全文获取类型
收费全文 | 8016篇 |
免费 | 835篇 |
国内免费 | 548篇 |
专业分类
化学 | 5663篇 |
晶体学 | 97篇 |
力学 | 422篇 |
综合类 | 46篇 |
数学 | 696篇 |
物理学 | 2475篇 |
出版年
2024年 | 18篇 |
2023年 | 123篇 |
2022年 | 227篇 |
2021年 | 304篇 |
2020年 | 276篇 |
2019年 | 271篇 |
2018年 | 208篇 |
2017年 | 213篇 |
2016年 | 315篇 |
2015年 | 289篇 |
2014年 | 371篇 |
2013年 | 567篇 |
2012年 | 703篇 |
2011年 | 701篇 |
2010年 | 492篇 |
2009年 | 435篇 |
2008年 | 549篇 |
2007年 | 465篇 |
2006年 | 441篇 |
2005年 | 385篇 |
2004年 | 324篇 |
2003年 | 266篇 |
2002年 | 265篇 |
2001年 | 171篇 |
2000年 | 130篇 |
1999年 | 123篇 |
1998年 | 107篇 |
1997年 | 83篇 |
1996年 | 91篇 |
1995年 | 77篇 |
1994年 | 50篇 |
1993年 | 55篇 |
1992年 | 50篇 |
1991年 | 53篇 |
1990年 | 27篇 |
1989年 | 25篇 |
1988年 | 23篇 |
1987年 | 20篇 |
1986年 | 16篇 |
1985年 | 16篇 |
1984年 | 13篇 |
1983年 | 10篇 |
1982年 | 11篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1977年 | 3篇 |
1973年 | 4篇 |
1971年 | 6篇 |
1970年 | 6篇 |
排序方式: 共有9399条查询结果,搜索用时 0 毫秒
71.
Two new three-dimensional oxychlorides are reported, Te(4)M(3)O(15).Cl (M = Nb(5+) or Ta(5+)). The isostructural materials were synthesized by chemical transport reactions utilizing TeO(2), M(2)O(5), and MCl(5) (M = Nb(5+) or Ta(5+)) as reagents. The compounds exhibit a three-dimensional cationic tunnel framework, with Cl(-) anions occupying the tunnels. Crystal data: monoclinic, space group C2/c, a = 18.9944(7) A, b = 7.8314(3) A, c = 21.1658(8) A, beta = 116.6400(10) degrees, Z = 8 (T = 295 K). 相似文献
72.
Yu Liu Yong Chen Shi-Zhao Kang Li Li Chun-Hua Diao Heng-Yi Zhang 《Journal of inclusion phenomena and macrocyclic chemistry》2003,47(1-2):91-95
Two novel benzo-15-crown-5 tethered β-cyclodextrins 1 and 2have been synthesized by coupling substituted benzo-15-crown-5 with correspondingβ-cyclodextrin derivatives. Their inclusion complexation behavior withrepresentative guests, such as cyclohexanol, cyclohexane carboxylic acid, cyclohexaneacetic acid, sodium cyclohexane carboxylate, and potassium cyclohexane carboxylate,was investigated in aqueous solution by means of fluorescence spectrometry. As compared with parent β-cyclodextrin, benzo-15-crown-5 tethered β-cyclodextrins 1–2 display significantly enhanced molecular binding abilities and selectivities towards model substrates, especially towards substrates containing alkali-metal cations. These results indicate that, bearing two recognition sites in a single molecule, these supramolecular architectures can strongly enhance the molecular binding ability of parent β-cyclodextrin by the cooperative binding of the β-cyclodextrin cavity and the crown ether moiety. Possessing a shorter linker, crown ether-β-cyclodextrin 2 shows much higher binding affinity with guest molecules than crown ether-β-cyclodextrin 1, which may be attributed to the binding size and molecular multiple recognition behavior between host and guest. 相似文献
73.
Jeong Hyun Kim Seung-Hyun Kang Il Nam Jung Kwan Mook Kim Bok Ryul Yoo Myong Euy Lee 《Journal of Sol-Gel Science and Technology》2004,32(1-3):31-35
Reaction of (triphenylmethyl)silanetriol (1) with cyclopentadienyltitanium trichloride (CpTiCl3) in the presence of triethylamine as a HCl scavenger gave both compounds of a partial open-cage type {[Ph3CSiO(OH)]3(Ph3CSiO3/2)(CpTiO3/2)4} (2) and cube type (Ph3CSiO3/2CpTiO3/2)4 (3). The 1:1 reaction of 1 and CpTiCl3 in toluene solvent at reflux temperature for 3 d afforded compounds 2 (22%) and 3 (36%). When 1 is reacted with a 1.5 fold excess of CpTiCl3 under the same conditions, compound 3 was obtained in high yield (81%) along with 2 in trace quantities. Compounds 2 and 3 were fully characterized by the analyses of 1H, 13C, 29Si NMR, IR, and FAB MS data. The solid-state structure of 3 was determined by a single crystal X-ray diffraction study. Compound 3 had shown to have catalytic activity for the oxidation of alkenes such as 1-octene, cyclooctene, and norbornene with t-butyl hydrogen peroxide. The effect of solvent was observed in this epoxidation reaction. The order of reactivity were decreased as follows: CHCl3 > hexane THF. 相似文献
74.
75.
The anodic reaction of Ni in an alkaline solution was studied by the tip–substrate voltammetry mode of scanning electrochemical microscopy (SECM) and cyclic voltammetry (CV). A platinum microdisc electrode was selected as the tip electrode, which functioned as a pH sensor with transient response capability. The pH value of the solution near the Ni electrode surface varied while the Ni substrate oxidation reaction occurred, and the pH variation could be detected by the tip faradic current. The cyclic voltammogram results showed that two types of hydroxides: i.e. α‐Ni(OH)2 and β‐Ni(OH)2 were formed during Ni oxidation in the lower potential region. In the proceedings of α‐Ni(OH)2 → γ‐NiOOH and β‐Ni(OH)2 → β‐NiOOH, the process of OH? concentration decrease in the solution was ahead and behind of electron transfer in the solid phase, respectively. These results indicate that the OH? adsorption process occurs as an elementary step in the former reaction and the H+ diffusion process from the inner to the outer layer of the solid phase occurs as a subsequent step in the latter reaction. The results also revealed that the oxide film on the Ni surface has a two‐layer structure. The real potential of the oxygen evolution reaction (OER) on the Ni surface with different cycles is also analyzed in the paper. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
76.
H. Moon S. W. Kim J. Lee S. K. Rhee E. S. Choi H. A. Kang I. H. Kim S. I. Hong 《Applied biochemistry and biotechnology》2003,111(2):65-79
As a novel feeding strategy for aptomizing human epidermal growth factor (hEGF) production with a recombinant Hansenula polymorpha DL-1 using the methanol oxidase (MOX) promoter in H. polymorpha DL-1, independent exponential feeding of two substrates was used. A simple kinetic model considering the cell growth on two
substrates was established and used to calculate the respective feeding rates of glycerol and methanol. In the fedbatch culture
with methanol-only feeding, the optimal set point of specific growth rate on methanol was found to be 0.10 h−1. When the fed-batch cultures were conducted by the independent feeding of glycerol and methanol, the actual specific growth
rate on glycerol and methanol was slightly lower than the set point of specific growth rate. By the uncoupled feeding of glycerol
and methanol the volumetric productivity of hEGF increased from 6.4 to 8.0 mg/(L·h), compared with methanol-only feeding. 相似文献
77.
Kang De Yao Tao Peng Han Bao Feng Yu Ying He 《Journal of polymer science. Part A, Polymer chemistry》1994,32(7):1213-1223
The aqueous swelling kinetics of a series of crosslinked chitosan (cr-CS) with glutaraldehyde (GA) interpenetrating polyether hydrogels have been studied as functions of pH, the N-deacetylation degree of chitosan, the amount of crosslinking agent, the electrolyte composition in solution, temperature, and gel composition. Based on these results, the swelling mechanism of the hydrogels was discussed. The release profiles of chlorhexidini acetas from the semi-IPN were also investigated. © 1994 John Wiley & Sons, Inc. 相似文献
78.
Sungzong Kang 《Journal of Molecular Structure》1973,17(1):127-142
The energy calculations using the INDO molecular orbital method and classical potential function show that the syn conformation of pyrimidine nucleosides having the C(2')-endo or C(2')-endo-C(3')-endo sugar ring puckering is as stable as the corresponding anti form.The O(2')-O(2') base-ribose hydrogen bonding significantly alters the ΦCN conformation by confining the allowed ΦCN ranges to about 150–210°. 相似文献
79.
Surface composition and property of film prepared with aqueous dispersion of polyurethaneurea-acrylate including fluorinated block copolymer 总被引:1,自引:0,他引:1
The aqueous dispersion of polyurethaneurea-acrylate (PUA) including small amount of fluorinated block copolymers containing carboxyl groups (PATF), which can be dissolved in water, was used to make films and the surface properties of these films were examined. The experimental data show that the modified PUA film exhibits a hydrophobic surface property, although the original surface of PUA film is hydrophilic. The surface composition of the modified PUA film was measured by ATR and XPS. The results indicate that there is a concentration gradient of the fluorine groups along the lines of thickness of the modified film and towards the outmost surface layer, resulting from the migration of fluorinated blocks to the air side surface of the modified PUA film during the film formation process. However, the PUA film can not be modified effectively by adding the sodium salt of PATF, since the urethane groups in the system are easy to occupy on the surface of the film. 相似文献
80.
Oxygen is electroreduced to water on a carbon cathode coated with wired bilirubin oxidase in a pH 7.4 0.15 M NaCl phosphate buffer solution at 37 °C at much lesser polarization than it is on a pure platinum cathode in 0.5 M H2SO4. While the wired bilirubin oxidase cathode operates for over a week in the aerated or oxygenated buffer solution, it is degraded rapidly when in serum. We reported earlier that in the presence of O2 an intermediate product of the electrooxidation of urate, which is a normal serum component, irreversibly damages the wired bilirubin oxidase and also reported that the electrocatalyst is irreversibly damaged, in the absence of urate, when it is brought, by disconnecting the electrode, to the O2/H2O half cell potential at pH 7.4. Here we report that a) dissolved bilirubin oxidase is irreversibly and rapidly damaged by urate in the presence of O2; and b) that the immobilized wired bilirubin oxidase electrocatalyst is not only irreversibly deactivated by urate in the presence of O2 in a few hours, but is initially reversibly deactivated, in 1 min or less, by the urate in the presence of O2. 相似文献