全文获取类型
收费全文 | 1197篇 |
免费 | 74篇 |
国内免费 | 3篇 |
专业分类
化学 | 978篇 |
晶体学 | 15篇 |
力学 | 16篇 |
数学 | 70篇 |
物理学 | 195篇 |
出版年
2023年 | 11篇 |
2022年 | 10篇 |
2021年 | 7篇 |
2020年 | 21篇 |
2019年 | 24篇 |
2018年 | 16篇 |
2017年 | 9篇 |
2016年 | 43篇 |
2015年 | 28篇 |
2014年 | 40篇 |
2013年 | 62篇 |
2012年 | 81篇 |
2011年 | 120篇 |
2010年 | 48篇 |
2009年 | 43篇 |
2008年 | 101篇 |
2007年 | 66篇 |
2006年 | 80篇 |
2005年 | 79篇 |
2004年 | 72篇 |
2003年 | 63篇 |
2002年 | 49篇 |
2001年 | 14篇 |
2000年 | 11篇 |
1999年 | 12篇 |
1998年 | 9篇 |
1997年 | 11篇 |
1996年 | 9篇 |
1995年 | 8篇 |
1994年 | 14篇 |
1992年 | 7篇 |
1991年 | 8篇 |
1990年 | 6篇 |
1989年 | 7篇 |
1988年 | 6篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 7篇 |
1983年 | 8篇 |
1982年 | 4篇 |
1981年 | 8篇 |
1980年 | 3篇 |
1979年 | 8篇 |
1978年 | 7篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1971年 | 3篇 |
1968年 | 2篇 |
1967年 | 2篇 |
排序方式: 共有1274条查询结果,搜索用时 31 毫秒
21.
Mechanism of gold adsorption by persimmon tannin gel. 总被引:1,自引:0,他引:1
Gold adsorption by persimmon tannin (PT) gel from a solution containing hydrogen tetrachloroaurate(III) was examined. A flow-rate examination in a column system indicated the reduction of Au(III) ion to Au(0). XRD patterns clarified the existence of Au(0) on the gel which adsorbed gold. The gel could also adsorb colloidal Au(0) prepared independently. A model consisting of ligand exchange, Au(III) reduction to Au(0), and resulting Au(0) adsorption by PT gel was presented for the gold adsorption mechanism. 相似文献
22.
Ishikawa A Takata T Kondo JN Hara M Kobayashi H Domen K 《Journal of the American Chemical Society》2002,124(45):13547-13553
A Ti-based oxysulfide, Sm(2)Ti(2)S(2)O(5), was studied as a visible light-driven photocatalyst. Under visible light (440 nm < or = lambda < or = 650 nm) irradiation, Sm(2)Ti(2)S(2)O(5) with a band gap of approximately 2 eV evolved H(2) or O(2) from aqueous solutions containing a sacrificial electron donor (Na(2)S-Na(2)SO(3) or methanol) or acceptor (Ag(+)) without any noticeable degradation. This oxysulfide is, therefore, a stable photocatalyst with strong reduction and oxidation abilities under visible-light irradiation. The electronic band structure of Sm(2)Ti(2)S(2)O(5) was calculated using the plane-wave-based density functional theory (DFT) program. It was elucidated that the S3p orbitals constitute the upper part of the valence band and these orbitals make an essential contribution to the small band gap energy. The conduction and valence bands' positions of Sm(2)Ti(2)S(2)O(5) were also determined by electrochemical measurements. It indicated that conduction and valence bands were found to have satisfactory potentials for the reduction of H(+) to H(2) and the oxidation of H(2)O to O(2) at pH = 8. This is consistent with the results of the photocatalytic reactions. 相似文献
23.
G. F. Goya R. C. Mercader M. B. Vassallo I. L. Botto R. Sáez Puche 《Hyperfine Interactions》1994,83(1):199-201
The oxidic phase FeMoVO7 of the Fe2O3-V2O5-MoO3 system has been synthesized. Susceptibility measurements from 4.2 K to room temperature display an antiferromagnetic behaviour with an effective magnetic moment of 5.80
b
. This value, and the measured Mössbauer isomer shift of 0.40±0.02 mm/s, are characteristic of high-spin Fe(III). The lowT
n
value of 15 K suggests a weak interaction among the Fe-O polyhedra. The relative small QS=0.28±0.02 mm/s found in this compound shows that the Fe-O polyhedra symmetry is close to octahedral and almost undistorted. 相似文献
24.
A bioassay-directed fractionation of the cytotoxic constituents of the Japanese sea hare Dolabella auricularia resulted in the isolation of two 35-membered depsipeptides dolastatin G (1) and nordolastatin G (2), which showed cytotoxicity against HeLa S(3) cells with IC(50) values of 1.0 and 5.3 &mgr;g/mL, respectively. The gross structures of these substances were established by spectroscopic analysis including 2D NMR techniques. The absolute stereostructure of 1 was determined by chiral HPLC analysis of amino acid components obtained from acid hydrolysis of 1 and by the enantioselective syntheses of two degradation products arising from polyketide portions. Nordolastatin G (2) is a congener that has the same absolute stereochemistry as that of 1. 相似文献
25.
Miura T Goto K Waragai H Matsumoto H Hirose Y Ohmae M Ishida HK Satoh A Inazu T 《The Journal of organic chemistry》2004,69(16):5348-5353
The Bfp-OH, a novel fluorous protecting reagent, was able to be easily prepared. The Bfp group was readily introduced to a carbohydrate, removed in high yield, and recyclable after cleavage. The use of the Bfp group made it possible to synthesize a pentasaccharide by minimal column chromatography purification. Each synthetic intermediate was able to be easily purified only by simple fluorous-organic solvent extraction and monitored by TLC, NMR, and MS. 相似文献
26.
Rapid synthesis of oligosaccharide moieties of globotriaosylceramide using fluorous protective group
Tsuyoshi MiuraToshiyuki Inazu 《Tetrahedron letters》2003,44(9):1819-1821
The use of the Bfp (bisfluorous chain type propanoyl) group as a fluorous protective group made it possible to rapidly synthesize galabiose and the Gb3 oligosaccharide derivatives by a simple fluorous-organic extraction purification. The fluorous oligosaccharide synthesis using the Bfp group is an excellent strategic alternative to solid phase oligosaccharide synthesis, and removes some of the disadvantages of the solid phase method. 相似文献
27.
Pilar Goya Juan Antonio Paez Wolfgang Pfleiderer 《Journal of heterocyclic chemistry》1984,21(3):861-864
Several pyrazino[2,3-c][1,2,6]thiadiazine 2,2-dioxide derivatives have been synthesized for the first time by condensation of suitable 4,5-diamino-1,2,6-thiadiazine 1,1-dioxides and symmetrical 1,2-dicarbonyl compounds. Structures of these compounds have been characterized by their elementary analyses, 1H-nmr and uv spectra as well as their pKa values. The most striking differences between this series and the corresponding pteridines are discussed. 相似文献
28.
Treatment of magnesium alkylidene carbenoids, generated from 1-chlorovinyl p-tolyl sulfoxides with isopropylmagnesium chloride at −78 °C in toluene, with 2-lithiothiophenes gave 2-alkenylated thiophenes in good to high yields. The intermediate of this reaction was found to be an alkenylmagnesium, which could be trapped with iodoalkanes and ethyl chloroformate. This procedure offers a novel and efficient one-pot synthesis of thiophenes having a disubstituted or a trisubstituted olefin at the 2-position from thiophenes in good yields. 相似文献
29.
Masao Matsuoka Tsuyoshi Matsuda June Tamaki Yoshifumi Yamamoto Chiaki Iwakura 《Research on Chemical Intermediates》2006,32(5):389-402
Laves-phase hydrogen storage alloy has a high potential for use as negative electrode material as alternative for the misch-metal-based
material. In order to improve the energy density and the rate capability of negative electrode, chemical and mechanical modification
of Lavesphase alloy with different stoichiometric ratios was carried out. Discharge capacity and high-rate dischargeabilty
was evaluated by electrochemical methods and the characterization of Laves-phase alloy was made by X-ray diffraction, SEM
observation and PCT measurement. The best result in discharge capacity could be obtained for stoichiometric Laves-phase alloy
with a composition of Zr0.9Ti0.1Ni1.1Co0.1Mn0.5V0.2Cr0.1 by boiling in 10 M KOH solution. On the other hand, the high-rate dischargeability was increased remarkably by introducing
mechanical grinding before alkali treatment. The cause for improved performance was discussed on the basis of thermodynamic
stability of metal hydride and changes in crystal structure and surface morphology influencing on diffusion coefficient and
diffusion path length of hydrogen. 相似文献
30.
Yan H Sato T Komago D Yamaguchi A Oyaizu K Yuasa M Otake K 《Langmuir : the ACS journal of surfaces and colloids》2005,21(26):12303-12308
A conductive polypyrrole (PPy) film was successfully synthesized in a homogeneous supercritical carbon dioxide (scCO2)/acetonitrile (AN) system. The occurrence of a homogeneous supercritical state was confirmed by observations of the phase behavior of the system through a high-pressure cell with a viewing window. The concentration of a supporting electrolyte, tetrabutylammonium hexafluorophosphate (TBAPF6), significantly changed the phase behavior of the scCO2/AN system. The polymerization rate of the film in that system decreased with further addition of CO2. This result suggested that the low viscosity of scCO2 did not play an important role in improving the growth rate of the PPy film. The low polymerization rate might have been due to the electron-transfer resistance arising from the low dielectric constant of scCO2/AN mixture. The roughness of the film prepared in the homogeneous scCO2/AN system was 1/10 that synthesized in AN itself as a solvent. The slow growth of film and the high diffusion rate of the monomer seemed to account for the smooth flat film formation. 相似文献