全文获取类型
收费全文 | 5517篇 |
免费 | 644篇 |
国内免费 | 788篇 |
专业分类
化学 | 2720篇 |
晶体学 | 69篇 |
力学 | 138篇 |
综合类 | 72篇 |
数学 | 1002篇 |
物理学 | 1680篇 |
无线电 | 1268篇 |
出版年
2024年 | 10篇 |
2023年 | 52篇 |
2022年 | 85篇 |
2021年 | 97篇 |
2020年 | 126篇 |
2019年 | 134篇 |
2018年 | 140篇 |
2017年 | 167篇 |
2016年 | 196篇 |
2015年 | 173篇 |
2014年 | 230篇 |
2013年 | 370篇 |
2012年 | 346篇 |
2011年 | 367篇 |
2010年 | 270篇 |
2009年 | 347篇 |
2008年 | 359篇 |
2007年 | 393篇 |
2006年 | 341篇 |
2005年 | 310篇 |
2004年 | 265篇 |
2003年 | 266篇 |
2002年 | 195篇 |
2001年 | 195篇 |
2000年 | 184篇 |
1999年 | 153篇 |
1998年 | 133篇 |
1997年 | 121篇 |
1996年 | 127篇 |
1995年 | 117篇 |
1994年 | 97篇 |
1993年 | 66篇 |
1992年 | 82篇 |
1991年 | 65篇 |
1990年 | 54篇 |
1989年 | 54篇 |
1988年 | 42篇 |
1987年 | 32篇 |
1986年 | 34篇 |
1985年 | 24篇 |
1984年 | 20篇 |
1983年 | 10篇 |
1982年 | 19篇 |
1981年 | 18篇 |
1980年 | 12篇 |
1979年 | 12篇 |
1978年 | 10篇 |
1977年 | 7篇 |
1976年 | 9篇 |
1973年 | 6篇 |
排序方式: 共有6949条查询结果,搜索用时 15 毫秒
991.
Joseph Costandy Vasileios K. Michalis Athanassios K. Stubos Ioannis G. Economou 《Molecular physics》2016,114(18):2672-2687
ABSTRACTWe report extensive molecular dynamics simulation results of pure methane and carbon dioxide hydrates at pressure and temperature conditions that are of interest to various practical applications. We focus on the calculation of the lattice constants of the two pure hydrates and their dependence on pressure and temperature. The calculated lattice constants are correlated using second order polynomials which are functions of either temperature or pressure. Finally, the obtained correlations are used in order to calculate two derivative properties, namely the isothermal compressibility and the isobaric thermal expansion coefficient. The current simulation results are also compared against reported experimental measurements and other simulation studies and good agreement is found for the case of isothermal compressibility. On the other hand, for the case of isobaric thermal expansion coefficient good agreement is found only with other simulation studies, while the simulation studies are in disagreement with experiments, particularly at low temperatures. 相似文献
992.
Shipra Sagar Binitendra Naath Mongal Abhijit Dutta Paritosh Mondal William Lewis Nadis Saba 《Journal of Coordination Chemistry》2016,69(15):2364-2376
Schiff base pyridin-2-ylimino methyl naphthanol (HL) was synthesized and characterized by spectroscopic (FTIR, ESIMS, and NMR) techniques. The ligand was reacted with perchlorate salts of Mn+2, Co+2, and Ni+2. ESIMS mass spectra indicate the formation of mononuclear complex ML2 for all three complexes. CoL2 crystallizes in P21/n space group, adopting a distorted tetrahedral geometry where Co is in a N2O2 donor environment. Structure of the Co complex was optimized by DFT calculation. Solution-phase complexation between the ligand and the three metals ions: Mn+2, Co+2, and Ni+2 (pH 7.2 in tris buffer), in CH3CN–H2O was performed spectrophotometrically by UV–vis spectral study. Job’s plot from each titration suggests a 1 : 2 metal to ligand combination. The association constants for the formation of ML2 are as follows: Mn (19.80 × 103 M?1), Co (14.54 × 103 M?1) and Ni (19.04 × 103 M?1). 相似文献
993.
To find metal ion recognition by L (L = O2N2-donor naphthodiaza-crown macrocyclic ligand), the complexes [ML]2+ (M = Cd, Hg and Pb) were synthesized and characterized by IR, 1H, 13C NMR, and mass spectrometry, as well as elemental microanalysis. Hg(II) showed perceptible enhancement of the fluorescence of L in which ultra-low limit of detection for Hg(II) by L was determined as 1 nM in ethanol and DMSO. L reserved selectivity of Hg(II) in its binary mixtures with metal cations in solution. A 1 : 1 stoichiometry was found for the interaction of Hg(II) with L while Benesi–Hildebrand method was applied to calculate its complexation binding constant (KBH) employing fluorescence spectrophotometry. The monitoring of the chemical shifts in 1H NMR spectra of these complexes demonstrated that the central macrocycle of L was tailored for the size of Hg(II). Density functional theory calculations using B3LYP/6–31G* basis set demonstrated that the macrocycle cavity of L was properly fitted for complex formation with Hg(II) cation, while both Cd(II) and Pb(II) cations did not form strong bonds with L from inadequate cation size. The present study shows detection method of Hg(II) and also possible application of naphthodiaza as an appropriate fluorophore macrocyclic ligand for detecting other metal ions. 相似文献
994.
Using a one-pot synthetic approach, a single isomer of bis(diethylenetriamine)cobalt(III) cation, [Co(dien)2]3+ is obtained in bulk from the isomeric mixture (s-fac : u-fac : mer is 7 : 28 : 65) using sodium salts of benzoates (BBz-bromobenzoate, DNBz-dinitrobenzoate, MBz-methylbenzoate) in aqueous medium. Herein, we report the syntheses and characterization of three complexes of composition mer-[Co(dien)2]Cl(p-BBz)2·H2O (1), s-fac-[Co(dien)2](o,p-DNBz)3·H2O (2) and mer-[Co(dien)2]Cl(p-MBz)2·4H2O (3) in the continuation of our earlier work, where benzoate (Bz), p-chlorobenzoate (CBz), p-nitrobenzoate (NBz) and p-aminobenzoate (ABz) were used. The isomeric identification of complex cation was initially made on the basis of spectroscopic characterization (UV–visible, IR and NMR). The binding properties of [Co(dien)2]3+ with benzoates (p-BBz, o,p-DNBz, p-MBz, Bz, CBz, NBz or ABz) have been studied using standard UV–visible spectroscopic titrations in aqueous medium and comparison indicate ion association constants of s-fac > mer. The single-crystal X-ray diffraction structure analysis of 3 reveals the presence of discrete ions ([Co(dien)2]3+, chloride, p-MBz) along with four lattice water molecules. The structure of 3, with formula [Co(dien)2](p-MBz)2Cl·4H2O, consists of alternating layers made of benzoate ions and layers made of [Co(dien)2]3+, chloride and water molecules. These layers result in the formation of their respective columns and intermolecular cohesion of p-MBz within the columns of [Co(dien)2]3+ is achieved via electrostatic and H-bonding interactions. 相似文献
995.
Polyetherimide hybrid films containing 5–40% silica were prepared through a sol-gel process and thermal imidization by using methyltriethoxysilane as precursor of the inorganic network and a poly(amic acid) resulting from polycondensation reaction of 2,2-bis[4-(4-aminophenoxy)phenyl]propane with 2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride. The properties of these films, morphology, water vapor sorption capacity, free surface energy, mechanical, thermal and electrical characteristics, were studied. The films exhibited good thermal stability, having an initial decomposition temperature above 470 °C and glass transition temperature in the range of 187–200 °C. They showed low dielectric constant and low dielectric loss in a large frequency field. Gas permeation tests using small molecules (He, N2, O2 and CO2) at 6 bar and 30 °C indicated that the hybrid films containing higher silica content showed higher permeability for all the tested gases. 相似文献
996.
Flexible and lead-free piezoelectric nanocomposites were synthesized with BaTiO3 nanowires (filler) and poly(vinylidene fluoride) (PVDF) (matrix), and the piezoelectric performances of the composites were systematically studied by varying the aspect ratio (AR) and volume fraction of the nanowire and poling time. BaTiO3 nanowires with AR of 18 were synthesized and incorporated into PVDF to improve the piezoelectric performance of the composites. It was found that high AR significantly increased the dielectric constant up to 64, which is over 800% improvement compared to those from the composites containing spheroid shape BaTiO3 nanoparticles. In addition, the dielectric constant and piezoelectric coefficient were also enhanced by increasing the concentration of BaTiO3 nanowires. The piezoelectric coefficient with 50-vol% BaTiO3 nanowires embedded in PVDF displayed 61 pC/N, which is much higher than nanocomposites with spheroid shape BaTiO3 nanoparticles as well as comparable to, if not better, other nanoparticle-filled polymer composites. Our results suggest that it is possible to fabricate nanocomposites with proper mechanical and piezoelectric properties by utilizing proper AR fillers. 相似文献
997.
998.
999.
本文主要研究了不能全含于开半球中的一些特殊曲面.利用Lr算子的相关性质,证明了对S~(n+1)中紧致r-极小超曲面,如果第二基本形式的秩rank(h_(ij))r,则其不全含在S~(n+1)的一个开半球中. 相似文献
1000.