全文获取类型
收费全文 | 403篇 |
免费 | 23篇 |
国内免费 | 2篇 |
专业分类
化学 | 303篇 |
晶体学 | 2篇 |
力学 | 16篇 |
数学 | 26篇 |
物理学 | 81篇 |
出版年
2024年 | 2篇 |
2023年 | 16篇 |
2022年 | 11篇 |
2021年 | 14篇 |
2020年 | 20篇 |
2019年 | 20篇 |
2018年 | 6篇 |
2017年 | 7篇 |
2016年 | 21篇 |
2015年 | 12篇 |
2014年 | 9篇 |
2013年 | 18篇 |
2012年 | 23篇 |
2011年 | 30篇 |
2010年 | 11篇 |
2009年 | 12篇 |
2008年 | 21篇 |
2007年 | 30篇 |
2006年 | 27篇 |
2005年 | 16篇 |
2004年 | 16篇 |
2003年 | 12篇 |
2002年 | 9篇 |
2001年 | 2篇 |
2000年 | 6篇 |
1999年 | 3篇 |
1998年 | 3篇 |
1996年 | 2篇 |
1992年 | 2篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 3篇 |
1985年 | 1篇 |
1984年 | 7篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1979年 | 4篇 |
1978年 | 1篇 |
1977年 | 3篇 |
1976年 | 1篇 |
1960年 | 1篇 |
1940年 | 1篇 |
1939年 | 1篇 |
1938年 | 1篇 |
1935年 | 2篇 |
1932年 | 3篇 |
1930年 | 1篇 |
1924年 | 1篇 |
排序方式: 共有428条查询结果,搜索用时 15 毫秒
61.
Patricia J. Nance Niklas B. Thompson Paul H. Oyala Jonas C. Peters 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(19):6286-6290
Species with 2‐center, 3‐electron (2c/3e?) σ bonds are of interest owing to their fascinating electronic structures and potential for interesting reactivity patterns. Report here is the synthesis and characterization of a pair of zerovalent (d9) trigonal pyramidal Rh and Ir complexes that feature 2c/3e? σ bonds to the Si atom of a tripodal tris(phosphine)silatrane ligand. X‐ray diffraction, continuous wave and pulse electron paramagnetic resonance, density‐functional theory calculations, and reactivity studies have been used to characterize these electronically distinctive compounds. The data available highlight a 2c/3e? bonding framework with a σ*‐SOMO of metal 4‐ or 5dz2 parentage that is partially stabilized by significant mixing with Si (3pz) and metal (5‐ or 6pz) orbitals. Metal‐ligand covalency thus buffers the expected destabilization of transition‐metal (TM)‐silyl σ*‐orbitals by d–p mixing, affording well‐characterized examples of TM–main group, and hence polar, 2c/3e? σ “half‐bonds”. 相似文献
62.
Prashanth W. Menezes Carsten Walter Jan Niklas Hausmann Rodrigo Beltrn‐Suito Christopher Schlesiger Sebastian Praetz Valeriy Yu. Verchenko Andrei V. Shevelkov Matthias Driess 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(46):16722-16727
Erstmals wurden, in einen intermetallischen Vorläuferansatz, durch In‐situ‐Elektrokonversion von Mangangallid (MnGa4) hochleistungsfähige und langzeitstabile MnOx‐basierte Elektrokatalysatoren für die Wasseroxidation in alkalischem Medium hergestellt. Überraschend führt seine Elektrokorrosion, unter gleichzeitigem Verlust von Ga, gleichzeitig zu drei kristallinen Typen von MnOx‐Mineralien mit verschiedenen Strukturen und induzierten Defekten: Birnessit δ‐MnO2, Feitknechtit β‐MnOOH und Hausmannit α‐Mn3O4. Das Vorkommen und die intrinsische Stabilität von aktiven MnIII/MnIV‐Zentren in den drei gebildeten MnOx‐Phasen erklärt die hervorragende Effizienz und Stabilität des Systems für die elektrokatalytische Wasseroxidation. Nach der elektrophoretischen Abscheidung des MnGa4‐Vorläufers auf elektrisch leitfähigem Nickelschaum wurde ein niedriges Überpotential von 291 mV bei der Stromdichte von 10 mA cm?2 erreicht, das praktisch den Überpotentialen von edelmetallbasierten Katalysatoren entspricht und für mehr als fünf Tage beständig ist. 相似文献
63.
Lena Quambusch Ina Landel Laura Depta Jrn Weisner Niklas Uhlenbrock Matthias P. Müller Franziska Glanemann Kristina Althoff Jens T. Siveke Daniel Rauh 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(52):18999-19005
Isoforms of protein kinase Akt are involved in essential processes including cell proliferation, survival, and metabolism. However, their individual roles in health and disease have not been thoroughly evaluated. Thus, there is an urgent need for perturbation studies, preferably mediated by highly selective bioactive small molecules. Herein, we present a structure‐guided approach for the design of structurally diverse and pharmacologically beneficial covalent‐allosteric modifiers, which enabled an investigation of the isoform‐specific preferences and the important residues within the allosteric site of the different isoforms. The biochemical, cellular, and structural evaluations revealed interactions responsible for the selective binding profiles. The isoform‐selective covalent‐allosteric Akt inhibitors that emerged from this approach showed a conclusive structure–activity relationship and broke ground in the development of selective probes to delineate the isoform‐specific functions of Akt kinases. 相似文献
64.
Sebastian Schroeder Christina Strauch Niklas Gaelings Meike Niggemann 《Angewandte Chemie (International ed. in English)》2019,58(15):5119-5123
A new concept for selectivity control in carbocation‐driven reactions has been identified which allows for the chemo‐, regio‐, and stereoselective addition of nucleophiles to alkynes—assisted vinyl cation formation—enabled by a Li+‐based supramolecular framework. Mechanistic analysis of a model complex (Li2NTf2+?3 H2O) confirms that solely the formation of a complex between the incoming nucleophile and the transition state of the alkyne protonation is responsible for the resulting selective N addition to the vinyl cation. Into the bargain, a general, operationally simple synthetic procedure to previously inaccessible vinyl triflimides is provided. 相似文献
65.
Gustavsson M Haller E Mark MJ Danzl JG Rojas-Kopeinig G Nägerl HC 《Physical review letters》2008,100(8):080404
We report on the control of interaction-induced dephasing of Bloch oscillations for an atomic Bose-Einstein condensate in an optical lattice. We quantify the dephasing in terms of the width of the quasimomentum distribution and measure its dependence on time for different interaction strengths which we control by means of a Feshbach resonance. For minimal interaction, the dephasing time is increased from a few to more than 20 thousand Bloch oscillation periods, allowing us to realize a BEC-based atom interferometer in the noninteracting limit. 相似文献
66.
We discuss the relative speeds DeltaV of inertial particles suspended in a highly turbulent gas when the Stokes number, a dimensionless measure of their inertia, is large. We identify a mechanism giving rise to the distribution P(DeltaV) approximately exp(-C|DeltaV|(4/3)) (for some constant C). Our conclusions are supported by numerical simulations, and by the analytical solution of a model equation of motion. The results determine the rate of collisions between suspended particles. They are relevant to the hypothesized mechanism for formation of planets by aggregation of dust particles in circumstellar nebula. 相似文献
67.
Both compressible and incompressible Navier-Stokes solvers can be used and are used to solve incompressible turbulent flow problems. In the compressible case, the Mach number is then considered as a solver parameter that is set to a small value, M ≈0.1, in order to mimic incompressible flows. This strategy is widely used for high-order discontinuous Galerkin (DG) discretizations of the compressible Navier-Stokes equations. The present work raises the question regarding the computational efficiency of compressible DG solvers as compared to an incompressible formulation. Our contributions to the state of the art are twofold: Firstly, we present a high-performance DG solver for the compressible Navier-Stokes equations based on a highly efficient matrix-free implementation that targets modern cache-based multicore architectures with Flop/Byte ratios significantly larger than 1. The performance results presented in this work focus on the node-level performance, and our results suggest that there is great potential for further performance improvements for current state-of-the-art DG implementations of the compressible Navier-Stokes equations. Secondly, this compressible Navier-Stokes solver is put into perspective by comparing it to an incompressible DG solver that uses the same matrix-free implementation. We discuss algorithmic differences between both solution strategies and present an in-depth numerical investigation of the performance. The considered benchmark test cases are the three-dimensional Taylor-Green vortex problem as a representative of transitional flows and the turbulent channel flow problem as a representative of wall-bounded turbulent flows. The results indicate a clear performance advantage of the incompressible formulation over the compressible one. 相似文献
68.
69.
Clemens K. Blasius Niklas F. Heinrich Dr. Vladislav Vasilenko Prof. Lutz H. Gade 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16108-16111
A readily activated iron alkyl precatalyst effectively catalyzes the highly enantioselective hydroboration of N-alkyl imines. Employing a chiral bis(oxazolinylmethylidene)isoindoline pincer ligand, the asymmetric reduction of various acyclic N-alkyl imines provided the corresponding α-chiral amines in excellent yields and with up to >99 % ee. The applicability of this base metal catalytic system was further demonstrated with the synthesis of the pharmaceuticals Fendiline and Tecalcet. 相似文献
70.
Amit Kumar Trevor Janes Subrata Chakraborty Prosenjit Daw Niklas vonWolff Raanan Carmieli Yael Diskin‐Posner David Milstein 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(11):3411-3415
We report a C?C bond‐forming reaction between benzyl alcohols and alkynes in the presence of a catalytic amount of KOtBu to form α‐alkylated ketones in which the C=O group is located on the side derived from the alcohol. The reaction proceeds under thermal conditions (125 °C) and produces no waste, making the reaction highly atom efficient, environmentally benign, and sustainable. Based on our mechanistic investigations, we propose that the reaction proceeds through radical pathways. 相似文献