全文获取类型
收费全文 | 5011篇 |
免费 | 695篇 |
国内免费 | 725篇 |
专业分类
化学 | 3765篇 |
晶体学 | 45篇 |
力学 | 410篇 |
综合类 | 34篇 |
数学 | 512篇 |
物理学 | 1665篇 |
出版年
2024年 | 14篇 |
2023年 | 91篇 |
2022年 | 176篇 |
2021年 | 205篇 |
2020年 | 203篇 |
2019年 | 196篇 |
2018年 | 158篇 |
2017年 | 167篇 |
2016年 | 201篇 |
2015年 | 207篇 |
2014年 | 236篇 |
2013年 | 353篇 |
2012年 | 410篇 |
2011年 | 433篇 |
2010年 | 295篇 |
2009年 | 259篇 |
2008年 | 313篇 |
2007年 | 247篇 |
2006年 | 257篇 |
2005年 | 239篇 |
2004年 | 180篇 |
2003年 | 179篇 |
2002年 | 170篇 |
2001年 | 141篇 |
2000年 | 127篇 |
1999年 | 140篇 |
1998年 | 97篇 |
1997年 | 90篇 |
1996年 | 92篇 |
1995年 | 74篇 |
1994年 | 52篇 |
1993年 | 67篇 |
1992年 | 48篇 |
1991年 | 50篇 |
1990年 | 41篇 |
1989年 | 36篇 |
1988年 | 25篇 |
1987年 | 20篇 |
1986年 | 19篇 |
1985年 | 20篇 |
1984年 | 13篇 |
1983年 | 13篇 |
1982年 | 12篇 |
1981年 | 9篇 |
1980年 | 7篇 |
1976年 | 8篇 |
1975年 | 6篇 |
1973年 | 7篇 |
1972年 | 5篇 |
1970年 | 4篇 |
排序方式: 共有6431条查询结果,搜索用时 15 毫秒
101.
[reaction: see text] Effective epoxidation of lipophilic alkenes using hydrogen peroxide was accomplished with the manganese sulfate/bicarbonate catalytic system in an ionic liquid at room temperature. 相似文献
102.
An efficient approach is described for using accurate ab initio calculations to determine the rates of elementary condensation and evaporation processes that lead to nucleation of aqueous aerosols. The feasibility of the method is demonstrated in an application to evaporation rates of water dimer at 230 K. The method, known as ABC-FEP (ab initio/classical free energy perturbation), begins with a calculation of the potential of mean force for the dissociation (evaporation) of small water clusters using a molecular dynamics (MD) simulation with a model potential. The free energy perturbation is used to calculate how changing from the model potential to a potential calculated from ab initio methods would alter the potential of mean force. The difference in free energy is the Boltzmann-weighted average of the difference between the ab initio and classical potential energies, with the average taken over a sample of configurations from the MD simulation. In principle, the method does not require a highly accurate model potential, though more accurate potentials require fewer configurations to achieve a small sampling error in the free energy perturbation step. To test the feasibility of obtaining accurate potentials of mean force from ab initio calculations at a modest number of configurations, the free energy perturbation method has been used to correct the errors when some standard models for bulk water (SPC, TIP4P, and TIP4PFQ) are applied to water dimer. To allow a thorough exploration of sampling issues, a highly accurate fit to results of accurate ab initio calculations, known as SAPT-5s, as been used a proxy for the ab initio calculations. It is shown that accurate values for a point on the potential of mean force can be obtained from any of the water models using ab initio calculations at only 50 configurations. Thus, this method allows accurate simulations of small clusters without the need to develop water models specifically for clusters. 相似文献
103.
Blum AS Ren T Parish DA Trammell SA Moore MH Kushmerick JG Xu GL Deschamps JR Pollack SK Shashidhar R 《Journal of the American Chemical Society》2005,127(28):10010-10011
Reported in this contribution are the synthesis, characterization, and charge transport properties of wire-like Ru2(ap)4(OPEn), where ap is 2-anilinopyridinate and OPE is -(CCC6H4)nSCH2CH2SiMe3 with n = 1 (1) and 2 (2). Scanning tunneling microscopy (STM) measurements of compound 2 inserted into a SAM of C11 thiol reveal that molecule 2 exhibits (i) the stochastic switching characteristic of wire molecules embedded in insulating SAMs and (ii) higher conductivity than the C11 thiol SAM. More importantly, analysis of the molecular electronic decay constant (beta) exhibits a decrease of at least 15% as compared to purely organic molecular analogues. Hence, the transport characteristics of molecules can be significantly improved for nanoscale electronics through the incorporation of a Ru2 fragment into conjugated backbone. 相似文献
104.
The O?˙ chemical ionization mass spectrri of the C8H10 alkylbenzenes, o-, m-. andp -xylene and ethylbenzene, show formation of [M ? H + O]?, [M ? H]?, [M ? H2]?˙ and, for the xylenes, [M ? CH3 + O]? as primary reaction products; the relative importance of these products depends on the isomer. However, [OH]? is a primary product from reaction of O?˙ with both the C8H10 isomers and hydrogen-containing impurities; [OH]? reacts further with the alkylbenzenes to produce [M ? H]? with the result that the chemical ionization mass spectra depend on experimental conditions such as sample size and the presence of impurities. The collision-induced charge inversion mass spectra of the [M ? H + O]? and [M ? H]? products allow only distinction of ethylbenzene from the xylenes. However, the collision-induced charge inversion mass spectra of the [M ? H2]?˙ ions show differences which allow identification of each isomer. 相似文献
105.
Paranemic crossover (PX) DNA is a four-stranded coaxial DNA complex containing a central dyad axis that relates two flanking parallel double helices. The strands are held together exclusively by Watson-Crick base pairing. The key feature of the structure is that the two adjacent parallel DNA double helices form crossovers at every point possible. Hence, reciprocal crossover points flank the central dyad axis at every major or minor groove separation. This motif has been modeled and characterized in an oligonucleotide system; a minor groove separation of five nucleotide pairs and major groove separations of six, seven, or eight nucleotide pairs produce stable PX DNA molecules; a major groove separation of 9 nucleotide pairs is possible at low concentrations. Every strand undergoes a crossover every helical repeat (11, 12, 13, or 14 nucleotides), but the structural period of each strand corresponds to two helical repeats (22, 24, 26, or 28 nucleotides). Nondenaturing gel electrophoresis shows that the molecules are stable, forming well-behaved complexes. PX DNA can be produced from closed dumbbells, demonstrating that the molecule is paranemic. Ferguson analysis indicates that the molecules are similar in shape to DNA double crossover molecules. Circular dichroism spectra are consistent with B-form DNA. Thermal transition profiles suggest a premelting transition in each of the molecules. Hydroxyl radical autofootprinting analysis confirms that there is a crossover point at each of the positions expected in the secondary structure. These molecules are generalized Holliday junctions. 相似文献
106.
Peng Yang Xuan Wang Bo Li Yixuan Yang Jinfeng Yue Yanrui Suo Huarong Tong Gang He Xiaojie Lu Gong Chen 《Chemical science》2021,12(16):5804
A highly efficient and versatile method for construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation of alkyl and aryl thiols with aryl iodides under mild conditions is developed. The method exhibits a broad substrate scope for thiols, aryl iodides and amino acid units. Peptide macrocycles of a wide range of size and composition can be readily assembled in high yield from various easily accessible building blocks. This method has been successfully employed to prepare an 8-million-membered tetrameric cyclic peptide DNA-encoded library (DEL). Preliminary screening of the DEL library against protein p300 identified compounds with single digit micromolar inhibition activity.A highly efficient and versatile method for construction of peptide macrocycles via palladium-catalyzed intramolecular S-arylation of alkyl and aryl thiols with aryl iodides under mild conditions is developed. 相似文献
107.
Preparation and Characterization of Three-dimensionally Ordered Crystalline Macroporous CeO2 总被引:2,自引:0,他引:2
Xi Yan ZHANG Tong Wen WANG Wen Qing JIANG Di WU Ling LIU Ai Hong DUAN 《中国化学快报》2005,16(8):1109-1112
Three-dimensional ordered macroporous (3DOM) materials are of great potential importance in catalysis, selective separation, sensor arrays and communications with optical band gaps1. Many results in the synthesis of 3DOM materials have been reported, such as closed-packed silica spheres or polystyrenes (PS) templating routes for silica2, metal oxides1-6 and metals7. Recently, poly(methyl methacrylate) (PMMA) colloidal crystal templates have been used to prepare 3DOM materials of metals8,… 相似文献
108.
硅氧烷乳液聚合过程中大颗粒形成机理研究:Ⅰ.阳离子型乳液的耐电解质… 总被引:5,自引:1,他引:5
探讨了二甲基聚硅氧烷阳离子型乳液耐电解质稳定性的影响因素。结果表明,加入少量的非离子型表面活性剂与阳离子型乳化剂并用进行乳液聚合,可以保护乳液粒子,防止由于电解质引的乳液粒子的相互凝聚而形成大颗粒。 相似文献
109.
110.
Selective hydrogenation of α,β‐unsaturated carbonyls into saturated carbonyls is important to obtain remunerative products. However, it is still a challenge to achieve high activity and selectivity under mild conditions. Herein, Pd, Ir and bimetallic Pd‐Ir nanoparticles were uniformly deposited with high dispersity on the surface of SiC by a facile impregnation method, respectively. The as‐prepared Pd/SiC catalysts efficiently hydrogenate cinnamaldehyde to hydrocinnamaldehyde at room temperature and atmospheric pressure, and the activity of Pd/SiC is observed further enhanced by adding Ir component (conversion of 100%). In addition, the dependence of Pd‐Ir catalyst activity on Pd/Ir molar ratio confirms a synergistic effect between Ir and Pd, which originates from the electron transfer between Pd and Ir. 相似文献