全文获取类型
收费全文 | 21023篇 |
免费 | 3062篇 |
国内免费 | 3989篇 |
专业分类
化学 | 16389篇 |
晶体学 | 436篇 |
力学 | 1012篇 |
综合类 | 357篇 |
数学 | 2491篇 |
物理学 | 7389篇 |
出版年
2024年 | 41篇 |
2023年 | 204篇 |
2022年 | 546篇 |
2021年 | 582篇 |
2020年 | 609篇 |
2019年 | 654篇 |
2018年 | 581篇 |
2017年 | 567篇 |
2016年 | 787篇 |
2015年 | 928篇 |
2014年 | 1094篇 |
2013年 | 1565篇 |
2012年 | 1703篇 |
2011年 | 1777篇 |
2010年 | 1444篇 |
2009年 | 1400篇 |
2008年 | 1690篇 |
2007年 | 1531篇 |
2006年 | 1400篇 |
2005年 | 1213篇 |
2004年 | 1094篇 |
2003年 | 940篇 |
2002年 | 1051篇 |
2001年 | 886篇 |
2000年 | 740篇 |
1999年 | 528篇 |
1998年 | 312篇 |
1997年 | 320篇 |
1996年 | 274篇 |
1995年 | 247篇 |
1994年 | 229篇 |
1993年 | 199篇 |
1992年 | 176篇 |
1991年 | 127篇 |
1990年 | 118篇 |
1989年 | 109篇 |
1988年 | 60篇 |
1987年 | 61篇 |
1986年 | 48篇 |
1985年 | 43篇 |
1984年 | 35篇 |
1983年 | 27篇 |
1982年 | 22篇 |
1981年 | 19篇 |
1980年 | 18篇 |
1979年 | 10篇 |
1978年 | 15篇 |
1977年 | 7篇 |
1976年 | 8篇 |
1973年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
Qihao Wu Song‐Wei Li Heng Xu Hong Wang Pei Hu Hao Zhang Cheng Luo Kai‐Xian Chen Bastien Nay Yue‐Wei Guo Xu‐Wen Li 《Angewandte Chemie (International ed. in English)》2020,59(29):12105-12112
Placobranchus ocellatus is well known to produce diverse and complex γ‐pyrone polypropionates. In this study, the chemical investigation of P. ocellatus from the South China Sea led to the discovery and identification of ocellatusones A–D, a series of racemic non‐γ‐pyrone polyketides with novel skeletons, characterized by a bicyclo[3.2.1]octane ( 1 , 2 ), a bicyclo[3.3.1]nonane ( 3 ) or a mesitylene‐substituted dimethylfuran‐3(2H)‐one core ( 4 ). Extensive spectroscopic analysis, quantum chemical computation, chemical synthesis, and/or X‐ray diffraction analysis were used to determine the structure and absolute configuration of the new compounds, including each enantiomer of racemic compounds 1 – 4 after chiral HPLC resolution. An array of new and diversity‐generating rearrangements is proposed to explain the biosynthesis of these unusual compounds based on careful structural analysis and comparison with six known co‐occurring γ‐pyrones ( 5 – 10 ). Furthermore, the successful biomimetic semisynthesis of ocellatusone A ( 1 ) confirmed the proposed rearrangement through an unprecedented acid induced cascade reaction. 相似文献
972.
Wuqian Guo Xitao Liu Shiguo Han Yi Liu Zhiyun Xu Maochun Hong Junhua Luo Zhihua Sun 《Angewandte Chemie (International ed. in English)》2020,59(33):13879-13884
Although two‐dimensional (2D) metal–halide double perovskites display versatile physical properties due to their huge structural compatibility, room‐temperature ferroelectric behavior has not yet been reported for this fascinating family. Here, we designed a room‐temperature ferroelectric material composed of 2D halide double perovskites, (chloropropylammonium)4AgBiBr8, using an organic asymmetric dipolar ligand. It exhibits concrete ferroelectricity, including a Curie temperature of 305 K and a notable spontaneous polarization of ≈3.2 μC cm?2, triggered by dynamic ordering of the organic cation and the tilting motion of heterometallic AgBr6/BiBr6 octahedra. Besides, the alternating array of inorganic perovskite sheets and organic cations endows large mobility‐lifetime product (μτ=1.0×10?3 cm2 V?1) for detecting X‐ray photons, which is almost tenfold higher than that of CH3NH3PbI3 wafers. As far as we know, this is the first study on an X‐ray‐sensitive ferroelectric material composed of 2D halide double perovskites. Our findings afford a promising platform for exploring new ferroelectric materials toward further device applications. 相似文献
973.
Sang Kyu Park Hong Sun Hyunjoong Chung Bijal B. Patel Fengjiao Zhang Daniel W. Davies Toby J. Woods Kejie Zhao Ying Diao 《Angewandte Chemie (International ed. in English)》2020,59(31):13004-13012
Like silicon, single crystals of organic semiconductors are pursued to attain intrinsic charge transport properties. However, they are intolerant to mechanical deformation, impeding their application in flexible electronic devices. Such contradictory properties, namely exceptional molecular ordering and mechanical flexibility, are unified in this work. We found that bis(triisopropylsilylethynyl)pentacene (TIPS‐P) crystals can undergo mechanically induced structural transitions to exhibit superelasticity and ferroelasticity. These properties arise from cooperative and correlated molecular displacements and rotations in response to mechanical stress. By utilizing a bending‐induced ferroelastic transition of TIPS‐P, flexible single‐crystal electronic devices were obtained that can tolerate strains (?) of more than 13 % while maintaining the charge carrier mobility of unstrained crystals (μ>0.7 μ0). Our work will pave the way for high‐performance ultraflexible single‐crystal organic electronics for sensors, memories, and robotic applications. 相似文献
974.
Kangjae Lee Seojin Lee Namhoon Kim Seonyul Kim Sungwoo Hong 《Angewandte Chemie (International ed. in English)》2020,59(32):13379-13384
A general strategy for visible‐light‐enabled site‐selective trifluoromethylative pyridylation of unactivated alkenes has been developed using pyridines and triflic anhydride (Tf2O). Intriguingly, the N‐triflylpyridinium salts, generated in situ from pyridines and Tf2O, serve as effective modular bifunctional reagents to install both CF3 and pyridyl groups to various olefins while controlling C4‐selectivity in radical addition to the pyridine core. This synthetic route exhibited broad substrate scope under metal‐free and mild photocatalytic conditions, granting efficient access to valuable C4‐alkylated pyridines and quinolines without requiring prefunctionalization of the reaction site. 相似文献
975.
Jun Hu Nan Zhang Pan‐Ke Zhang Yun Chen Xing‐Hua Xia Hong‐Yuan Chen Jing‐Juan Xu 《Angewandte Chemie (International ed. in English)》2020,59(41):18244-18248
We report a new mass spectrometric method for detecting electrogenerated intermediates. This approach is based on simultaneous activation of electrospray ionization and redox reaction on a wireless bipolar ultramicroelectrode, which is fabricated in the tip of a quartz nanopipette. The hollow structure of the ultramicroelectrode permits rapid transferring the transient species from electrode–electrolyte interfaces into the gas phase for mass spectrometric identification on the time scale of microseconds. The long‐sought fleeting intermediates including TPrA.+, whose lifetime in solution is only 200 μs, and catecholamine o‐semiquinone radicals, the second‐order rate constant of which is typically 109 m ?1 s?1, were successfully identified, helping clarify the previously hidden reaction pathways. Accordingly, our method may have wide applicability in exploring the dynamics of many electrochemical reactions, especially their ultrafast initial steps. 相似文献
976.
Le Hoang Vien Le Thi Hanh Tran Thi Hong Thanh Nguyen Van Nam Nguyen Hoai 《Natural product research》2020,34(8):1061-1067
AbstractFrom the MeOH extract of the Vietnamese sea cucumber Holothuria edulis, eight triterpene glycosides (1–8), including one new compound namely holothurin A5 (1), were isolated by using various chromatographic separations. Their structures were established by spectroscopic experiments including 1D, 2D NMR and HR-ESI-MS. Holothurin A5 (1) has a hydroperoxy group at C-25. To the best of our knowledge, this is the first report of this group in triterpene saponins obtained from sea cucumbers to date. In addition, the in vitro cytotoxicity against five human cancer cell lines (HepG2, KB, LNCaP, MCF7 and SK-Mel2) of all isolated compounds was also evaluated using SRB assays. 相似文献
977.
Du Min Zhang Feng Zhang Xiaofei Dong Wentao Sang Yuanhua Wang Jianjun Liu Hong Wang Shuhua 《中国科学:化学(英文版)》2020,63(12):1767-1776
Science China Chemistry - Rechargeable aqueous zinc ion batteries (ZIBs), with the easy operation, cost effectiveness, and high safety, are emerging candidates for high-energy wearable/portable... 相似文献
978.
Li‐Ming Zhao Xia‐Qiang Shen Qian Liu Wei Wu Hao‐Hong Li Zhi‐Rong Chen Yi Li 《化学:亚洲杂志》2020,15(1):136-147
Host‐guest encapsulation of functional organic dye into a porous metal‐organic framework can give rise to the development of new functional materials. In this work, by intercalating the stilbazolium‐type dye (DEAST)I (4′‐diethylamino‐N‐methyl stilbazolium) into four lanthanide layered metal‐organic complexes (Ln‐LMOCs), i. e. {[Ln(BTB)(H2O)2]?3(DMF)?2(H2O)}n (Ln=La (1), Nd (2), Sm (3), Er (4)), four responsive (DEAST)I@Ln‐LMOC composites have been prepared, serving as multifunctional performance platform. The core–shell structures of (DEAST)I@Ln‐LMOC composites have been fully characterized by IR, UV/Vis, PXRD, SEM, TEM, TGA and ESR. Significantly, after intercalation of dyes, the (DEAST)I@Ln‐LMOC composites exhibit enhanced luminescent sensing properties in detecting Fe3+ with much higher water stabilities. The luminescent sensing behavior stems from the fluorescence resonance energy transfer (FRET) from the π‐electron‐rich BTB ligands to the Fe3+, and their higher water stabilities are induced by electrostatic interactions and lower porosity. Specially, the characteristic emissions of Sm3+ will not be affected after the encapsulation guest dyes, which provide a theoretical guide for the modulation of luminescence devices. Finally, better ion conductivities and diminished photocurrents can be achieved after the embedding of the functional organic dye. In all, the formation of (DEAST)I@Ln‐LMOC composites with core–shell structures can be utilized as a multifunctional platform with good stability. 相似文献
979.
980.
This paper studies the contact vibration problem of an elastic half-space coated with functionally graded materials (FGMs) subject to a rigid spherical punch. A static force superimposing a dynamic time-harmonic force acts on the rigid spherical punch. Firstly, we give the static contact problem of FGMs by a least-square fitting approach. Next, the dynamic contact pressure is solved by employing the perturbation method. Lastly, the dynamic contact stiffness with different dynamic contact displacement conditions is derived for the FGM coated half-space. The effects of the gradient index, coating thickness, internal friction, and punch radius on the dynamic contact stiffness factor are discussed in detail. 相似文献