全文获取类型
收费全文 | 1186篇 |
免费 | 124篇 |
国内免费 | 98篇 |
专业分类
化学 | 778篇 |
晶体学 | 22篇 |
力学 | 61篇 |
综合类 | 4篇 |
数学 | 171篇 |
物理学 | 372篇 |
出版年
2023年 | 17篇 |
2022年 | 21篇 |
2021年 | 32篇 |
2020年 | 28篇 |
2019年 | 34篇 |
2018年 | 36篇 |
2017年 | 30篇 |
2016年 | 39篇 |
2015年 | 48篇 |
2014年 | 70篇 |
2013年 | 92篇 |
2012年 | 92篇 |
2011年 | 100篇 |
2010年 | 65篇 |
2009年 | 48篇 |
2008年 | 58篇 |
2007年 | 61篇 |
2006年 | 63篇 |
2005年 | 45篇 |
2004年 | 50篇 |
2003年 | 29篇 |
2002年 | 27篇 |
2001年 | 25篇 |
2000年 | 25篇 |
1999年 | 18篇 |
1998年 | 11篇 |
1997年 | 18篇 |
1996年 | 15篇 |
1995年 | 17篇 |
1994年 | 11篇 |
1993年 | 8篇 |
1992年 | 11篇 |
1991年 | 11篇 |
1990年 | 11篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1987年 | 5篇 |
1986年 | 6篇 |
1985年 | 8篇 |
1984年 | 10篇 |
1982年 | 7篇 |
1981年 | 9篇 |
1980年 | 21篇 |
1979年 | 6篇 |
1977年 | 8篇 |
1976年 | 5篇 |
1974年 | 6篇 |
1973年 | 6篇 |
1972年 | 4篇 |
1969年 | 4篇 |
排序方式: 共有1408条查询结果,搜索用时 31 毫秒
11.
Spectroscopic characterization of effective components anthraquinones in Chinese medicinal herbs binding with serum albumins 总被引:2,自引:0,他引:2
Bi S Song D Kan Y Xu D Tian Y Zhou X Zhang H 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(1-3):203-212
The interactions of serum albumins such as human serum albumin (HSA) and bovine serum albumin (BSA) with emodin, rhein, aloe-emodin and aloin were assessed employing fluorescence quenching and absorption spectroscopic techniques. The results obtained revealed that there are relatively strong binding affinity for the four anthraquinones with HSA and BSA and the binding constants for the interactions of anthraquinones with HSA or BSA at 20 degrees C were obtained. Anthraquinone-albumin interactions were studied at different temperatures and in the presence of some metal ions. And the competition binding of anthraquinones with serum albumins was also discussed. The Stern-Volmer curves suggested that the quenching occurring in the reactions was the static quenching process. The binding distances and transfer efficiencies for each binding reactions were calculated according to the F?ster theory of non-radiation energy transfer. Using thermodynamic equations, the main action forces of these reactions were also obtained. The reasons of the different binding affinities for different anthraquinone-albumin reactions were probed from the point of view of molecular structures. 相似文献
12.
Kai Kang Cheng-you Kan Yi Du De-shan Liu 《高分子科学》2005,(5):479-485
Soap-free poly(methyl methacrylate-ethyl acrylate-methacrylic acid) latex particles with narrow size distribution were synthesized by seeded emulsion polymerization, and the porous particles were created by a stepwise alkali/acid treatment method. Effects of acid treatment conditions on the particle morphology were investigated. Results show that one to three pores were formed inside most of particles after post-treatment. At pH 7.0, when the treatment temperature was lower than 70℃, the size of particles and the volume of pores remained almost unchanged, and these two values increased significantly when the temperature was higher than 70℃. Both the particle size and the pore volume decreased with the increase of initial pH value and treatment time in the acid treatment. As the pH was below 4.0 and the treatment time was longer than 180 min, the particles shrunk in size. 相似文献
13.
Jovi Tze Wai Kan 《Tetrahedron letters》2004,45(33):6357-6359
Poly(ethylene glycol) (PEG) was used for the immobilization of α,α,α-trifluoroacetophenone and the utility of this supported ketone has been examined in dioxirane mediated epoxidation of alkenes. The PEG-ketone reagent was found to be an effective homogeneous catalyst for the epoxidation of a variety of alkenes in the presence of Oxone® and was readily recovered from the reaction mixtures and reused. 相似文献
14.
D.-G. Chen D.-S. Wu H. Zhang Y.-C. Zhang Y.-J. Gong Z.-G. Kan 《Journal of solid state chemistry》2004,177(11):3927-3933
A novel compound Ba2ZnV2O8 has been synthesized in high temperature solution reaction and its crystal structure has been characterized by means of single crystal X-ray diffraction analysis. It crystallizes in monoclinic system and belongs to space group P21/c with a=7.9050(16), b=16.149(3), , β=90.49(3). It builds up from 1-D branchy chains of [ZnV2O84−]∞, and the Ba2+ cations are located in the space among these chains. The IR spectrum, ultraviolet-visible diffuse reflection integral spectrum and fluorescent spectra of this compound have been investigated. The calculated results of energy band structure by the density functional theory method show that the solid-state compound of Ba2ZnV2O8 is an insulator with direct band gap of 3.48 eV. The calculated total and partial density of states indicate that the top valence bands are contributions from the mixings of O-2p, V-3d, and Zn-3d states and low conduction bands mostly originate from unoccupied antibonding states between the V-3d and O-2p states. The V-O bonds are mostly covalence characters and Zn-O bonds are mostly ionic interactions, and the ionic interaction strength is stronger between the Ba-O than between the Zn-O. The refractive index of nx, ny, and nz is estimated to be 1.7453, 1.7469, and 1.7126, respectively, at wavelength of 1060 nm for Ba2ZnV2O8 crystal. 相似文献
15.
Acetophenone photo-sensitized addition of indene to cyclic fluoro-olefins (1,2-dichlorohexafluorocyclopentene-1, 1,2-dichlorotetrafluorocyclobutene-1 and hexafluorocyclobutene) gave the corresponding cycloadducts in satisfactory yields. The cycloadducts obtained predominantly had exo configuration.Some reactions such as reduction, oxidation, dechlorination and halogenation, of the cycloadducts were also studied. 相似文献
16.
Wender PA Baryza JL Bennett CE Bi FC Brenner SE Clarke MO Horan JC Kan C Lacôte E Lippa B Nell PG Turner TM 《Journal of the American Chemical Society》2002,124(46):13648-13649
Macrocycle 1 is a new highly potent analogue of bryostatin 1, a promising anti-cancer agent currently in human clinical trials. In vitro, 1 displays picomolar affinity for PKC and exhibits over 100-fold greater potency than bryostatin 1 when tested against various human cancer cell lines. Macrocycle 1 can be generated in clinically required amounts by chemical synthesis in only 19 steps (LLS) and represents a new clinical lead for the treatment of cancer. 相似文献
17.
18.
Ma C Kwok WM Chan WS Zuo P Wai Kan JT Toy PH Phillips DL 《Journal of the American Chemical Society》2005,127(5):1463-1472
A combined femtosecond Kerr gated time-resolved fluorescence (fs-KTRF) and picosecond Kerr gated time-resolved resonance Raman (ps-KTR(3)) study is reported for two p-hydroxyphenacyl (pHP) caged phototriggers, HPDP and HPA, in neat acetonitrile and water/acetonitrile (1:1 by volume) solvents. Fs-KTRF spectroscopy was employed to characterize the spectral properties and dynamics of the singlet excited states, and the ps-KTR(3) was used to monitor the formation and subsequent reaction of triplet state. These results provide important evidence for elucidation of the initial steps for the pHP deprotection mechanism. An improved fs-KTRF setup was developed to extend its detectable spectral range down to the 270 nm UV region while still covering the visible region up to 600 nm. This combined with the advantage of KTRF in directly monitoring the temporal evolution of the overall fluorescence profile enables the first time-resolved observation of dual fluorescence for pHP phototriggers upon 267 nm excitation. The two emitting components were assigned to originate from the (1)pipi (S(3)) and (1)npi (S(1)) states, respectively. This was based on the lifetime, the spectral location, and how these varied with the type of solvent. By correlating the dynamics of the singlet decay with the triplet formation, a direct (1)npi --> (3)pipi ISC mechanism was found for these compounds with the ISC rate estimated to be approximately 5 x 10(11) s(-)(1) in both solvent systems. These photophysical processes were found to be little affected by the kind of leaving group indicating the common local pHP chromophore is largely responsible for the fluorescence and relevant deactivation processes. The triplet lifetime was found to be approximately 420 and 2130 ps for HPDP and HPA, respectively, in the mixed solvent compared to 150 and 137 ns, respectively, in neat MeCN. The solvent and leaving group dependent quenching of the triplet is believed to be associated with the pHP deprotection photochemistry and indicates that the triplet is the reactive precursor for pHP photorelease reactions for the compounds examined in this study. 相似文献
19.
The activation energy of the enzyme-catalyzed reaction for uric acid decreases markedly in the presence of o-phenanthroline, which activates the bioelectrochemicla activity of the polypyrrole uricase electrode. The response current of the enzyme electrodeis independent of the concentration of o-phenanthroline. Based on the experimental results, the mechamsm of the enzyme-catalyzed reaction for uric acid in the presence of o-phenanthroline is presented as follows: E+A→EA, EA+S EAS, EAS→EA+P, where E, A, S and P are the enzyme, activator, substrate and product, respectively. The effects of pH value, potential and the uric acid concentration on the response currents of the uricase electrode have been studied in the presence of o-phenanthroline. In the presence of o-phenanthroline, the response current of the enzyme electrode increase linearly with increasing concentration of uric acid in the region of 0.07 to 0.67 mmol·L~(-1), therefore the polypyrrole uricase electrode which has once lost its activity can be activated and used again to determine the substrate concentration. 相似文献
20.
Reliability bounds in DFRA class with known mean and variance 总被引:1,自引:0,他引:1
RELIABILITYBOUNDSINDFRACLASSWITHKNOWNMEAN AND VARIANCECHENGKAN(程侃)(InstituteofAppliedMathematics,theChineseAcademyofScience,B... 相似文献