
Wu Fang Guo Xiaoxue Hao Gazi Hu Yubing Jiang Wei 《Journal of Solid State Electrochemistry》2019,23(9):2627-2637
Journal of Solid State Electrochemistry - Developing low-cost and earth-abundant electrocatalysts with high activity for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER)... 相似文献
43.
For a general dyadic grid, we give a Calderón–Zygmund type decomposition, which is the principle fact about the multilinear maximal function on the upper half‐spaces. Using the decomposition, we study the boundedness of . We obtain a natural extension to the multilinear setting of Muckenhoupt's weak‐type characterization. We also partially obtain characterizations of Muckenhoupt's strong‐type inequalities with one weight. Assuming the reverse Hölder's condition, we get a multilinear analogue of Sawyer's two weight theorem. Moreover, we also get Hytönen–Pérez type weighted estimates. 相似文献
44.
Acta Mathematicae Applicatae Sinica, English Series - The generalized estimating equations(GEE) approach is perhaps one of the most widely used methods for longitudinal data analysis. While the GEE... 相似文献
45.
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
46.
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
47.
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
48.
Fan‐Li Zhang Jun Yi Wei Peng Petar M. Radjenovic Hua Zhang Zhong‐Qun Tian Jian‐Feng Li 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(35):12261-12265
The fundamental understanding of the subtle interactions between molecules and plasmons is of great significance for the development of plasmon‐enhanced spectroscopy (PES) techniques with ultrahigh sensitivity. However, this information has been elusive due to the complex mechanisms and difficulty in reliably constructing and precisely controlling interactions in well‐defined plasmonic systems. Herein, the interactions in plasmonic nanocavities of film‐coupled metallic nanocubes (NCs) are investigated. Through engineering the spacer layer, molecule–plasmon interactions were precisely controlled and resolved within 2 nm. Efficient energy exchange interactions between the NCs and the surface within the 1–2 nm range are demonstrated. Additionally, optical dressed molecular excited states with a huge Lamb shift of ≈7 meV at the single‐molecule (SM) level were observed. This work provides a basis for understanding the underlying molecule–plasmon interaction, paving the way for fully manipulating light–matter interactions at the nanoscale. 相似文献
49.
We study ground states of two-component Bose–Einstein condensates (BEC) with trapping potentials in , where the intraspecies interaction and the interspecies interaction ?β are both attractive, , , and β are all positive. The existence and non-existence of ground states are classified completely by investigating equivalently the associated -critical constraint variational problem. The uniqueness and symmetry-breaking of ground states are also analyzed under different types of trapping potentials as , where () is fixed and w is the unique positive solution of in . The semi-trivial limit behavior of ground states is tackled in the companion paper [12]. 相似文献
50.
Sidra Jabeen Zhe Zeng Mohammednoor Altarawneh Xiangpeng Gao Anam Saeed Bogdan Z. Dlugogorski 《国际化学动力学杂志》2019,51(9):696-710
This contribution investigates thermal decomposition of leucine, as a representative model compound for amino acids in algal biomass. We map out potential energy surface for a wide array of unimolecular and self-condensation reactions operating in the decomposition of leucine. Decarboxylation and dehydration of leucine ensues by eliminating CO2 and –OH, respectively, from the –COOH group attached to the α-carbon. The molecular channel for deamination involves cleavage of NH2 from α-carbon of leucine. The activation energies for direct elimination of CO2, NH3, and H2O from a leucine molecule lie within 20.7 kJ/mol of each other. Activation energies for these decomposition pathways reside below the bond dissociation enthalpy of H–C(α) of 323.1 kJ/mol. The decarboxylation, deamination, and dehydration pathways, via radical-prompted pathways, systematically require lower energy barriers, in reference to closed-shell reaction corridors. Detailed computations at the CBS-QB3 level provide the Arrhenius rate parameters for the unimolecular and bimolecular reactions, and standard enthalpies of formation, standard entropies, and heat capacities for all the products and intermediates. A kinetic analysis of gas-phase reactions, within the context of a plug-flow reactor model, accounts qualitatively for the formation of major products observed experimentally in the thermal degradation of the condensed-phase leucine. Among notable N-containing species, the model predicts the prevailing of NH3 over HCN and HNCO, in addition to corresponding appreciable concentrations of amines, imines, and nitriles. Our detailed kinetic investigation illustrates a negligible contribution of the self-condensation reactions of leucine in the gas phase. 相似文献