全文获取类型
收费全文 | 7479篇 |
免费 | 1394篇 |
国内免费 | 1173篇 |
专业分类
化学 | 5583篇 |
晶体学 | 159篇 |
力学 | 403篇 |
综合类 | 96篇 |
数学 | 907篇 |
物理学 | 2898篇 |
出版年
2024年 | 28篇 |
2023年 | 150篇 |
2022年 | 280篇 |
2021年 | 307篇 |
2020年 | 325篇 |
2019年 | 328篇 |
2018年 | 309篇 |
2017年 | 286篇 |
2016年 | 359篇 |
2015年 | 448篇 |
2014年 | 473篇 |
2013年 | 526篇 |
2012年 | 689篇 |
2011年 | 748篇 |
2010年 | 543篇 |
2009年 | 439篇 |
2008年 | 539篇 |
2007年 | 469篇 |
2006年 | 404篇 |
2005年 | 350篇 |
2004年 | 287篇 |
2003年 | 283篇 |
2002年 | 346篇 |
2001年 | 252篇 |
2000年 | 142篇 |
1999年 | 139篇 |
1998年 | 89篇 |
1997年 | 68篇 |
1996年 | 77篇 |
1995年 | 75篇 |
1994年 | 55篇 |
1993年 | 37篇 |
1992年 | 39篇 |
1991年 | 33篇 |
1990年 | 39篇 |
1989年 | 22篇 |
1988年 | 12篇 |
1987年 | 10篇 |
1986年 | 6篇 |
1985年 | 14篇 |
1984年 | 7篇 |
1983年 | 6篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
61.
Xiaojuan Liu Qingqing Wen Prof. Dr. Li Xiang Dr. Xuebing Leng Prof. Dr. Yaofeng Chen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5494-5499
The synthesis and catalytic applications of trivalent rare-earth metal alkyl complexes have been well developed, but the chemistry of divalent rare-earth metal alkyl complexes lagged much behind. Herein, we report the synthesis, structure, and catalytic applications of a samarium(II) monoalkyl complex supported by a β-diketiminato-based tetradentate ligand, [LSmCH(SiMe3)2] (L=[MeC(NDipp)CHC(Me)NCH2CH2N(Me)CH2CH2NMe2]−, Dipp=2,6-(iPr)2C6H3). This complex is synthesized by the salt metathesis reaction of samarium iodide [LSm(μ-I)]2 and KCH(SiMe3)2 in 63 % yield. Its structure is characterized by single-crystal X-ray diffraction, showing a distorted square-pyramid coordination geometry. This samarium(II) monoalkyl complex exhibits high catalytic activity in the hydrosilylation of aryl and methyl-substituted unsymmetrical internal alkynes with secondary hydrosilanes, selectively providing the α-(E) products in high yields. 相似文献
62.
Dr. Xiang Hao Kaixiang Yang Hairong Wang Prof. Feng Peng Prof. Haiyang Yang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(11):4344-4349
Non-Newtonian fluids are ubiquitous in daily life and industrial applications. Herein, we report an intelligent fluidic system integrating two distinct non-Newtonian rheological properties mediated by an autocatalytic enzyme reaction. Associative polyelectrolytes bearing a small amount of ionic and alkyl groups are engineered: by carefully balancing the charge density and the hydrophobic effect, the polymer solutions demonstrate a unique shear thickening property at low pH while shear thinning at high pH. The urea-urease clock reaction is utilized to program a feedback-induced pH change, leading to a strong upturn of the nonlinear viscoelastic properties. As long as the chemical fuel is supplied, two distinct non-Newtonian states can be achieved with a tunable lifetime span. As a proof of concept, we demonstrate how the physical energy-driven nonequilibrium properties can be manipulated by a chemical-fueled process. 相似文献
63.
Yunjie Xiang Suoping Peng Shaohui Zheng 《International journal of quantum chemistry》2020,120(1):e26047
Organic solar cell of silol dithiophene based D2-A-D1-A-D2/PC71BM (D: donor part; A: acceptor part; 1 and 2 denote different units) possesses promising power conversion efficiency. Researchers have studied D2-A-D1-A-D2 molecules carefully, including the effects of the different number of terminal thiophenes, the different central moiety (D1), and the length of the alkyl chain. However, there are few investigations, especially theoretical studies, on the influences of different A (acceptor) units on the properties of D2-A-D1-A-D2 molecule. In the present work, we have designed and modeled five new D2-A-D1-A-D2 (D2 = bithiophene and D1 = silol dithiophene) donors by changing A units (A = diketopyrrolopyrrole, naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole, 5-fluoro-2,1,3-benzoselenadiazole, benzobisthiadiazole, and thiazolo[5,4-d]thiazole). We have applied density functional theory (DFT) and time-dependent DFT to predict their ground-state electronic structures and the UV–vis spectra, and the open circuit voltages (Vocs) of organic solar cells of D2-A-D1-A-D2/PC71BM. Based on the calculated results, we find that bithiophene thiazolo[5,4-d]thiazole siloldithiophene (BTTS) (D2 = bithiophene, A = thiazolo[5,4-d]thiazole, D1 = silol dithiophene) possesses the highest lowest unoccupied molecular orbital (−2.60 eV) and the lowest highest occupied molecular orbital (−5.33 eV) energies, and the strongest absorption in the visible region. Besides, the solar cell of BTTS/PC71BM has the highest Voc of 1.02 V. These results indicate that it may be a promising donor. In contrast, bithiophene benzobisthiadiazole siloldithiophene (BBBS) (A = benzobisthiadiazole) has low absorption strength in the visible region, which indicates that it may not be a suitable donor material. 相似文献
64.
Jun-Jie Tian Zhao-Ying Yang Xin-Shen Liang Ning Liu Chen-Yu Hu Xian-Shuang Tu Xiang Li Prof. Dr. Xiao-Chen Wang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(42):18610-18614
Herein, we report that highly chemoselective and enantioselective reduction of 2-vinyl-substituted pyridines has been achieved for the first time. The reaction, which uses chiral spiro-bicyclic bisboranes as catalysts and HBpin and an acidic amide as reducing reagents, proceeds through a cascade process involving 1,4-hydroboration followed by transfer hydrogenation of a dihydropyridine intermediate. The retained double bond in the reduction products permits their conversion to natural products and other useful heterocyclic compounds by simple transformations. 相似文献
65.
Radical-Cation Cascade to Aryltetralin Cyclic Ether Lignans Under Visible-Light Photoredox Catalysis
Dr. Jia-Chen Xiang Dr. Qian Wang Prof. Dr. Jieping Zhu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(47):21381-21388
The development of concise, sustainable, and cost-effective synthesis of aryltetralin lignans, bearing either a fused lactone or cyclic ether, is of significant medicinal importance. Reported is that in the presence of Fukuzumi's acridinium salt under blue LED irradiation, functionalized dicinnamyl ether derivatives are converted into aryltetralin cyclic ether lignans with concurrent generation of three stereocenters in good to high yields with up to 20:1 diastereoselectivity. Oxidation of an alkene to the radical cation is key to the success of this formal Diels–Alder reaction of electronically mismatched diene and dienophile. Applying this methodology, six natural products, aglacin B, aglacin C, sulabiroin A, sulabiroin B, gaultherin C, and isoshonanin, are synthesized in only two to three steps from readily available biomass-derived monolignols. A revised structure is proposed for gaultherin C. 相似文献
66.
Zhou Shuiping Zhou Xiaoyang Tang Gen Guo Xiang Pang Aimin 《Journal of Thermal Analysis and Calorimetry》2020,140(5):2529-2540
Journal of Thermal Analysis and Calorimetry - Differences of thermal decomposition characteristics and combustion properties between CL-20-based propellants and HMX-based propellants were... 相似文献
67.
Chen Dan Dan He Zhi Qiang Wang Min Wu Di Chen Xiang Ying Zhang Zhong Jie 《Journal of Solid State Electrochemistry》2020,24(3):641-654
Journal of Solid State Electrochemistry - In the present work, we demonstrate a strategy of combining boron doping and porosity engineering for a highly modulated carbon component and pore... 相似文献
68.
We classify all Leibniz conformal algebras of rank two. 相似文献
69.
Xiang Hao Kaixiang Yang Hairong Wang Feng Peng Haiyang Yang 《Angewandte Chemie (International ed. in English)》2020,59(11):4314-4319
Non‐Newtonian fluids are ubiquitous in daily life and industrial applications. Herein, we report an intelligent fluidic system integrating two distinct non‐Newtonian rheological properties mediated by an autocatalytic enzyme reaction. Associative polyelectrolytes bearing a small amount of ionic and alkyl groups are engineered: by carefully balancing the charge density and the hydrophobic effect, the polymer solutions demonstrate a unique shear thickening property at low pH while shear thinning at high pH. The urea‐urease clock reaction is utilized to program a feedback‐induced pH change, leading to a strong upturn of the nonlinear viscoelastic properties. As long as the chemical fuel is supplied, two distinct non‐Newtonian states can be achieved with a tunable lifetime span. As a proof of concept, we demonstrate how the physical energy‐driven nonequilibrium properties can be manipulated by a chemical‐fueled process. 相似文献
70.
Long-term pulmonary exposure to multi-walled carbon nanotubes (MWCNTs) may promote breast cancer metastasis and rapid colonization in the lungs and other organs according to recent research conducted by Prof.Chunying Chen,Prof.Tao Zhu and their colleagues,published in Nature Nanotechnology [1]. 相似文献