全文获取类型
收费全文 | 12732篇 |
免费 | 2158篇 |
国内免费 | 1921篇 |
专业分类
化学 | 9352篇 |
晶体学 | 252篇 |
力学 | 769篇 |
综合类 | 148篇 |
数学 | 1244篇 |
物理学 | 5046篇 |
出版年
2024年 | 37篇 |
2023年 | 214篇 |
2022年 | 529篇 |
2021年 | 542篇 |
2020年 | 518篇 |
2019年 | 516篇 |
2018年 | 472篇 |
2017年 | 467篇 |
2016年 | 672篇 |
2015年 | 679篇 |
2014年 | 823篇 |
2013年 | 1031篇 |
2012年 | 1270篇 |
2011年 | 1285篇 |
2010年 | 907篇 |
2009年 | 892篇 |
2008年 | 894篇 |
2007年 | 800篇 |
2006年 | 774篇 |
2005年 | 659篇 |
2004年 | 486篇 |
2003年 | 332篇 |
2002年 | 355篇 |
2001年 | 294篇 |
2000年 | 242篇 |
1999年 | 189篇 |
1998年 | 168篇 |
1997年 | 123篇 |
1996年 | 94篇 |
1995年 | 87篇 |
1994年 | 73篇 |
1993年 | 67篇 |
1992年 | 63篇 |
1991年 | 56篇 |
1990年 | 45篇 |
1989年 | 26篇 |
1988年 | 20篇 |
1987年 | 13篇 |
1986年 | 9篇 |
1985年 | 16篇 |
1984年 | 15篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1981年 | 11篇 |
1980年 | 10篇 |
1979年 | 7篇 |
1971年 | 2篇 |
1965年 | 2篇 |
1959年 | 2篇 |
1957年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
应用灰色系统理论和最小二乘原理,推导出连续GM(1,N)模型,并将该模型用于高效液相色谱中溶质保留行为的预测.研究了烷烃、烷基苯及对羟基苯甲酸酯等化合物的容量因子与流动相组成、容量因子与碳数、保留时间与温度、保留时间与碳数的关系,并建立了相应的数学模型,经验证,预测结果良好. 相似文献
102.
A series of 2-cyano-3-methylthio-3-substituted methylaminoacrylates were synthesized as herbicidal inhibitors of photosystem Ⅱ (PSⅡ) electron transport, in order to estimate the effect of fluorine atom, pyridyl group, chirality and ester chain on activity. The important intermediate 2-fluoro-5-aminomethylpyridine was synthesized with high yield. The bioassay results showed that most of rifle compounds had high herbicidal activity in postemergence treatment. The introduction of an a-methyl into the 3-substituted methylamino could improve the activity notably. The replacement of hydrogen by chlorine or fluorine group and phenyl by pyridyl group showed different effects, and at the same time, the ester chain affected the activity too. 相似文献
103.
A new method for inductively coupled plasma atomic emission spectrometry (ICP-AES) determination of trace Sc and Y, based on gaseous compound introduction into the plasma as their thenoyltrifluoroacetone (TTA) complexes by electrothermal vaporization was developed. Using the reagent TTA as chemical modifier can not only enhance the analytical signals, but also reduce the vaporization temperature. At a temperature of 1,000 °C the trace Sc and Y can be vaporized completely into ICP. The factors affecting the formation of the chelate and its vaporization behavior, such as drying time, vaporization temperature/time, reaction medium and the amount of TTA, were investigated in detail. Under the optimized conditions (drying temperature/time 100 °C/10 s, vaporization temperature/time 1,000 °C/4 s), the limits of detection for Sc and Y were 19 pg and 34 pg (3), respectively, and the relative standard deviations for Sc and Y were 4.2% (c
Sc=0.2 g mL–1; n=7) and 2.6% (c
Y=0.5 g mL–1; n=7). The linear ranges of the calibration graphs cover three orders of magnitude. The method was applied to the analysis of the biological reference materials (GBW 07602, bush branches and leaves; GBW 07604, poplar leaves), and the results obtained were in good agreement with the certified values. 相似文献
104.
This phase was discovered following direct fusion of the elements in welded Nb tubes at 550 degrees C and equilibration at 300 degrees C for 1 week. Single-crystal X-ray diffraction analysis reveals that KNa(3)In(9) crystallizes in an orthorhombic system (Cmca, Z = 8, a = 9.960(1) A, b =16.564(2) A, c = 17.530(2) A, 23 degrees C). The structure contains a three-dimensional indium network built of layers of empty In(12) icosahedra that are each 12-bonded and interconnected by 4-bonded indium atoms that also form zigzag chains. All cations bridge between cluster faces or edges, and their mixed sizes appear critical to the stability of this particular structure, which does not occur in either binary system. Both empirical electron counting and EHTB band structure calculations on the macroanion indicate that the bonding in this structure is closed-shell, whereas resistivity and magnetic susceptibility measures show that the compound is a moderately poor metal. 相似文献
105.
Biochemistry is a branch subject of chemistry, which is the study of chemical structures and processes associated with living organisms. COVID-19 pandemic is a problem for human beings. From the perspective of biochemistry, this paper demonstrates the chemical structure and interactions of SARS-CoV-2's spike protein and its receptor (human angiotensin converting enzyme 2), and summarizes the related research progresses. The authors hope to provide insights for the development of COVID-19 vaccine. 相似文献
106.
Synthesis of the third-order nonlinear materials:bis (1,4-dihydroxynaphthalene) tetrathiafulvalene and bis (1,4-dialkoxylnaphthalene) tetrathiafulvalene has been achieved in four steps, starting from 2,3-dichloro-1,4-naphthaquinone. The materials exhibit larger third-order nonlinear optical susceptibilities χ. 相似文献
107.
纳米核壳式铜-锡双金属粉的制备及性能研究 总被引:7,自引:0,他引:7
A kind of novel core-shell Cu-Sn bimetallic nanoparticles has been prepared by a new method (displacement method), in which Sn was made to cover on the surface of Cu nano-core. The preparation method and reaction mechanism have been discussed. This reaction happened under the existence of coordinate agent-(NH2)2CS and protective agent PVP. The nanoparticles prepared were with a core-shell structure, granule diameter between 50~100 nm and good dispersing capability. The Cu-Sn nanoparticles proposed has better oxidation-resistant ability than Cu nanoparticles with corresponding granule diameter and can be applied as lubricant additives as well as antibacterial agent. When the additive amount is very low (0.1wt‰~0.5wt‰), it can improve the PB of the lubricant by 92%~106%, and also enhance its antiwear characteristics and friction-reducing properties. At the concentration of 1 000 ppm, it can reach an antibacterial ratio of 99.99%. 相似文献
108.
The catalytic effect of chiral Lewis acids on the hetero-Diels-Alder reaction between aldehydes and Danishefsky's diene (1) has been investigated. A variety of combinations of different ligands and Lewis acids have been examined as catalysts for the hetero-Diels-Alder reaction between benzaldehyde and 1, and it has been found that the readily accessible Ti(IV)-H(8)-BINOL (TiHBOL) complex is a very effective catalyst for the reaction, leading to products with very high enantioselectivity (up to 99% ee) and yield (92%). The hetero-Diels-Alder reaction of other aldehydes with 1 under the catalysis of TiHBOL is a general reaction which proceeds well with very high enantioselectivity and isolated yield for various aldehydes at 0 degrees C to room temperature. Based on the experimental results, the proposed mechanism of the hetero-Diels-Alder reaction and the dihedral angle effects of ligands are discussed. 相似文献
109.
Hamed M. Abu El-Nader 《Transition Metal Chemistry》1995,20(3):316-319
Summary The kinetics of the thermal decomposition of thetris-oxalactocobaltate(III) complex has been investigated in the presence of EtOH and (CH2OH)2 spectrophotometrically in the 50–70 ± 0.1 ° C range. The rate of the reaction decreases upon the addition of either of the alcohols to the reaction medium, whereas the activation energy increases. The thermodynamic parameters were calculated and are discussed in terms of the solvation effects. The influence of the dielectric constants of the solvent mixtures on the rate has been studied. A free radical mechanism is proposed and discussed. 相似文献
110.
Wang B Oleschuk RD Horton JH 《Langmuir : the ACS journal of surfaces and colloids》2005,21(4):1290-1298
Chemical force titrations-measurements of the adhesive interaction between a pair of suitably chemically modified atomic force microscopy (AFM) tip and sample surfaces as a function of pH-have been carried out for various combinations of silanol, amine, carboxylic acid, and sulfonic acid functional groups on both tip and sample. The primary surface material studied was poly(dimethylsiloxane) (PDMS). Surface modification was carried out using a plasma oxidation process to form silanol sites; further modification with amine or sulfonic acid sites was carried out by reaction of the silanol sites with the appropriate trialkoxysilane derivative. AFM tips were also modified using trialkoxysilane compounds. In the cases of tip/sample combinations with the same functional group on each, surface pK(1/2) values could be determined. In several "mixed" tip/sample combinations, a peak appeared in the titration curve midway between the surface pK(1/2) values of the tip and sample, consistent with an ionic H-bonding model for the interactions. The amine/sulfonic acid pair showed more complex behavior; the amine-terminated tip/sulfonic acid-terminated PDMS surface force titration curve consisted of two peaks centered at pH 4 and pH 8. Reversing the tip/sample pair resulted in the peak positions being shifted upward by 1.0 pH unit. The peak appearing at lower pH is assigned to electrostatic interactions between the two oppositely charged surfaces, whereas the higher pH peak is believed to arise due to ionic H-bonding interactions. AFM images show the effects on surface patterning of amine- and sulfonic acid-modified PDMS surfaces that have undergone two different oxidation methods (air plasma oxidation and Tesla coil oxidation). The surface morphologies of freshly prepared and 24 h aged air plasma oxidized PDMS are also discussed in this study. 相似文献