全文获取类型
收费全文 | 27948篇 |
免费 | 1098篇 |
国内免费 | 265篇 |
专业分类
化学 | 18882篇 |
晶体学 | 269篇 |
力学 | 951篇 |
综合类 | 8篇 |
数学 | 2460篇 |
物理学 | 6741篇 |
出版年
2023年 | 149篇 |
2022年 | 313篇 |
2021年 | 503篇 |
2020年 | 469篇 |
2019年 | 478篇 |
2018年 | 355篇 |
2017年 | 340篇 |
2016年 | 771篇 |
2015年 | 669篇 |
2014年 | 841篇 |
2013年 | 1553篇 |
2012年 | 2017篇 |
2011年 | 2194篇 |
2010年 | 1344篇 |
2009年 | 1195篇 |
2008年 | 1794篇 |
2007年 | 1696篇 |
2006年 | 1598篇 |
2005年 | 1509篇 |
2004年 | 1331篇 |
2003年 | 1041篇 |
2002年 | 998篇 |
2001年 | 705篇 |
2000年 | 596篇 |
1999年 | 355篇 |
1998年 | 263篇 |
1997年 | 306篇 |
1996年 | 356篇 |
1995年 | 275篇 |
1994年 | 286篇 |
1993年 | 287篇 |
1992年 | 278篇 |
1991年 | 220篇 |
1990年 | 165篇 |
1989年 | 142篇 |
1988年 | 149篇 |
1987年 | 120篇 |
1986年 | 98篇 |
1985年 | 173篇 |
1984年 | 121篇 |
1983年 | 100篇 |
1982年 | 125篇 |
1981年 | 90篇 |
1980年 | 81篇 |
1978年 | 82篇 |
1977年 | 88篇 |
1976年 | 94篇 |
1975年 | 104篇 |
1974年 | 81篇 |
1973年 | 103篇 |
排序方式: 共有10000条查询结果,搜索用时 187 毫秒
801.
Determination of pesticides in soil by liquid-phase microextraction and gas chromatography-mass spectrometry 总被引:4,自引:0,他引:4
Trace amounts of pesticides in soil were determined by liquid-phase microextraction (LPME) coupled to gas chromatography-mass spectrometry (GC-MS). The technique involved the use of a small amount (3 microl) of organic solvent impregnated in a hollow fiber membrane, which was attached to the needle of a conventional GC syringe. The organic solvent was repeatedly discharged into and withdrawn from the porous polypropylene hollow fiber by a syringe pump, with the pesticides being extracted from a 4 ml aqueous soil sample into the organic solvent within the hollow fiber. Aspects of the developed procedure such as organic solvent selection, extraction time, movement pattern of plunger, concentrations of humic acid and salt, and the proportion of organic solvent in the soil sample, were optimized. Limits of detection (LOD) were between 0.05 and 0.1 microg/g with GC-MS analysis under selected-ion monitoring (SIM). Also, this method provided good precision ranging from 6 to 13%; the relative standard deviations were lower than 10% for most target pesticides (at spiked levels of 0.5 microg/g in aqueous soil sample). Finally, the results were compared to those achieved using solid-phase microextraction (SPME). The results demonstrated that LPME was a fast (within 4 min) and accurate method to determine trace amounts of pesticides in soil. 相似文献
802.
The reaction of prop‐1‐ene‐1,3‐sultone 1 with a variety of nitrile oxides 3 afforded novel [3+2] cycloaddition products 4 in good yield. The cycloaddition reaction achieved excellent regioselectivity. 相似文献
803.
A microdialysis junction is employed as the interface for on-line coupling of capillary isoelectric focusing with transient isotachophoresis-zone electrophoresis in a two-dimensional separation system. Capillary isoelectric focusing not only provides high-resolution separation of tryptic peptides based on their differences in isoelectric point, but also potentially allows the analysis of low-abundance proteins with a typical concentration factor of 50-100 times. Carrier ampholytes, employed for the creation of a pH gradient during focusing, are further utilized as the leading electrolyte in the second separation dimension, transient isotachophoresis-zone electrophoresis. Many peptides which have the same isoelectric point would most likely have different charge-to-mass ratios, and thus different electrophoretic mobilities in zone electrophoresis. Two-dimensional separation of proteolytic peptides is demonstrated using standard proteins, including cytochrome c, ribonuclease A, and carbonic anhydrase II. The maximum peak capacity is estimated to be around approximately 1600 and can be significantly increased by simply increasing the capillary column length and manipulating the range of pH gradient in isoelectric focusing. In addition to enhanced separation efficiency and resolution, this two-dimensional electrokinetic separation system permits sensitive and comprehensive analysis of peptide fragments, especially when integrated with electrospray ionization mass spectrometry for peptide/protein identification. 相似文献
804.
A highly sensitive and specific enzyme-linked immunosorbent assay (ELISA) method has been developed for the determination of 20(S)-protopanaxatriol (PPT), one of the major aglycones of dammarane-type ginseng saponins. Polyclonal antibodies raised against ginsenoside F1 (GF1)-bovine serum albumin showed high reactivities to PPT and GF1, whereas they exhibited minor or even no cross-reactivities to other ginsenosides and protopanaxadiol (0.19%). The working range of this method extends from 50 pg ml−1 to 20 ng ml−1 of PPT. The assay reported here has been validated against an HPLC technique using PPT-containing samples and was shown to correlate closely (γ=0.993). This ELISA could be a useful tool for the determination of PPT contained in biological fluids and plant materials. 相似文献
805.
Chen CH Hwang BJ Wang GR Sarma LS Tang MT Liu DG Lee JF 《The journal of physical chemistry. B》2005,109(46):21566-21575
We report in situ X-ray absorption spectroscopy (XAS) investigations on the formation of palladium-platinum (Pd/Pt) bimetallic clusters at the early stage within the water-in-oil microemulsion system of water/AOT/n-heptane. The reduction of palladium and platinum ions and the formation of corresponding clusters are monitored as a function of dosage of reducing agent, hydrazine (N(2)H(5)OH). Upon successive addition of the reducing agent, hydrazine (N(2)H(5)OH), five distinguishable steps are observed in the formation process of Pd/Pt clusters at the early stage. Both in situ X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analysis for both the Pd K-edge and Pt L(III)-edge revealed the formation of Pd/Pt bimetallic clusters. A corresponding structural model is proposed for each step to provide a detailed insight into the nucleation and growth mechanism of Pd/Pt bimetallic clusters. We also discussed the atomic distribution of Pd and Pt atoms in Pd/Pt bimetallic clusters based on the calculated XAS structural parameters. 相似文献
806.
Joonho Lee Wataru Shimoda Toshihiro Tanaka 《Monatshefte für Chemie / Chemical Monthly》2005,40(10):1829-1834
Temperature dependence of the surface tension of liquid Sn–Ag and Sn–Cu base lead-free solder alloys and oxygen partial pressure
dependence of liquid Sn–Ag alloy were evaluated using the experimental data obtained, respectively, by the constrained drop
method and the sessile drop method in the previous studies [1, 2]. The temperature dependences of the surface tension have
maximum positive values when the mol fraction of Ag and Cu is about 0.7, while those for pure liquid Sn, Ag, and Cu have negative
values. The calculated values based on Butler’s equations were found to be in reasonable agreement with those of the experimental data. The oxygen partial pressure dependences
of the surface tension of liquid Sn–Ag alloys at 1253 K have a minimum value when the mol fraction of Ag is about 0.9 and
the oxygen partial pressure is less than about 10−13 atm. From this, it is considered that the oxygen adsorption increased by adding Ag to Sn when the mol fraction of Ag is less
than 0.9. 相似文献
807.
Strong pulse sequences can be used to control the position and width of the molecular wave packet. In this paper we propose a new scheme to maximally compress the wave packet in a quasistatic way by freezing it at a peculiar adiabatic potential shaped by two laser pulses. The dynamic principles of the scheme and the characteristic effect of the different control parameters are presented and analyzed. We use two different molecular models, electronic potentials modeled by harmonic oscillators, with the same force constants, and the Na(2) dimer, to show the typical yield that can be obtained in compressing the initial (minimum width) molecular wave function. 相似文献
808.
Won Young Jung Seung Hee Baek Seong Soo Park Gun-Dae Lee Euh Duck Jeong Hyun Gyu Kim Seong-Soo Hong 《Reaction Kinetics and Catalysis Letters》2007,91(2):233-240
The nanosized titania and TiO2/SiO2 particles were prepared by the microwave-hydrothermal method. The effect of physical properties TTIP/TEOS ratio and calcination
temperature has been investigated. The major phase of the pure TiO2 particle is of the anatase structure, and a rutile peak was observed above 800°C. In TiO2/SiO2 particles, however, no significant rutile phase was observed, although the calcination temperature was 900°C. No peaks for
the silica crystal phase were observed at either silica/titania ratio. The crystallite size of TiO2/SiO2 particles decreases as compared to pure TiO2 at high calcination temperatures. The TiO2/SiO2 particles show higher activity on the photocatalytic decomposition of orange II as compared to pure TiO2 particles. 相似文献
809.
New (diamine)platinum(II) complexes A(2)PtX(2) (A(2) = trans-(+/-)-1,2-diaminocyclohexane (DACH), tetrahydro-4H-pyran-4,4-diylbis(methylamine)(THPDMA); X(2) = 9-fluorenylidenemalonate(FM), benzhydrylidenemalonate(BHM)) have been synthesized and characterized by means of multinuclear NMR spectroscopy and X-ray analysis. (DACH)Pt(FM) crystallizes in space group P2(1)/c with eight formula units in a cell of dimensions a = 20.071(7) ?, b = 12.717(3) ?, c = 24.512(6) ?, beta = 103.25(2) degrees, and V = 6090(3) ?.(3) (DACH)Pt(BHM) crystallizes in space group P&onemacr; with four molecular units in a cell of dimensions a = 11.048(3) ?, b = 13.639(3) ?, c = 14.043(6) ?, alpha = 90.17(3) degrees, beta = 91.31(4) degrees, gamma = 89.98(3) degrees, and V = 2116(1) ?(3). The platinum atom in both complexes adopts a typical square planar arrangement with two nitrogen atoms in cis position. The 9-fluorenylidene and benzhydrylidene groups of the amine ligands chelated to platinum are strikingly bent up by 88.8(3) and 80.8(2) degrees, respectively, from the platinum square plane in the solid state. Variable temperature (1)H NMR spectra of the title complexes in dimethyl sulfoxide solution reveals that the amine proton resonances are sensitive to the fluxional motion of the remote arylidene groups, and suggests that interconversion occurs between two "bent-up" and "bent-down" forms. The prominent difference between the FM and BHM complexes is observed in solution, due to the presence or absence of the angle constraint of the anionic coligands. 相似文献
810.
Hirotaka Kudo Marvin L. Tedjamulia Raymond N. Castle Milton L. Lee 《Journal of heterocyclic chemistry》1984,21(1):185-192
We describe the synthesis of thieno[2,3-c]dibenzothiophene ( 6 ), thieno[3,2-c]dibenzothiophene ( 10 ), thieno-[3,2-a]dibenzothiophene ( 14 ), thieno[2,3-a]dibenzothiophene ( 16 ), benzo[1,2-b:4,3-b]bisbenzo[b]thiophene ( 18 ), benzo[1,2--6:3,4-b]bisbenzo[b]thiophene ( 20 ), benzo[2,1--6:3,4-b]bisbenzo[b]thiophene ( 22 ), benzo[1,2-b:3,4-g]bisbenzo[b]thiophene ( 27 ), benzo[1,2-b:4,3-e]bisbenzo[b]thiophene ( 29 ), benzo[2,1--6:3,4-g]bisbenzo[b]thiophene ( 36 ), benzo[2,1--6:4,3-e]bisbenzo[b]thiophene ( 38 ), benzo[1,2--6:4,3-g]bisbenzo[b]thiophene ( 41 ), benzo[1,2-b:4,5-g]bisbenzo[b]thiophene ( 42 ), benzo[1,2-b:3,4-e]bisbenzo[b]thiophene ( 44 ) and benzo-[1,2-b:5,4-e]bisbenzo[b]thiophene ( 45 ). 相似文献