全文获取类型
收费全文 | 43195篇 |
免费 | 3174篇 |
国内免费 | 4902篇 |
专业分类
化学 | 29098篇 |
晶体学 | 395篇 |
力学 | 1982篇 |
综合类 | 694篇 |
数学 | 7221篇 |
物理学 | 11881篇 |
出版年
2023年 | 590篇 |
2022年 | 701篇 |
2021年 | 1526篇 |
2020年 | 1231篇 |
2019年 | 1197篇 |
2018年 | 939篇 |
2017年 | 1101篇 |
2016年 | 1380篇 |
2015年 | 1372篇 |
2014年 | 1722篇 |
2013年 | 3115篇 |
2012年 | 2245篇 |
2011年 | 2576篇 |
2010年 | 2185篇 |
2009年 | 2813篇 |
2008年 | 2906篇 |
2007年 | 3163篇 |
2006年 | 2422篇 |
2005年 | 1698篇 |
2004年 | 1536篇 |
2003年 | 1456篇 |
2002年 | 1211篇 |
2001年 | 1221篇 |
2000年 | 864篇 |
1999年 | 689篇 |
1998年 | 698篇 |
1997年 | 590篇 |
1996年 | 629篇 |
1995年 | 535篇 |
1994年 | 556篇 |
1993年 | 582篇 |
1992年 | 533篇 |
1991年 | 366篇 |
1990年 | 286篇 |
1989年 | 235篇 |
1988年 | 259篇 |
1987年 | 219篇 |
1986年 | 225篇 |
1985年 | 330篇 |
1984年 | 236篇 |
1983年 | 143篇 |
1982年 | 295篇 |
1981年 | 476篇 |
1980年 | 426篇 |
1979年 | 473篇 |
1978年 | 370篇 |
1977年 | 281篇 |
1976年 | 238篇 |
1974年 | 75篇 |
1973年 | 150篇 |
排序方式: 共有10000条查询结果,搜索用时 78 毫秒
11.
A simple, sensitive and rapid ultra‐high‐performance liquid chromatography–electrospray ionization–tandem mass spectrometry method was developed and validated for the quantification of warfarin and 7‐hydroxy warfarin in Sprague Dawley (SD) rats. Animals were administered a single dose of warfarin sodium formulations (crystalline and amorphous) at 12 mg/kg via oral gavage and blood was drawn over a 96‐h time course. Sample process recoveries, matrix effect and analyte stability were determined. The linearity for warfarin and 7‐hydroxy warfarin was from 5 to 2000 ng/mL in blank SD rat plasma. Correlation coefficients (r2) for standard calibration curves were >.98 and analytes quantified within ±15% of target at all calibrator concentrations. The average percent accuracy and precision for intra‐ and inter‐day were 93.7%–113.8% and ≤12.1%, respectively, for warfarin and 7‐hydroxy warfarin, across the quality control standards (5, 10, 500, 1800 and 2000 ng/mL). Acceptable analytical recovery (>55%) was achieved with process efficiencies >41.5% and matrix effects <139.9% over the analytical range. Both analytes were stable in stock solution, autosampler, benchtop and three cycles of freeze–thaw with percent accuracy ≥90.2% and precision (percent relative standard deviation) ≤14%. The validated method was successfully applied to a pre‐clinical bioavailability study of crystalline and amorphous warfarin sodium formulations in SD rats. 相似文献
12.
Sachin B. Pandya Urmila H. Patel Kaushik P. Chaudhary Bhavesh N. Socha Nikita J. Patel Bhupesh S. Bhatt 《应用有机金属化学》2019,33(12)
Novel cobalt complex of 4‐amino‐N‐(6‐chloropyridazin‐3‐yl)benzene sulfonamide (sulfachloropyridazine) has been synthesized and characterized by elemental analysis, FT‐IR spectroscopy and magnetic susceptibility (VSM). Cobalt complex of Sulfachloropyridazine (Co‐SCP) crystallized in monoclinic space group P21/n with Z = 4. The structure is solved by direct method and refined to R = 0.099 for 4720 reflections with I ?4σ(I). The results of FT‐IR spectra suggest the binding of cobalt atom to the sulfonamide ligand which is in agreement with the crystal structure determination. In crystal structure, molecule is linked via, C‐H … π, C‐Cl … π and π … π intermolecular interactions. The computational studies like the optimization energy and root means square deviation compare with single crystal structure, frontier molecular orbital (Homo‐Lumo energy) and binding energy of the Co‐SCP has been carried out using DFT/B3LYP level of theory in gaseous phase. Hirshfeld surfaces and the 2D‐fingerprint analysis are performed to study the nature of interactions and their measurable contributions towards crystal packing. The interaction of the complex with DNA is investigated using viscosity measurement and absorption titration studies. The result shows the complex bind to DNA with intercalative mode with high DNA‐binding constant (Kb). Also, in vivo and in vitro cytotoxic studies are performed using S. pombe cells and brine shrimp lethality bioassay. DNA‐cleavage study shows better cleaving ability of the complex. 相似文献
13.
Petr P. Sharin Sofia P. Yakovleva Susanna N. Makharova Maria I. Vasilieva Vasilii I. Popov 《Composite Interfaces》2019,26(1):53-65
The structural-phase state of the contact zone and the factors that influence on the strength of diamond retention in the diamond carbide composites were determined. Composites were obtained by the new hybrid technology that eliminates the reheating of the metalized coating. The elaborated technology combines the thermal diffusion metallization of a diamond and the sintering by the scheme of self-dosed impregnation in a one-stage technological cycle. By the methods of electron microscopy, X-ray diffraction analysis, and Raman spectroscopy the structural and phase characteristics of the interphase boundary were investigated. The improvement of chemical and mechanical adhesion between the diamond and carbide matrix was obtained. It was shown that the specific productivity of the samples with a metalized diamond component is 39% higher than those without metallization. 相似文献
14.
Yasuhito Tanaka 《Operations Research Letters》2019,47(5):406-409
We study a dynamic free-entry oligopoly with sluggish entry and exit of firms under general demand and cost functions. We show that the number of firms in a steady-state open-loop solution for a dynamic free-entry oligopoly is smaller than that at static equilibrium and that the number of firms in a steady-state memoryless closed-loop solution is larger than that in an open-loop solution. 相似文献
15.
This paper develops a framework to deal with the unconditional superclose analysis of
nonlinear parabolic equation. Taking the finite element pair $Q_{11}/Q_{01} × Q_{10}$ as an example,
a new mixed finite element method (FEM) is established and the $τ$ -independent superclose
results of the original variable $u$ in $H^1$-norm and the flux variable $\mathop{q} \limits ^{\rightarrow}= −a(u)∇u$ in $L^2$-norm are deduced ($τ$ is the temporal partition parameter). A key to our analysis is an
error splitting technique, with which the time-discrete and the spatial-discrete systems are
constructed, respectively. For the first system, the boundedness of the temporal errors is obtained. For the second system, the spatial superclose results are presented unconditionally, while the previous literature always only obtain the convergent estimates or require
certain time step conditions. Finally, some numerical results are provided to confirm the
theoretical analysis, and show the efficiency of the proposed method. 相似文献
16.
17.
The electrochemical behavior of austenitic stainless steel (Type 304) in 3 M sulfuric acid with 3.5% recrystallized sodium chloride at specific concentrations of butan-1-ol was investigated with the aid of potentiodynamic polarization, open circuit measurement and weight loss technique. Butan-1-ol effectively inhibited the steel corrosion with a maximum inhibition efficiency of 78.7% from weight-loss analysis and 80.9% from potentiodynamic polarization test at highest concentration studied. Adsorption of the compound obeyed the Freundlich isotherm. Thermodynamic calculations reveal physiochemical interactions and spontaneous adsorption mechanism. Surface characterizations showed the absence of corrosion products and topographic modifications of the steel. Statistical analysis depicts the overwhelming influence and statistical significance of inhibitor concentration on the inhibition performance. 相似文献
18.
Gunasekaran Balamurugan Sundarraman Balaji Rengan Ramesh Nattamai S.P. Bhuvanesh 《应用有机金属化学》2019,33(1)
A panel of six new arene Ru (II)‐NHC complexes 2a‐f , (NHC = 1,3‐diethyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1a , 1,3‐dicyclohexylmethyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1b and 1,3‐dibenzyl‐(5,6‐dimethyl)benzimidazolin‐2‐ylidene 1c ) were synthesized from the transmetallation reaction of Ag‐NHC with [(η6‐arene)RuCl2]2 and characterized. The ruthenium (II)‐NHC complexes 2a‐f were developed as effective catalysts for α‐alkylation of ketones and synthesis of bioactive quinoline using primary/amino alcohols as coupling partners respectively. The reactions were performed with 0.5 mol% catalyst load in 8 h under aerobic condition and the maximum yield was up to 96%. Besides, the different alkyl wingtips on NHC and arene moieties were studied to differentiate the catalytic robustness of the complexes in the transformations. 相似文献
19.
Antonin Desmecht Dr. Debobrata Sheet Claude Poleunis Prof. Sophie Hermans Prof. Olivier Riant 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(6):1436-1440
The chemical functionalization of carbon nanotubes is often a prerequisite prior to their use in various applications. The covalent grafting of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (BPin) functional groups directly on the surface of multi- and single-walled carbon nanotubes, activated by nucleophilic addition of nBuLi, was carried out. Thermogravimetric analysis (TGA) coupled with mass spectrometry, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ions mass spectrometry (ToF-SIMS) confirmed the efficiency of this methodology and proved the integrity and covalent grafting of the BPin functional groups. These groups were further reacted with various nucleophiles in the presence of a copper(II) source in the conditions of the aerobic Chan–Lam–Evans coupling. The resulting materials were characterized by TGA, XPS and ToF-SIMS. This route is efficient, reliable and among the scarce reactions that enable the direct grafting of heteroatoms at carbonaceous material surfaces. 相似文献
20.
The behaviors of ferromagnetic transition metals of the first period: Fe, Co and Ni are examined within density functional theory calculations in two dimensional carbon extended networks using model structure LiC6. Around geometry optimized structures, the energy-volume equations of states considering non magnetic and spin polarized configurations established ferromagnetic ground states with magnetizations –reduced with respect to the metals’– of 2 μB for FeC6 and 1 μB for CoC6 while no magnetic solution could be identified for NiC6. In the D6h point group of the P6/mmm space group lm decomposition of the d states results with increasing energy into doublet state E1g with d(x2-y2) and d(xy); singlet state A1g d(z2) and doublet state E2g d(xz) and d(yz) lying on EF and responsible of the onset of magnetic moments. This was mirrored via molecular orbital approach with a construct of Fe embedded between two extended carbon networks thus validating the model structure proposed for TC6 compounds. The 100% polarization in one spin channel allows proposing potential uses in spintronics applications. 相似文献