全文获取类型
收费全文 | 5973篇 |
免费 | 248篇 |
国内免费 | 43篇 |
专业分类
化学 | 2689篇 |
晶体学 | 53篇 |
力学 | 192篇 |
数学 | 1388篇 |
物理学 | 934篇 |
无线电 | 1008篇 |
出版年
2023年 | 67篇 |
2022年 | 116篇 |
2021年 | 179篇 |
2020年 | 183篇 |
2019年 | 199篇 |
2018年 | 205篇 |
2017年 | 175篇 |
2016年 | 299篇 |
2015年 | 177篇 |
2014年 | 263篇 |
2013年 | 423篇 |
2012年 | 372篇 |
2011年 | 363篇 |
2010年 | 223篇 |
2009年 | 246篇 |
2008年 | 294篇 |
2007年 | 265篇 |
2006年 | 210篇 |
2005年 | 183篇 |
2004年 | 168篇 |
2003年 | 130篇 |
2002年 | 127篇 |
2001年 | 111篇 |
2000年 | 94篇 |
1999年 | 64篇 |
1998年 | 48篇 |
1997年 | 56篇 |
1996年 | 76篇 |
1995年 | 67篇 |
1994年 | 57篇 |
1993年 | 66篇 |
1992年 | 53篇 |
1991年 | 60篇 |
1990年 | 40篇 |
1989年 | 40篇 |
1988年 | 40篇 |
1987年 | 45篇 |
1986年 | 47篇 |
1985年 | 49篇 |
1984年 | 37篇 |
1983年 | 29篇 |
1982年 | 36篇 |
1981年 | 35篇 |
1980年 | 24篇 |
1979年 | 43篇 |
1978年 | 33篇 |
1977年 | 26篇 |
1976年 | 28篇 |
1975年 | 25篇 |
1973年 | 16篇 |
排序方式: 共有6264条查询结果,搜索用时 234 毫秒
951.
Electrochemical Reduction of Carbon Dioxide to Methanol on Hierarchical Pd/SnO2 Nanosheets with Abundant Pd–O–Sn Interfaces 下载免费PDF全文
Wuyong Zhang Qing Qin Dr. Lei Dai Ruixuan Qin Dr. Xiaojing Zhao Xumao Chen Daohui Ou Dr. Jie Chen Dr. Tracy T Chuong Prof. Binghui Wu Prof. Nanfeng Zheng 《Angewandte Chemie (International ed. in English)》2018,57(30):9475-9479
Electrochemical conversion of CO2 into fuels using electricity generated from renewable sources helps to create an artificial carbon cycle. However, the low efficiency and poor stability hinder the practical use of most conventional electrocatalysts. In this work, a 2D hierarchical Pd/SnO2 structure, ultrathin Pd nanosheets partially capped by SnO2 nanoparticles, is designed to enable multi‐electron transfer for selective electroreduction of CO2 into CH3OH. Such a structure design not only enhances the adsorption of CO2 on SnO2, but also weakens the binding strength of CO on Pd due to the as‐built Pd–O–Sn interfaces, which is demonstrated to be critical to improve the electrocatalytic selectivity and stability of Pd catalysts. This work provides a new strategy to improve electrochemical performance of metal‐based catalysts by creating metal oxide interfaces for selective electroreduction of CO2. 相似文献
952.
Dr. Gerrit Jürjens Dr. Sören M. M. Schuler Dr. Michael Kurz Dr. Sylvain Petit Dr. Cédric Couturier Dr. Frédéric Jeannot Fabian Nguyen Dr. Raffael C. Wende Prof. Dr. Peter E. Hammann Prof. Dr. Daniel N. Wilson Dr. Eric Bacqué Dr. Christoph Pöverlein Dr. Armin Bauer 《Angewandte Chemie (International ed. in English)》2018,57(37):12157-12161
The total synthesis of the naturally occurring antibiotic GE81112A, a densely functionalized tetrapeptide, is reported. Comparison of spectral data with those of the natural product and the lack of biological activity of the synthesized compound led us to revise the published configuration of the 3‐hydroxypipecolic acid moiety. This hypothesis was fully validated by the synthesis of the corresponding epimer. 相似文献
953.
Dr. Nguyen Van Nghia Dr. Saibal Jana Surendran Sujith Ji Yeon Ryu Prof. Junseong Lee Prof. Sang Uck Lee Prof. Min Hyung Lee 《Angewandte Chemie (International ed. in English)》2018,57(38):12483-12488
An approach to the design of nido‐carborane‐based luminescent compounds that can exhibit thermally activated delayed fluorescence (TADF) is proposed. 7,8‐Dicarba‐nido‐undecaboranes (nido‐carboranes) having various 8‐R groups (R=H, Me, i‐Pr, Ph) are appended to the meta or para position of the phenyl ring of the dimesitylphenylborane (PhBMes2) acceptor, forming donor–acceptor compounds (nido‐ m1 – m4 and nido‐ p1 – p4 ). The bulky 8‐R group and meta substitution of the nido‐carborane are essential to attain a highly twisted arrangement between the donor and acceptor moieties, leading to a very small energy splitting between the singlet and triplet excited states (ΔEST <0.05 eV for nido‐ m2 , ‐ m3 , and ‐ p3 ). These compounds exhibit efficient TADF with microsecond‐range lifetimes. In particular, nido‐ m2 and ‐ m3 display aggregation‐induced emission (AIE) with TADF properties. 相似文献
954.
Glycosyl‐Substituted Dicarboxylates as Detergents for the Extraction,Overstabilization, and Crystallization of Membrane Proteins 下载免费PDF全文
Dr. Kim‐Anh Nguyen Dr. Marine Peuchmaur Sandrine Magnard Dr. Romain Haudecoeur Dr. Cédric Boyère Saravanan Mounien Ikram Benammar Veronica Zampieri Dr. Sébastien Igonet Dr. Vincent Chaptal Dr. Anass Jawhari Prof. Ahcène Boumendjel Dr. Pierre Falson 《Angewandte Chemie (International ed. in English)》2018,57(11):2948-2952
To tackle the problems associated with membrane protein (MP) instability in detergent solutions, we designed a series of glycosyl‐substituted dicarboxylate detergents (DCODs) in which we optimized the polar head to clamp the membrane domain by including, on one side, two carboxyl groups that form salt bridges with basic residues abundant at the membrane–cytoplasm interface of MPs and, on the other side, a sugar to form hydrogen bonds. Upon extraction, the DCODs 8 b , 8 c , and 9 b preserved the ATPase function of BmrA, an ATP‐binding cassette pump, much more efficiently than reference or recently designed detergents. The DCODs 8 a , 8 b , 8 f , 9 a , and 9 b induced thermal shifts of 20 to 29 °C for BmrA and of 13 to 21 °C for the native version of the G‐protein‐coupled adenosine receptor A2AR. Compounds 8 f and 8 g improved the diffraction resolution of BmrA crystals from 6 to 4 Å. DCODs are therefore considered to be promising and powerful tools for the structural biology of MPs. 相似文献
955.
Plasmonic Hotspots in Air: An Omnidirectional Three‐Dimensional Platform for Stand‐Off In‐Air SERS Sensing of Airborne Species 下载免费PDF全文
Gia Chuong Phan‐Quang Dr. Hiang Kwee Lee Hao Wen Teng Charlynn Sher Lin Koh Barnabas Qinwei Yim Dr. Eddie Khay Ming Tan Wee Lee Tok Dr. In Yee Phang Prof. Dr. Xing Yi Ling 《Angewandte Chemie (International ed. in English)》2018,57(20):5792-5796
Molecular‐level airborne sensing is critical for early prevention of disasters, diseases, and terrorism. Currently, most 2D surface‐enhanced Raman spectroscopy (SERS) substrates used for air sensing have only one functional surface and exhibit poor SERS‐active depth. “Aerosolized plasmonic colloidosomes” (APCs) are introduced as airborne plasmonic hotspots for direct in‐air SERS measurements. APCs function as a macroscale 3D and omnidirectional plasmonic cloud that receives laser irradiation and emits signals in all directions. Importantly, it brings about an effective plasmonic hotspot in a length scale of approximately 2.3 cm, which affords 100‐fold higher tolerance to laser misalignment along the z‐axis compared with 2D SERS substrates. APCs exhibit an extraordinary omnidirectional property and demonstrate consistent SERS performance that is independent of the laser and analyte introductory pathway. Furthermore, the first in‐air SERS detection is demonstrated in stand‐off conditions at a distance of 200 cm, highlighting the applicability of 3D omnidirectional plasmonic clouds for remote airborne sensing in threatening or inaccessible areas. 相似文献
956.
Dr. Tatsuki Kurokawa Dr. Shigeki Kiyonaka Dr. Eiji Nakata Dr. Masayuki Endo Shohei Koyama Emiko Mori Nam Ha Tran Huyen Dinh Dr. Yuki Suzuki Kumi Hidaka Dr. Masaaki Kawata Dr. Chikara Sato Prof. Hiroshi Sugiyama Prof. Takashi Morii Prof. Yasuo Mori 《Angewandte Chemie (International ed. in English)》2018,57(10):2586-2591
In native systems, scaffolding proteins play important roles in assembling proteins into complexes to transduce signals. This concept is yet to be applied to the assembly of functional transmembrane protein complexes in artificial systems. To address this issue, DNA origami has the potential to serve as scaffolds that arrange proteins at specific positions in complexes. Herein, we report that Kir3 K+ channel proteins are assembled through zinc‐finger protein (ZFP)‐adaptors at specific locations on DNA origami scaffolds. Specific binding of the ZFP‐fused Kir3 channels and ZFP‐based adaptors on DNA origami were confirmed by atomic force microscopy and gel electrophoresis. Furthermore, the DNA origami with ZFP binding sites nearly tripled the K+ channel current activity elicited by heterotetrameric Kir3 channels in HEK293T cells. Thus, our method provides a useful template to control the oligomerization states of membrane protein complexes in vitro and in living cells. 相似文献
957.
Bagrat A. Shainyan Elena N. Suslova Tran Dinh Phien Sergey A. Shlykov Erich Kleinpeter 《Tetrahedron》2018,74(32):4299-4307
1-(Dimethylamino)-1-phenyl-1-silacyclohexane 1, was synthesized, and its molecular structure and conformational properties studied by gas-phase electron diffraction (GED), low temperature 13C NMR spectroscopy and quantum-chemical calculations. The predominance of the 1-Phax conformer (1-Pheq:1-Phax ratio of 20:80%, ΔG°(317?K)?=??0.87?kcal/mol) in the gas phase is close to the theoretically estimated conformational equilibrium. In solution, low temperature NMR spectroscopy showed analyzable decoalescence of Cipso and C(1,5) carbon signals in 13C NMR spectra at 103?K. Opposite to the gas state in the freon solution employed (CD2Cl2/CHFCl2/CHFCl2?=?1:1:3), which is still liquid at 100?K, the 1-Pheq conformer was found to be the preferred one [(1-Pheq: 1-Phax?=?77%: 23%, K?=?77/23?=?2.8; ?ΔG°?=??RT ln K (at 103?K)?=?0.44?±?0.1?kcal/mol]. When comparing 1 with 1-phenyl-1-(X)silacylohexanes (X?=?H, Me, OMe, F, Cl), studied so far, the trend of predominance of the Phax conformer in the gas phase and of the Pheq conformer in solution is confirmed. 相似文献
958.
Huynh Le Thanh Nguyen Tran Thi Thuy Dung Nguyen Hoang Hai Au Nguyen Thi Thu Trang Tran Van Man Grag Akhil Le My Loan Phung 《Journal of Solid State Electrochemistry》2018,22(7):2247-2254
Journal of Solid State Electrochemistry - Olivine LiFePO4 (LFP) is a promising cathode material for high-rated lithium-ion batteries. However, olivine faced a severe disadvantage of low... 相似文献
959.
Total Synthesis of (6R,10R,13R,14R,16R,17R,19S,20R,21R,24S, 25S,28S,30S,32R,33R,34R,36S,37S,39R)‐Azaspiracid‐3 Reveals Non‐Identity with the Natural Product 下载免费PDF全文
Nathaniel T. Kenton Dr. Daniel Adu‐Ampratwum Dr. Antony A. Okumu Dr. Zhigao Zhang Dr. Yong Chen Dr. Son Nguyen Dr. Jianyan Xu Dr. Yue Ding Dr. Pearse McCarron Dr. Jane Kilcoyne Prof. Dr. Frode Rise Prof. Dr. Alistair L. Wilkins Dr. Christopher O. Miles Prof. Dr. Craig J. Forsyth 《Angewandte Chemie (International ed. in English)》2018,57(3):805-809
A convergent and stereoselective total synthesis of the previously assigned structure of azaspiracid‐3 has been achieved by a late‐stage Nozaki–Hiyama–Kishi coupling to form the C21?C22 bond with the C20 configuration unambiguously established from l ‐(+)‐tartaric acid. Postcoupling steps involved oxidation to an ynone, modified Stryker reduction of the alkyne, global deprotection, and oxidation of the resulting C1 primary alcohol to the carboxylic acid. The synthetic product matched naturally occurring azaspiracid‐3 by mass spectrometry, but differed both chromatographically and spectroscopically. 相似文献
960.
Abdullah H. Alshehri Kissan Mistry Viet Huong Nguyen Khaled H. Ibrahim David Muoz‐Rojas Mustafa Yavuz Kevin P. Musselman 《Advanced functional materials》2019,29(7)
A quantum‐tunneling metal‐insulator‐metal (MIM) diode is fabricated by atmospheric pressure chemical vapor deposition (AP‐CVD) for the first time. This scalable method is used to produce MIM diodes with high‐quality, pinhole‐free Al2O3 films more rapidly than by conventional vacuum‐based approaches. This work demonstrates that clean room fabrication is not a prerequisite for quantum‐enabled devices. In fact, the MIM diodes fabricated by AP‐CVD show a lower effective barrier height (2.20 eV) at the electrode–insulator interface than those fabricated by conventional plasma‐enhanced atomic layer deposition (2.80 eV), resulting in a lower turn on voltage of 1.4 V, lower zero‐bias resistance, and better asymmetry of 107. 相似文献