全文获取类型
收费全文 | 1067篇 |
免费 | 94篇 |
国内免费 | 5篇 |
专业分类
化学 | 849篇 |
晶体学 | 14篇 |
力学 | 18篇 |
数学 | 121篇 |
物理学 | 164篇 |
出版年
2023年 | 29篇 |
2022年 | 32篇 |
2021年 | 45篇 |
2020年 | 63篇 |
2019年 | 54篇 |
2018年 | 22篇 |
2017年 | 30篇 |
2016年 | 52篇 |
2015年 | 61篇 |
2014年 | 45篇 |
2013年 | 56篇 |
2012年 | 66篇 |
2011年 | 79篇 |
2010年 | 38篇 |
2009年 | 42篇 |
2008年 | 44篇 |
2007年 | 40篇 |
2006年 | 44篇 |
2005年 | 23篇 |
2004年 | 16篇 |
2003年 | 18篇 |
2002年 | 18篇 |
2001年 | 13篇 |
2000年 | 10篇 |
1999年 | 11篇 |
1998年 | 13篇 |
1996年 | 5篇 |
1995年 | 7篇 |
1994年 | 4篇 |
1993年 | 9篇 |
1992年 | 5篇 |
1991年 | 8篇 |
1990年 | 8篇 |
1989年 | 11篇 |
1988年 | 9篇 |
1987年 | 6篇 |
1986年 | 5篇 |
1985年 | 9篇 |
1984年 | 5篇 |
1983年 | 5篇 |
1982年 | 10篇 |
1981年 | 8篇 |
1980年 | 8篇 |
1979年 | 4篇 |
1977年 | 15篇 |
1976年 | 8篇 |
1975年 | 10篇 |
1974年 | 6篇 |
1973年 | 8篇 |
1937年 | 5篇 |
排序方式: 共有1166条查询结果,搜索用时 31 毫秒
981.
Tim Mller Fabian Scholten Trung Ngo Thanh Ilya Sinev Janis Timoshenko Xingli Wang Zarko Jovanov Manuel Gliech Beatriz Roldan Cuenya Ana Sofia Varela Peter Strasser 《Angewandte Chemie (International ed. in English)》2020,59(41):17974-17983
The direct electrochemical conversion of carbon dioxide (CO2) into multi‐carbon (C2+) products still faces fundamental and technological challenges. While facet‐controlled and oxide‐derived Cu materials have been touted as promising catalysts, their stability has remained problematic and poorly understood. Herein we uncover changes in the chemical and morphological state of supported and unsupported Cu2O nanocubes during operation in low‐current H‐Cells and in high‐current gas diffusion electrodes (GDEs) using neutral pH buffer conditions. While unsupported nanocubes achieved a sustained C2+ Faradaic efficiency of around 60 % for 40 h, the dispersion on a carbon support sharply shifted the selectivity pattern towards C1 products. Operando XAS and time‐resolved electron microscopy revealed the degradation of the cubic shape and, in the presence of a carbon support, the formation of small Cu‐seeds during the surprisingly slow reduction of bulk Cu2O. The initially (100)‐rich facet structure has presumably no controlling role on the catalytic selectivity, whereas the oxide‐derived generation of under‐coordinated lattice defects, can support the high C2+ product yields. 相似文献
982.
Fabian M. Hrmann Christoph Kerzig Tim S. Chung Andreas Bauer Oliver S. Wenger Thorsten Bach 《Angewandte Chemie (International ed. in English)》2020,59(24):9659-9668
Chiral eniminium salts, prepared from α,β‐unsaturated aldehydes and a chiral proline derived secondary amine, underwent, upon irradiation with visible light, a ruthenium‐catalyzed (2.5 mol %) intermolecular [2+2] photocycloaddition to olefins, which after hydrolysis led to chiral cyclobutanecarbaldehydes (17 examples, 49–74 % yield), with high diastereo‐ and enantioselectivities. Ru(bpz)3(PF6)2 was utilized as the ruthenium catalyst and laser flash photolysis studies show that the catalyst operates exclusively by triplet‐energy transfer (sensitization). A catalytic system was devised with a chiral secondary amine co‐catalyst. In the catalytic reactions, Ru(bpy)3(PF6)2 was employed, and laser flash photolysis experiments suggest it undergoes both electron and energy transfer. However, experimental evidence supports the hypothesis that energy transfer is the only productive quenching mechanism. Control experiments using Ir(ppy)3 showed no catalysis for the intermolecular [2+2] photocycloaddition of an eniminium ion. 相似文献
983.
Dr. Fabian Eisenreich Prof. Dr. E. W. Meijer Prof. Dr. Anja R. A. Palmans 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(45):10355-10361
Photoredox catalysis has recently emerged as a powerful synthesis tool in organic and polymer chemistry. In contrast to the great achievements realized in organic solvents, performing photocatalytic processes efficiently in aqueous media encounters several challenges. Here, it is presented how amphiphilic single-chain polymeric nanoparticles (SCPNs) can be utilized as small reactors to conduct light-driven chemical reactions in water. By incorporating a phenothiazine (PTH) catalyst into the polymeric scaffold, metal-free reduction and C−C cross-coupling reactions can be carried out upon exposure to UV light under ambient conditions. The versatility of this approach is underlined by a large substrate scope, tolerance towards oxygen, and excellent recyclability. This approach thereby contributes to a sustainable and green way of implementing photoredox catalysis. 相似文献
984.
Dr. Florian Albrecht Dulce Rey Dr. Shadi Fatayer Dr. Fabian Schulz Dr. Dolores Pérez Dr. Diego Peña Dr. Leo Gross 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(51):23189-23193
Glaser-like coupling of terminal alkynes by thermal activation is extensively used in on-surface chemistry. Here we demonstrate an intramolecular version of this reaction performed by atom manipulation. We used voltage pulses from the tip to trigger a Glaser-like coupling between terminal alkyne carbons within a custom-synthesized precursor molecule adsorbed on bilayer NaCl on Cu(111). Different conformations of the precursor molecule and the product were characterized by molecular structure elucidation with atomic force microscopy and orbital density mapping with scanning tunneling microscopy, accompanied by density functional theory calculations. We revealed partially dehydrogenated intermediates, providing insight into the reaction pathway. 相似文献
985.
The first total synthesis of (−)-rotundone has been accomplished from (+)-(R)-limonene and therefore for the first time from an unrelated monoterpene instead of modifying structurally closely related sesquiterpene precursors such as α-guaiene. Challenges such as intermediates with stereocenters prone to epimerization by enolization were overcome by designing a β-methyl-keto route starting from (+)-(R)-limonene which finally gave (−)-rotundone by Nazarov cyclization of a precursor 13a . Diastereomer (−)-epi-rotundone was separated from (−)-rotundone chromatographically. An alternative route from rac-citronellal provided a diastereomer mixture of racemic Nazarov precursor 13 through a TRIP-catalyzed intramolecular aldolization, thus indicating that the Nazarov cyclization precursor 13a is in principle accessible from (−)-(S)-citronellal. The 11-step synthesis from (+)-(R)-limonene with ca. 1 % overall yield confirmed the absolute configuration of (−)-rotundone and provided samples of good olfactory quality. 相似文献
986.
A Glycan Array-Based Assay for the Identification and Characterization of Plant Glycosyltransferases
Dr. Colin Ruprecht Dr. Max P. Bartetzko Dr. Deborah Senf Dr. Anna Lakhina Dr. Peter J. Smith Dr. Maria J. Soto Hyunil Oh Dr. Jeong-Yeh Yang Dr. Digantkumar Chapla Dr. Daniel Varon Silva Prof. Dr. Mads H. Clausen Prof. Dr. Michael G. Hahn Prof. Dr. Kelley W. Moremen Prof. Dr. Breeanna R. Urbanowicz Prof. Dr. Fabian Pfrengle 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(30):12593-12598
Growing plants with modified cell wall compositions is a promising strategy to improve resistance to pathogens, increase biomass digestibility, and tune other important properties. In order to alter biomass architecture, a detailed knowledge of cell wall structure and biosynthesis is a prerequisite. We report here a glycan array-based assay for the high-throughput identification and characterization of plant cell wall biosynthetic glycosyltransferases (GTs). We demonstrate that different heterologously expressed galactosyl-, fucosyl-, and xylosyltransferases can transfer azido-functionalized sugar nucleotide donors to selected synthetic plant cell wall oligosaccharides on the array and that the transferred monosaccharides can be visualized “on chip” by a 1,3-dipolar cycloaddition reaction with an alkynyl-modified dye. The opportunity to simultaneously screen thousands of combinations of putative GTs, nucleotide sugar donors, and oligosaccharide acceptors will dramatically accelerate plant cell wall biosynthesis research. 相似文献
987.
4OR - A Correction to this paper has beed published: 10.1007/s10288-020-00442-1 相似文献
988.
The optimization of target conflicts between the various tire properties dominates the development of modern vehicle tires. Therefore, the tire became a very complex high‐tech‐product. Every single step is a very challenging process, starting with the raw materials and their mixing, going on to the shaping of the singe parts and finishing with the building of the uncured tire and the vulcanization. A very important raw material is the natural rubber. As it is a natural product, it has some special chemical and physical properties which need some special attention during the processing. 相似文献
989.
Fabian M. Schaller Sebastian C. Kapfer Myfanwy E. Evans Matthias J.F. Hoffmann Tomaso Aste Mohammad Saadatfar 《哲学杂志》2013,93(31-33):3993-4017
AbstractSeveral approaches to quantitative local structure characterization for particulate assemblies, such as structural glasses or jammed packings, use the partition of space provided by the Voronoi diagram. The conventional construction for spherical mono-disperse particles, by which the Voronoi cell of a particle is that of its centre point, cannot be applied to configurations of aspherical or polydisperse particles. Here, we discuss the construction of a Set Voronoi diagram for configurations of aspherical particles in three-dimensional space. The Set Voronoi cell of a given particle is composed of all points in space that are closer to the surface (as opposed to the centre) of the given particle than to the surface of any other; this definition reduces to the conventional Voronoi diagram for the case of mono-disperse spheres. An algorithm for the computation of the Set Voronoi diagram for convex particles is described, as a special case of a Voronoi-based medial axis algorithm, based on a triangulation of the particles’ bounding surfaces. This algorithm is further improved by a pre-processing step based on morphological erosion, which improves the quality of the approximation and circumvents the problems associated with small degrees of particle–particle overlap that may be caused by experimental noise or soft potentials. As an application, preliminary data for the volume distribution of disordered packings of mono-disperse oblate ellipsoids, obtained from tomographic imaging, is computed. 相似文献
990.