全文获取类型
收费全文 | 1904篇 |
免费 | 40篇 |
国内免费 | 6篇 |
专业分类
化学 | 1306篇 |
晶体学 | 30篇 |
力学 | 43篇 |
数学 | 332篇 |
物理学 | 239篇 |
出版年
2021年 | 13篇 |
2020年 | 24篇 |
2019年 | 21篇 |
2018年 | 13篇 |
2016年 | 23篇 |
2015年 | 27篇 |
2014年 | 35篇 |
2013年 | 70篇 |
2012年 | 62篇 |
2011年 | 95篇 |
2010年 | 40篇 |
2009年 | 41篇 |
2008年 | 83篇 |
2007年 | 95篇 |
2006年 | 82篇 |
2005年 | 67篇 |
2004年 | 69篇 |
2003年 | 73篇 |
2002年 | 50篇 |
2001年 | 21篇 |
2000年 | 15篇 |
1998年 | 12篇 |
1997年 | 25篇 |
1996年 | 33篇 |
1995年 | 27篇 |
1994年 | 24篇 |
1993年 | 24篇 |
1992年 | 23篇 |
1991年 | 16篇 |
1990年 | 20篇 |
1989年 | 25篇 |
1988年 | 19篇 |
1987年 | 28篇 |
1986年 | 20篇 |
1985年 | 42篇 |
1984年 | 38篇 |
1983年 | 36篇 |
1982年 | 37篇 |
1981年 | 31篇 |
1980年 | 13篇 |
1979年 | 27篇 |
1978年 | 38篇 |
1977年 | 32篇 |
1976年 | 33篇 |
1975年 | 35篇 |
1974年 | 24篇 |
1973年 | 21篇 |
1972年 | 13篇 |
1970年 | 12篇 |
1966年 | 16篇 |
排序方式: 共有1950条查询结果,搜索用时 19 毫秒
1.
BIT Numerical Mathematics - In this article we address the problem of minimizing a strictly convex quadratic function using a novel iterative method. The new algorithm is based on the well-known... 相似文献
2.
Ein elektronenreiches cyclisches (Alkyl)(amino)carben auf Au(111)-, Ag(111)- und Cu(111)-Oberflächen
Anne Bakker Dr. Matthias Freitag Elena Kolodzeiski Peter Bellotti Dr. Alexander Timmer Dr. Jindong Ren Bertram Schulze Lammers Daniel Moock Prof. Dr. Herbert W. Roesky Dr. Harry Mönig Dr. Saeed Amirjalayer Prof. Dr. Harald Fuchs Prof. Dr. Frank Glorius 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13745-13749
3.
Xing Huang Detre Teschner Maria Dimitrakopoulou Alexey Fedorov Benjamin Frank Ralph Kraehnert Frank Rosowski Harry Kaiser Stephan Schunk Christiane Kuretschka Robert Schlgl Marc‐Georg Willinger Annette Trunschke 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(26):8801-8805
The direct conversion of syngas to ethanol, typically using promoted Rh catalysts, is a cornerstone reaction in CO2 utilization and hydrogen storage technologies. A rational catalyst development requires a detailed structural understanding of the activated catalyst and the role of promoters in driving chemoselectivity. Herein, we report a comprehensive atomic‐scale study of metal–promoter interactions in silica‐supported Rh, Rh–Mn, and Rh–Mn–Fe catalysts by aberration‐corrected (AC) TEM. While the catalytic reaction leads to the formation of a Rh carbide phase in the Rh–Mn/SiO2 catalyst, the addition of Fe results in the formation of bimetallic Rh–Fe alloys, which further improves the selectivity and prevents the carbide formation. In all promoted catalysts, Mn is present as an oxide decorating the metal particles. Based on the atomic insight obtained, structural and electronic modifications induced by promoters are revealed and a basis for refined theoretical models is provided. 相似文献
4.
5.
Dr. Joseph N. Capilato Stefan A. Harry Dr. Maxime A. Siegler Prof. Thomas Lectka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202103922
As appreciation for nonclassical hydrogen bonds has progressively increased, so have efforts to characterize these interesting interactions. Whereas several kinds of C−H hydrogen bonds have been well-studied, much less is known about the R3N+−C−H⋅⋅⋅X variety. Herein, we present crystallographic and spectroscopic evidence for the existence of these interactions, with special relevance to Selectfluor chemistry. Of particular note is the propensity for Lewis bases to engage in nonclassical hydrogen bonding over halogen bonding with the electrophilic F atom of Selectfluor. Further, the first examples of 1H NMR experiments detailing R3N+−C−H⋅⋅⋅X (X=O, N) hydrogen bonds are described. 相似文献
6.
He Zhu Dr. Qiang Chen Dr. Igor Rončević Dr. Kirsten E. Christensen Prof. Harry L. Anderson 《Angewandte Chemie (International ed. in English)》2023,62(31):e202307035
π-Conjugated nanoribbons attract interest because of their unusual electronic structures and charge-transport behavior. Here, we report the synthesis of a series of fully edge-fused porphyrin-anthracene oligomeric ribbons (dimer and trimer), together with a computational study of the corresponding infinite polymer. The porphyrin dimer and trimer were synthesized in high yield, via oxidative cyclodehydrogenation of singly linked precursors, using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and trifluoromethanesulfonic acid (TfOH). The crystal structure of the dimer shows that the central π-system is flat, with a slight S-shaped wave distortion at each porphyrin terminal. The extended π-conjugation causes a dramatic red-shift in the absorption spectra: the absorption maxima of the fused dimer and trimer appear at 1188 nm and 1642 nm, respectively (for the nickel complexes dissolved in toluene). The coordinated metal in the dimer was changed from Ni to Mg, using p-tolylmagnesium bromide, providing access to free-base and Zn complexes. These results open a versatile avenue to longer π-conjugated nanoribbons with integrated metalloporphyrin units. 相似文献
7.
Caterpillar Track Complexes in Template‐Directed Synthesis and Correlated Molecular Motion 下载免费PDF全文
Shiqi Liu Dr. Dmitry V. Kondratuk Dr. Sophie A. L. Rousseaux Dr. Guzmán Gil‐Ramírez Dr. Melanie C. O'Sullivan Jonathan Cremers Prof. Tim D. W. Claridge Prof. Harry L. Anderson 《Angewandte Chemie (International ed. in English)》2015,54(18):5355-5359
Small alterations to the structure of a star‐shaped template totally change its mode of operation. The hexapyridyl template directs the conversion of a porphyrin dimer to the cyclic hexamer, but deleting one pyridine site changes the product to the cyclic decamer, while deleting two binding sites changes the product to the cyclic octamer. This surprising switch in selectivity is explained by the formation of 2:1 caterpillar track complexes, in which two template wheels bind inside the nanoring. Caterpillar track complexes can also be prepared by binding the hexapyridyl template inside the 8‐ and 10‐porphyrin nanorings. NMR exchange spectroscopy (EXSY) experiments show that these complexes exhibit correlated motion, in which the conrotatory rotation of the two template wheels is coupled to rotation of the nanoring track. In the case of the 10‐porphyrin system, the correlated motion can be locked by binding palladium(II) dichloride between the two templates. 相似文献
8.
Chaw-Keong Yong Patrick Parkinson Dmitry V. Kondratuk Wei-Hsin Chen Andrew Stannard Alex Summerfield Johannes K. Sprafke Melanie C. O'Sullivan Peter H. Beton Harry L. Anderson Laura M. Herz 《Chemical science》2015,6(1):181-189
Rings of chlorophyll molecules harvest sunlight remarkably efficiently during photosynthesis in purple bacteria. The key to their efficiency lies in their highly delocalized excited states that allow for ultrafast energy migration. Here we show that a family of synthetic nanorings mimic the ultrafast energy transfer and delocalization observed in nature. π-Conjugated nanorings with diameters of up to 10 nm, consisting of up to 24 porphyrin units, are found to exhibit excitation delocalization within the first 200 fs of light absorption. Transitions from the first singlet excited state of the circular nanorings are dipole-forbidden as a result of symmetry constraints, but these selection rules can be lifted through static and dynamic distortions of the rings. The increase in the radiative emission rate in the larger nanorings correlates with an increase in static disorder expected from Monte Carlo simulations. For highly symmetric rings, the radiative rate is found to increase with increasing temperature. Although this type of thermally activated superradiance has been theoretically predicted in circular chromophore arrays, it has not previously been observed in any natural or synthetic systems. As expected, the activation energy for emission increases when a nanoring is fixed in a circular conformation by coordination to a radial template. These nanorings offer extended chromophores with high excitation delocalization that is remarkably stable against thermally induced disorder. Such findings open new opportunities for exploring coherence effects in nanometer molecular rings and for implementing these biomimetic light-harvesters in man-made devices. 相似文献
9.
Dr. Michael Peter Mercer Sam Affleck Dr. Edgardo Maximiliano Gavilán-Arriazu Dr. Alana Aragón Zülke Dr. Philip A. Maughan Shivam Trivedi Prof. Maximilian Fichtner Dr. Anji Reddy Munnangi Prof. Ezequiel P. M. Leiva Prof. Harry Ernst Hoster 《Chemphyschem》2022,23(5):e202100748
Sodium-ion batteries (NIBs) utilize cheaper materials than lithium-ion batteries (LIBs) and can thus be used in larger scale applications. The preferred anode material is hard carbon, because sodium cannot be inserted into graphite. We apply experimental entropy profiling (EP), where the cell temperature is changed under open circuit conditions. EP has been used to characterize LIBs; here, we demonstrate the first application of EP to any NIB material. The voltage versus sodiation fraction curves (voltage profiles) of hard carbon lack clear features, consisting only of a slope and a plateau, making it difficult to clarify the structural features of hard carbon that could optimize cell performance. We find additional features through EP that are masked in the voltage profiles. We fit lattice gas models of hard carbon sodiation to experimental EP and system enthalpy, obtaining: 1. a theoretical maximum capacity, 2. interlayer versus pore filled sodium with state of charge. 相似文献
10.
Harry Biller Swantje Lerch Katharina Tölke Dr. Hans-Georg Stammler Prof. Dr. Berthold Hoge Prof. Dr. Thomas Strassner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(53):13325-13329
We synthesized new imidazolium-based tunable aryl alkyl ionic liquids (TAAILs) with the weakly coordinating tetrakis(pentafluoroethyl)gallate anion, [Ga(C2F5)4]−. Phenyl and phenyl derivatives (2-Me, 4-OMe, 2,4-F) were combined with varying alkyl chain lengths at the imidazolium core leading to TAAILs, which were investigated with regard to their viscosity, conductivity, and electrochemical window and compared to EMIM and BMIM standard cations. Remarkable low viscosities of 29 cP at 25 °C for [BMIM][Ga(C2F5)4] were achieved. However, the EMIM and BMIM gallates show electrochemical instability, releasing pentafluoroethane at a voltage of 1.5 V. The 2-Me-substituted gallate-TAAILs slowly decompose over several weeks, whereas all other gallate-TAAILs showed no decomposition at all. With electrochemical windows of up to 5.15 V and low viscosities in a range of 66–162 cP, the gallate-TAAILs are promising candidates as electrolytes in electrochemical applications. 相似文献