全文获取类型
收费全文 | 36421篇 |
免费 | 6777篇 |
国内免费 | 5751篇 |
专业分类
化学 | 26867篇 |
晶体学 | 575篇 |
力学 | 2342篇 |
综合类 | 395篇 |
数学 | 4027篇 |
物理学 | 14743篇 |
出版年
2024年 | 108篇 |
2023年 | 659篇 |
2022年 | 1307篇 |
2021年 | 1411篇 |
2020年 | 1474篇 |
2019年 | 1536篇 |
2018年 | 1326篇 |
2017年 | 1364篇 |
2016年 | 1790篇 |
2015年 | 1979篇 |
2014年 | 2398篇 |
2013年 | 2992篇 |
2012年 | 3491篇 |
2011年 | 3522篇 |
2010年 | 2618篇 |
2009年 | 2680篇 |
2008年 | 2898篇 |
2007年 | 2404篇 |
2006年 | 2233篇 |
2005年 | 1799篇 |
2004年 | 1344篇 |
2003年 | 1133篇 |
2002年 | 1145篇 |
2001年 | 926篇 |
2000年 | 750篇 |
1999年 | 617篇 |
1998年 | 444篇 |
1997年 | 402篇 |
1996年 | 354篇 |
1995年 | 286篇 |
1994年 | 289篇 |
1993年 | 224篇 |
1992年 | 175篇 |
1991年 | 143篇 |
1990年 | 139篇 |
1989年 | 88篇 |
1988年 | 80篇 |
1987年 | 61篇 |
1986年 | 70篇 |
1985年 | 47篇 |
1984年 | 24篇 |
1983年 | 28篇 |
1982年 | 13篇 |
1981年 | 14篇 |
1980年 | 9篇 |
1979年 | 19篇 |
1978年 | 7篇 |
1977年 | 11篇 |
1957年 | 8篇 |
1925年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
171.
Xing Yong Wang Jing Nan Cui Wei Min Ren Feng Li Chun Liang Lu Xu Hong Qian State Key Laboratory of Fine Chemicals Dalian University of Technology Dalian China School of Chemical Engineering Technology China University of Mining & Technology Xuzhou China Shanghai Key Laboratory of Chemical Biology East China University of Science Technology Shanghai China 《中国化学快报》2007,18(6):681-684
Baker's yeast mediated reduction of acenaphthenequinone within 4-10 h afforded mono-hydroxyacenaphthenone mainly with low enantioselectivity, the substrate and mono-hydroxyacenaphthenone product almost converted to dihydroxyacenaphthene after 48 h. By control of the reaction time and in the presence of DMF as co-solvent, the reduction of 6-substituted acenaphthenequinones under vigorous agitation afforded the corresponding 2-hydroxyacenaphthenones in 24-84% yields with 10-93% ee. 相似文献
172.
该文简述了电子显微技术的发展历程,并介绍了现代电子显微镜的新功能。针对生物纳米材料理化性能与功能应用的特殊性,结合研究实例,重点阐述运用电子显微结构表征与原位分析测试技术指导构建新颖纳米结构、揭示材料与细胞/组织相互作用并发挥功能的机制。并在此基础上,展望了电子显微技术在生物纳米材料研究领域的发展方向(大尺寸图像拼接、三维重构、动态原位实时成像)。 相似文献
173.
A nickel(Ⅱ) complex [Ni(La)2](NO3)2 (1) with bidentate racemic 1,2,2-trimethylcyclopentane-1,3-diamine ligand has been synthesized and characterized by IR, EA, ES-MS, and its X-ray diffraction study reveals that the nickel(Ⅱ) center is tetra-coordinated by one D- and one L- diamine ligands, and a three-dimensional hydrogen-bond-sustained network is formed in the solid state by means of the eight-membered N-H…O hydrogen bond cycle. This compound also supplies a good comparison to the chiral complex [Ni(Lb)2]Cl2·2H2O (2) (Lb=D-(+)-1,2,2-trimethylcyclopentane-1,3-diamine). CCDC: 218122. 相似文献
174.
Collagen methylation has been exploited in various applications involving living cells. We have observed correlation between the collagen methylation with the rate of cell proliferation in three-dimensional (3-D) microenvironment. To quantify the degree of collagen methylation, we have developed a capillary zone electrophoresis method. Using a polyvinyl alcohol-coated fused-silica capillary and UV detection at 200 nm, we have optimized pH and separated the native collagen into three major bands in phosphate buffer (50 mM, pH 2.5) with 0.05% hydroxypropylmethylcellulose. Under these conditions, the methylated collagens were separated into four major bands, which changed with different methylation reaction conditions. We propose an index to quantify the degree of collagen methylation that also correlates with their effects on cell proliferation. 相似文献
175.
Xi-Shang Sun Xing-Heng Wang Hai-Yan Tao Liang Wei Chun-Jiang Wang 《Chemical science》2020,11(40):10984
In this study, we developed an efficient Ir-catalyzed cascade umpolung allylation/2-aza-Cope rearrangement of tertiary α-trifluoromethyl α-amino acid derivatives for the preparation of a variety of quaternary α-trifluoromethyl α-amino acids in high yields with excellent enantioselectivities. The umpolung reactivity empowered by the activation of the key isatin-ketoimine moiety obviates the intractable enantioselectivity control in Pd-catalyzed asymmetric linear α-allylation. In combination with quasi parallel kinetic resolution or kinetic resolution, the generality of this method is further demonstrated by the first preparation of enantioenriched quaternary trifluoromethyl β-, γ-, δ- and ε-amino acid derivatives.In this study, we developed an efficient Ir-catalyzed cascade umpolung allylation/2-aza-Cope rearrangement for the preparation of a variety of quaternary trifluoromethyl α-ε-amino acids in high yields with excellent enantioselectivities. 相似文献
176.
We report herein an efficient catalytic epoxidation reaction for the synthesis of epoxyketone (tert-butyl ((S)-4-methyl-1-((R)-2-methyloxiran-2-yl)-1-oxopentan-2-yl)carbamate), which is an important synthetic intermediate of carfilzomib. 相似文献
177.
The action of a series of lanthanide chelate complexes LnL3, where Lu=La, Pr, Nd, Sm, Eu, Dy, Ho, Er and Yb; L= dbm (dibenzoylmethanato), dpm (dipivaloylmethanato), and acac acetylactonato), on nmr spectra of 2-butanol has been studied. The origin of shifting abilities and shifting sign of various lanthanide ions are explained by means of Bleaney's theory. 相似文献
178.
179.
SYNTHESIS OF MESOPOROUS POLY(STYRENE-co-MALEIC ANHYDRIDE)/SILICA HYBRID MATERIALS VIA A NONSURFACTANT-TEMPLATED SOL-GEL PROCESS* 总被引:1,自引:0,他引:1
Jie-bin Pang Kun-yuan Qiu Yen Wei Department of Polymer Science Engineering College of Chemistry Molecular Engineering Peking University Beijing China. Department of Chemistry Drexel University Philadelphia Pennsylvania USA. 《高分子科学》2000,(5):469-472
Mesoporous poly (styrene-co-maleic anhydride)/silica hybrid materials have been prepared. The synthesis wasachieved by the HCl-catalyzed sol-gel reactions of tetraethyl orthosilicate (TEOS) and styrene-maleic anhydride copolymerin the presence of 3-aminopropyl triethoxysilane (APTES) as a coupling agent and citric acid as a nonsurfactant template orpore-forming agent, followed by ethanol extraction. Characterization results from nitrogen sorption isotherms and powder X-ray diffraction indicate that polymer-modified mesoporous materials with large specific surface areas (e.g. 900 m~2/g) andpore volumes (e.g. 0.6 cm~3/g) could be prepared. As the citric acid concentration is increased, the specific surface areas, porevolumes and pore diameters of the hybrid materials increase. 相似文献
180.
Adsorption, desorption and activities of acid phosphatase on various colloidal particles from an Ultisol 总被引:1,自引:0,他引:1
Adsorption, desorption and activity of acid phosphatase on various soil colloidal particles and pure clay minerals were studied. Higher adsorption amounts and low percentage of desorption of acid phosphatase were found on fine soil clays (<0.2 μm). Electrostatic force and ligand exchange are the major driving forces that are involved in the adsorption of enzymes on soil clays. More enzyme molecules were adsorbed on soil clays in the presence of organic components. However, enzymes on organic clays were more easily released. One-third of the enzyme on goethite was adsorbed via ligand exchange process. Some other interactions, such as van der Waals force, hydrophobic force and hydrogen bonding may be more important in the adsorption of enzyme on kaolinite and the enzyme in this system cannot be easily removed. Coarse clays (0.2–2 μm) and inorganic soil clays had higher affinities for enzyme molecules than fine clays and organic clays, respectively. The activity of enzyme bound on soil clays was inhibited and the thermal stability was increased in the presence of organic matter. Data obtained in this study are helpful for a better understanding of the interactions of enzymes with inorganic and organic constituents in soil and associated environments. 相似文献