全文获取类型
收费全文 | 2522篇 |
免费 | 105篇 |
国内免费 | 19篇 |
专业分类
化学 | 1768篇 |
晶体学 | 17篇 |
力学 | 20篇 |
数学 | 429篇 |
物理学 | 412篇 |
出版年
2023年 | 14篇 |
2022年 | 20篇 |
2021年 | 49篇 |
2020年 | 58篇 |
2019年 | 69篇 |
2018年 | 53篇 |
2017年 | 54篇 |
2016年 | 107篇 |
2015年 | 84篇 |
2014年 | 109篇 |
2013年 | 176篇 |
2012年 | 175篇 |
2011年 | 220篇 |
2010年 | 128篇 |
2009年 | 111篇 |
2008年 | 165篇 |
2007年 | 145篇 |
2006年 | 137篇 |
2005年 | 96篇 |
2004年 | 94篇 |
2003年 | 63篇 |
2002年 | 65篇 |
2001年 | 28篇 |
2000年 | 22篇 |
1999年 | 21篇 |
1998年 | 27篇 |
1997年 | 18篇 |
1996年 | 24篇 |
1995年 | 16篇 |
1994年 | 8篇 |
1993年 | 20篇 |
1992年 | 12篇 |
1991年 | 13篇 |
1990年 | 8篇 |
1989年 | 9篇 |
1987年 | 17篇 |
1986年 | 8篇 |
1985年 | 10篇 |
1983年 | 9篇 |
1981年 | 8篇 |
1980年 | 10篇 |
1979年 | 10篇 |
1975年 | 8篇 |
1973年 | 8篇 |
1968年 | 7篇 |
1966年 | 7篇 |
1964年 | 7篇 |
1963年 | 11篇 |
1962年 | 7篇 |
1955年 | 9篇 |
排序方式: 共有2646条查询结果,搜索用时 656 毫秒
101.
102.
103.
Leo Valenta Petr Kovaí
ek Vclav Vale Zdenk Bastl Karolina A. Drogowska Timotheus A. Verhagen Radek Cibulka Martin Kalb
《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(5):1338-1342
Spatially resolved functionalization of 2D materials is highly demanded but very challenging to achieve. The chemical patterning is typically tackled by preventing contact between the reagent and material, which brings various accompanying challenges. Photochemical transformation on the other hand inherently provides remote high spatiotemporal resolution using the cleanest reagent—a photon. Herein, we combine two competing reactions on a graphene substrate to create functionalization patterns on a micrometer scale via the Mitsunobu reaction. The mild reaction conditions allow introduction of covalently dynamic linkages, which can serve as reversible labels for surface‐ or graphene‐enhanced Raman spectroscopy characterization of the patterns prepared. The proposed methodology thus provides a pathway for local introduction of arbitrary functional groups on graphene. 相似文献
104.
Marcin Libera Petr Formanek Leonard Schellkopf Barbara Trzebicka Andrzej Dworak Manfred Stamm 《Journal of polymer science. Part A, Polymer chemistry》2014,52(24):3488-3497
Dendritic copolymers comprising a hydrophobic core and hydrophilic shell with nearly equal numbers of hydroxyl groups in the shell and different densities in the core were prepared by a multi‐step process based on anionic ring‐opening polymerization. The diversity in the core density was obtained by using copolymer stars with poly(tert‐butyl‐glycidylether)‐block‐polyglycidol arms with nearly equal length of hydrophobic blocks and numbers of hydroxyl groups of polyglycidol but different numbers of arms as macroinitiators. The ability of the dendritic copolymers to serve as a nanocontainer for a ruthenium complex Ru(NH3)3Cl3 with anticancer properties was studied. The possibility of improving the water solubility of this poorly soluble drug by loading it onto dendritic copolymers was investigated. The hydroxyl groups of the dendritic copolymers were used for complexation of the ruthenium compound to the shell. The loading efficiency was analyzed by UV–vis spectroscopy. The dendritic nanoparticles in their hydrated state were visualized using cryo‐TEM. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3488–3497 相似文献
105.
Dr. Jana Hudecová Dr. Josef Kapitán Prof. Martin Dračínský Pavel Michal Dr. Václav Profant Prof. Petr Bouř 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(59):e202202045
The histidine residue has an exceptional affinity for metals, but solution structure of its complexes are difficult to study. For zinc and nickel complexes, Raman and Raman optical activity (ROA) spectroscopy methods to investigate the link between spectral shapes and the geometry were used. The spectra were recorded and interpreted on the basis of ionic equilibria, molecular dynamics, ab initio molecular dynamics, and density functional theory. For zwitterionic histidine the dominant tautomer was determined by the decomposition of experimental spectra into calculated subspectra. An octahedral structure was found to prevail for the ZnHis2 complex in solution, in contrast to a tetrahedral arrangement in the crystal phase. The solution geometry of NiHis2 is more similar to the octahedral structure found by X-ray. The Raman and ROA structural determinations of metal complexes are dependent on extensive computations, but reveal unique information about the studied systems. 相似文献
106.
107.
108.
Diana Gonzalez Joseph T. Golab Andrew J. Cigler James A. Kaduk 《Acta Crystallographica. Section C, Structural Chemistry》2020,76(7):706-715
The crystal structures of a new polymorph of dipotassium hydrogen citrate, 2K+·HC6H5O72?, and potassium rubidium hydrogen citrate, K+·Rb+·HC6H5O72?, have been solved and refined using laboratory powder X‐ray diffraction and optimized using density functional techniques. In the new polymorph of the dipotassium salt, KO7 and KO8 coordination polyhedra share corners and edges to form a three‐dimensional framework with channels parallel to the a axis and [111]. The hydrophobic methylene groups face each other in the channels. The un‐ionized carboxylic acid group forms a strong charge‐assisted hydrogen bond to the central ionized carboxylate group. The hydroxy group forms an intermolecular hydrogen bond to a different central carboxylate group. In the potassium rubidium salt, the K+ and Rb+ cations are disordered over two sites, in approximately 0.72:0.28 and 0.28:0.72 ratios. KO8 and RbO9 coordination polyhedra share corners and edges to form a three‐dimensional framework with channels parallel to the a axis. The un‐ionized carboxylic acid group forms a strong charge‐assisted hydrogen bond to an ionized carboxylate group. The hydroxy group forms an intermolecular hydrogen bond to the central carboxylate group. Density functional theory (DFT) calculations on the ordered cation structures suggest that interchange of K+ and Rb+ at the two cation sites changes the energy insignificantly. 相似文献
109.
Dr. Alexey A. Mikhaylov Dr. Alexander G. Medvedev Dr. Andrei V. Churakov Dmitry A. Grishanov Dr. Petr V. Prikhodchenko Prof. Dr. Ovadia Lev 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(9):2980-2986
Tellurium–peroxo complexes in aqueous solutions have never been reported. In this work, ammonium peroxotellurates (NH4)4Te2(μ‐OO)2(μ‐O)O4(OH)2 ( 1 ) and (NH4)5Te2(μ‐OO)2(μ‐O)O5(OH)?1.28 H2O?0.72 H2O2 ( 2 ) were isolated from 5 % hydrogen peroxide aqueous solutions of ammonium tellurate and characterized by single‐crystal and powder X‐ray diffraction analysis, by Raman spectroscopy and thermal analysis. The crystal structure of 1 comprises ammonium cations and a symmetric binuclear peroxotellurate anion [Te2(μ‐OO)2(μ‐O)O4(OH)2]4?. The structure of 2 consists of an unsymmetrical [Te2(μ‐OO)2(μ‐O)O5(OH)]5? anion, ammonium cations, hydrogen peroxide, and water. Peroxotellurate anions in both 1 and 2 contain a binuclear Te2(μ‐OO)2(μ‐O) fragment with one μ‐oxo‐ and two μ‐peroxo bridging groups. 125Te NMR spectroscopic analysis shows that the peroxo bridged bitellurate anions are the dominant species in solution, with 3–40 %wt H2O2 and for pH values above 9. DFT calculations of the peroxotellurate anion confirm its higher thermodynamic stability compared with those of the oxotellurate analogues. This is the first direct evidence for tellurium–peroxide coordination in any aqueous system and the first report of inorganic tellurium–peroxo complexes. General features common to all reported p‐block element peroxides could be discerned by the characterization of aqueous and crystalline peroxotellurates. 相似文献
110.
Advanced Sensing of Antibiotics with Magnetic Gold Nanocomposite: Electrochemical Detection of Chloramphenicol 下载免费PDF全文
Dr. Petr Jakubec Dr. Veronika Urbanová Dr. Zdenka Medříková Prof. Dr. Radek Zbořil 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14279-14284
The sensing and accurate determination of antibiotics in various environments represents a big challenge, mainly owing to their widespread use in medicine, veterinary practice, and other fields. Therefore, a new, simple electrochemical sensor for the detection of antibiotic chloramphenicol (CAP) has been developed in this work. The amplification strategy of the sensor is based on the application of magnetite nanostructures stabilized with carboxymethyl cellulose (Fe3O4‐CMC) and decorated with nanometer‐sized Au nanoparticles (NPs) (Fe3O4‐CMC@Au). In this case, CMC serves as a stabilizing agent, preventing the aggregation of Fe3O4 NPs, and hence, enabling the kinetic barrier for electron transport to be overcome, and the Au NPs serve as an electron‐conducting tunnel for better electron transport. As a proof of concept, the developed nanosensor is used for the detection of CAP in human urine samples, giving a recovery value of around 97 %, which indicates the high accuracy of the as‐prepared nanosensor. 相似文献