全文获取类型
收费全文 | 940篇 |
免费 | 51篇 |
国内免费 | 2篇 |
专业分类
化学 | 674篇 |
晶体学 | 3篇 |
力学 | 24篇 |
数学 | 73篇 |
物理学 | 219篇 |
出版年
2023年 | 17篇 |
2022年 | 22篇 |
2021年 | 24篇 |
2020年 | 30篇 |
2019年 | 13篇 |
2018年 | 12篇 |
2017年 | 14篇 |
2016年 | 33篇 |
2015年 | 28篇 |
2014年 | 33篇 |
2013年 | 50篇 |
2012年 | 80篇 |
2011年 | 86篇 |
2010年 | 50篇 |
2009年 | 33篇 |
2008年 | 42篇 |
2007年 | 49篇 |
2006年 | 42篇 |
2005年 | 43篇 |
2004年 | 30篇 |
2003年 | 27篇 |
2002年 | 22篇 |
2001年 | 10篇 |
2000年 | 15篇 |
1999年 | 13篇 |
1998年 | 8篇 |
1997年 | 10篇 |
1996年 | 11篇 |
1995年 | 10篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 9篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1985年 | 6篇 |
1980年 | 7篇 |
1979年 | 4篇 |
1977年 | 3篇 |
1976年 | 6篇 |
1975年 | 5篇 |
1974年 | 6篇 |
1973年 | 4篇 |
1972年 | 8篇 |
1971年 | 4篇 |
1969年 | 4篇 |
1967年 | 3篇 |
1955年 | 3篇 |
1913年 | 3篇 |
排序方式: 共有993条查询结果,搜索用时 0 毫秒
21.
Lei Liu Wes Lee Mingbin Yuan Chris Acha Michael B. Geherty Brandon Williams Osvaldo Gutierrez 《Chemical science》2020,11(12):3146
Design and implementation of the first (asymmetric) Fe-catalyzed intra- and intermolecular difunctionalization of vinyl cyclopropanes (VCPs) with alkyl halides and aryl Grignard reagents has been realized via a mechanistically driven approach. Mechanistic studies support the diffusion of alkyl radical intermediates out of the solvent cage to participate in an intra- or intermolecular radical cascade with a range of VCPs followed by re-entering the Fe radical cross-coupling cycle to undergo (stereo)selective C(sp2)–C(sp3) bond formation. This work provides a proof-of-concept of the use of vinyl cyclopropanes as synthetically useful 1,5-synthons in Fe-catalyzed conjunctive cross-couplings with alkyl halides and aryl/vinyl Grignard reagents. Overall, we provide new design principles for Fe-mediated radical processes and underscore the potential of using combined computations and experiments to accelerate the development of challenging transformations.Design and implementation of the first (asymmetric) Fe-catalyzed intra- and intermolecular difunctionalization of vinyl cyclopropanes (VCPs) with alkyl halides and aryl Grignard reagents has been realized via a mechanistically driven approach. 相似文献
22.
Walid M. Hikal Sanjoy K. Bhattacharia Mark W. Vaughn Brandon L. Weeks 《Molecules (Basel, Switzerland)》2022,27(17)
In this article, we report the in-situ nanoscale experimental measurement of sublimation rates, activation energy of sublimation, and diffusion coefficients of 2,4,6-trinitrotoluene (TNT) single crystals in air using atomic force microscopy (AFM). The crystals were prepared by slow evaporation at 5 °C using acetone-dissolved TNT. The mass loss was calculated by monitoring the shrinkage of the surface area of layered islands formed on the surface of the TNT crystals due to sublimation upon isothermal heating at temperatures below the melting point. The results suggest the sublimation process occurs via two-dimensional detachment of TNT molecules from the non-prominent facets on the crystal surface which imitates the nucleation and crystal growth process. Sublimation rates are one order of magnitude smaller than previously reported values. However, the calculated activation energy (112.15 ± 3.2 kJ/mol) and temperature-dependent sublimation rates agree well with the reported values for TNT thin films and microcrystals determined by UV-vis absorbance spectroscopy and quartz crystal microscopy (QCM) (90–141 kJ/mol). The average diffusion coefficient is (4.35 × 10–6 m2/s) which is within the range of the reported theoretical values with an average of 5.59 × 10–6 m2/s, and about 25% less than that determined using thermogravimetric analysis for powder TNT. 相似文献
23.
Dr. Kaveh Matinkhoo Antonio A. W. L. Wong Dr. Chido M. Hambira Brandon Kato Charlie Wei Dr. Christoph Müller Dr. Torsten Hechler Dr. Alexandra Braun Dr. Francesca Gallo Dr. Andreas Pahl Prof. David M. Perrin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(40):10282-10292
Alpha-amanitin, an extremely toxic bicyclic octapeptide extracted from the death-cap mushroom, Amanita phalloides, is a highly selective allosteric inhibitor of RNA polymerase II. Following on growing interest in using this toxin as a payload in antibody-drug conjugates, herein we report the synthesis and biochemical evaluation of several new derivatives of this toxin to probe the role of the trans-hydroxyproline (Hyp), which is known to be critical for toxicity. This structure activity relationship (SAR) study represents the first of its kind to use various Hyp-analogs to alter the conformational and H-bonding properties of Hyp in amanitin. 相似文献
24.
25.
26.
27.
William K. Bell Brandon M. Rawlings Brian K. Long R. Chad Webb B. Keith Keitz Lukas Häußling C. Grant Willson 《Journal of polymer science. Part A, Polymer chemistry》2014,52(19):2769-2775
A series of photocrosslinkable polymers bearing hyperpolarizable side chain chromophores was synthesized, poled and evaluated on the basis of the thermal stability of Second Harmonic Generation (SHG). Photoinitiation allowed for control of the onset of curing. Crosslinking was monitored by infrared spectroscopy and optimal conversion was achieved by applying a slow temperature ramp during exposure. The ultimate stability of the poled polymers was directly related to the number of crosslinking substituents that were attached to the chromophore pendant group. With two reactive groups per chromophore significant SHG was retained at temperatures above the initial polymer glass transition temperature. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2769–2775 相似文献
28.
Dr. Renata Kaczmarek Samuel Ward Dipra Debnath Taisiya Jacobs Alexander D. Stark Dariusz Korczyński Prof. Dr. Anil Kumar Prof. Dr. Michael D. Sevilla Dr. Sergey A. Denisov Dr. Viacheslav Shcherbakov Dr. Pascal Pernot Prof. Dr. Mehran Mostafavi Prof. Dr. Roman Dembinski Prof. Dr. Amitava Adhikary 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(43):9495-9505
The directionality of the hole-transfer processes between DNA backbone and base was investigated by using phosphorodithioate [P(S−)=S] components. ESR spectroscopy in homogeneous frozen aqueous solutions and pulse radiolysis in aqueous solution at ambient temperature confirmed initial formation of G.+-P(S−)=S. The ionization potential of G-P(S−)=S was calculated to be slightly lower than that of guanine in 5′-dGMP. Subsequent thermally activated hole transfer from G.+ to P(S−)=S led to dithiyl radical (P-2S.) formation on the μs timescale. In parallel, ESR spectroscopy, pulse radiolysis, and density functional theory (DFT) calculations confirmed P-2S. formation in an abasic phosphorodithioate model compound. ESR investigations at low temperatures and higher G-P(S−)=S concentrations showed a bimolecular conversion of P-2S. to the σ2-σ*1-bonded dimer anion radical [-P-2S 2S-P-]− [ΔG (150 K, DFT)=−7.2 kcal mol−1]. However, [-P-2S 2S-P-]− formation was not observed by pulse radiolysis [ΔG° (298 K, DFT)=−1.4 kcal mol−1]. Neither P-2S. nor [-P-2S 2S-P-]− oxidized guanine base; only base-to-backbone hole transfer occurs in phosphorodithioate. 相似文献
29.
Gerhard Gompper Clemens Bechinger Stephan Herminghaus Rolf Isele-Holder U. Benjamin Kaupp Hartmut Löwen Holger Stark Roland G. Winkler 《The European physical journal. Special topics》2016,225(11-12):2061-2064
Locomotion of autonomous microswimmers is a fascinating field at the cutting edge of science. It combines the biophysics of self-propulsion via motor proteins, artificial propulsion mechanisms, swimming strategies at low Reynolds numbers, the hydrodynamic interaction of swimmers, and the collective motion and synchronisation of large numbers of agents. The articles of this Special Issue are based on the lecture notes of an international summer school, which was organized by the DFG Priority Programme 1726 “Microswimmers – From Single Particle Motion to Collective Behaviour” in the fall of 2015. The minireviews provide a broad overview of the field, covering both elementary and advanced material, as well as selected areas from current research. 相似文献
30.
Pulsed electrohydrodynamic atomisation (EHDA) of aqueous 10 nm gold colloid in a full voltage-controlled form was investigated. By using 4 µm and 20 μm nozzles, electrified fluid jet was emitted and Au nanoparticles in the jet were deposited onto a silicon substrate. Scanning electron microscopy (SEM) revealed that different morphology of the artifact was formed by using different voltages pulses. Particularly, island-liked artifact down to 10 μm can be produced regularly in the case of cone-jet mode by low voltage pulse. Our results demonstrate pulsed EHDA is a promising approach in creating micro-patterns of colloid-based nanomaterials. 相似文献