全文获取类型
收费全文 | 1913篇 |
免费 | 117篇 |
国内免费 | 6篇 |
专业分类
化学 | 1673篇 |
晶体学 | 12篇 |
力学 | 19篇 |
数学 | 152篇 |
物理学 | 180篇 |
出版年
2024年 | 3篇 |
2023年 | 27篇 |
2022年 | 78篇 |
2021年 | 104篇 |
2020年 | 80篇 |
2019年 | 58篇 |
2018年 | 37篇 |
2017年 | 39篇 |
2016年 | 78篇 |
2015年 | 71篇 |
2014年 | 88篇 |
2013年 | 115篇 |
2012年 | 185篇 |
2011年 | 136篇 |
2010年 | 88篇 |
2009年 | 69篇 |
2008年 | 109篇 |
2007年 | 118篇 |
2006年 | 92篇 |
2005年 | 84篇 |
2004年 | 73篇 |
2003年 | 57篇 |
2002年 | 50篇 |
2001年 | 15篇 |
2000年 | 8篇 |
1999年 | 8篇 |
1998年 | 8篇 |
1997年 | 11篇 |
1996年 | 16篇 |
1995年 | 11篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 12篇 |
1991年 | 10篇 |
1990年 | 10篇 |
1989年 | 12篇 |
1988年 | 9篇 |
1987年 | 11篇 |
1986年 | 2篇 |
1985年 | 10篇 |
1984年 | 8篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1978年 | 4篇 |
1975年 | 1篇 |
1973年 | 1篇 |
1968年 | 1篇 |
1961年 | 2篇 |
1933年 | 1篇 |
排序方式: 共有2036条查询结果,搜索用时 15 毫秒
101.
Dr. Goutam Kumar Kole Dr. Julia Merz Dr. Anissa Amar Dr. Bruno Fontaine Dr. Abdou Boucekkine Dr. Jörn Nitsch Sabine Lorenzen Dr. Alexandra Friedrich Dr. Ivo Krummenacher Marta Košćak Prof. Dr. Holger Braunschweig Prof. Dr. Ivo Piantanida Prof. Dr. Jean-François Halet Prof. Dr. Klaus Müller-Buschbaum Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(8):2837-2853
Two N-methylpyridinium compounds and analogous N-protonated salts of 2- and 2,7-substituted 4-pyridyl-pyrene compounds were synthesised and their crystal structures, photophysical properties both in solution and in the solid state, electrochemical and spectroelectrochemical properties were studied. Upon methylation or protonation, the emission maxima are significantly bathochromically shifted compared to the neutral compounds, although the absorption maxima remain almost unchanged. As a result, the cationic compounds show very large apparent Stokes shifts of up to 7200 cm−1. The N-methylpyridinium compounds have a single reduction at ca. −1.5 V vs. Fc/Fc+ in MeCN. While the reduction process was reversible for the 2,7-disubstituted compound, it was irreversible for the mono-substituted one. Experimental findings are complemented by DFT and TD-DFT calculations. Furthermore, the N-methylpyridinium compounds show strong interactions with calf thymus (ct)-DNA, presumably by intercalation, which paves the way for further applications of these multi-functional compounds as potential DNA-bioactive agents. 相似文献
102.
Alexandra Mavridi-Printezi Arianna Menichetti Moreno Guernelli Prof. Dr. Marco Montalti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(66):16309-16319
Melanin-like nanomaterials have found application in a large variety of high economic and social impact fields as medicine, energy conversion and storage, photothermal catalysis and environmental remediation. These materials have been used mostly for their optical and electronic properties, but also for their high biocompatibility and simplicity and versatility of preparation. Beside this, their chemistry is complex and it yields structures with different molecular weight and composition ranging from oligomers, to polymers as well as nanoparticles (NP). The comprehension of the correlation of the different compositions and morphologies to the optical properties of melanin is still incomplete and challenging, even if it is fundamental also from a technological point of view. In this minireview we focus on scientific papers, mostly recent ones, that indeed examine the link between composition and structural feature and photophysical and photochemical properties proposing this approach as a general one for future research. 相似文献
103.
Raluca Nicoleta Darie Eduard Lack Franz Lang Jr. Martin Sova Alexandra Nistor Iuliana Spiridon 《International Journal of Polymer Analysis and Characterization》2014,19(5):453-467
New materials were obtained by incorporating in polypropylene (PP) matrix 60% wood wastes resulting after extraction with supercritical carbon dioxide, water, and ethanol. Structural, mechanical, thermal, and rheological characterizations, as well as moisture uptake of the composites, were evaluated before and after accelerated weathering. It was found that the extraction method influenced the composite properties due to the hydrophilic-hydrophobic balance. The addition of extracted fibers results in an increase in hardness and tensile properties and a decrease of impact strength as compared to PP. 相似文献
104.
Mihaela Badea Larisa Calu Mariana Carmen Chifiriuc Coralia Bleotu Alexandra Marin Sebastian Ion Gabriela Ioniţă Nicolae Stanică Luminiţa Măruţescu Veronica Lazăr Dana Marinescu Rodica Olar 《Journal of Thermal Analysis and Calorimetry》2014,118(2):1145-1157
A series of complexes of type [ML(CH3COO)(OH2)2] (M: Co, Ni; HL: 2-[(E)-1H-1,2,4-triazol-3-ylimino)methyl]phenol)) and [M2L2(CH3COO)2(OH2)n] (M: Cu, n = 2; M: Zn, n = 0) were synthesised by template condensation. The compounds were characterised with microanalytical, ESI–MS, IR, electronic, EPR spectra and magnetic data at room temperature. Based on the IR and ESI–MS spectra, a dinuclear structure with the acetate as bridge was proposed for Cu(II) and Zn(II) complexes. The dinuclear structure of Cu(II) complex is also consistent with both magnetic behaviour and EPR spectrum. The thermal analyses have evidenced processes as water elimination, acetate decomposition, as well as oxidative degradation of the Schiff base. The final decomposition product was the most stable metal oxide as indicated by powder X-ray diffraction. The cobalt and copper compounds exhibited a broad spectrum of antibacterial activity towards both planktonic and biofilm-embedded cells. The complexes exhibit a low cytotoxicity except for Cu(II) species that induces the early apoptosis for the HEp 2 cells. 相似文献
105.
Transfer Hydrogenation of Ketones Catalyzed by Surface‐Active Ruthenium and Rhodium Complexes in Water
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Alexander M. Kalsin Dr. Tat'yana A. Peganova Dr. Valentin V. Novikov Alexandra I. Zhamoytina Dr. Luca Gonsalvi Dr. Maurizio Peruzzini 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(3):846-854
An improved, high‐yield, one‐pot synthetic procedure for water‐soluble ligands functionalized with trialkyl ammonium side groups H2N(CH2)2NHSO2‐p‐C6H4CH2[NMe2(CnH2n+1)]+ ( [HL n ]+ ; n=8, 16) was developed. The corresponding new surface‐active complexes [(p‐cymene)RuCl( L n )] and [Cp*RhCl( L n )] (Cp*=η5‐C5Me5) were prepared and characterized. For n=16 micelles are formed in water at concentrations as low as 0.6 mM , as demonstrated by surface‐tension measurements. The complexes were used for catalytic transfer hydrogenation of ketones with formate in water. Highly active catalyst systems were obtained in the case of complexes bearing C16 tails due to their ability to be adsorbed at the water/substrate interface. The scope of these catalyst systems in aqueous solutions was extended from partially water soluble aryl alkyl ketones (acetophenone, butyrophenone) to hydrophobic dialkyl ketones (2‐dodecanone). 相似文献
106.
Exploring the Molecular Structure of Imidazolium–Silica‐Based Nanoparticle Networks by Combining Solid‐State NMR Spectroscopy and First‐Principles Calculations
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Marie‐Alexandra Neouze Martin Kronstein Dr. Marco Litschauer Dr. Michael Puchberger Dr. Cristina Coelho Prof. Christian Bonhomme Prof. Christel Gervais Dr. Frederik Tielens 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(46):15188-15196
A DFT‐based molecular model for imidazolium–silica‐based nanoparticle networks (INNs) is presented. The INNs were synthesized and characterized by using small‐angle X‐ray scattering (SAXS), NMR spectroscopy, and theoretical ab initio calculations. 11B and 31P HETCOR CP MAS experiments were recorded. Calculated 19F NMR spectroscopy results, combined with the calculated anion–imidazolium (IM) distances, predicted the IM chain density in the INN, which was also confirmed from thermogravimetric analysis/mass spectrometry results. The presence of water molecules trapped between the nanoparticles is also suggested. First considerations on possible π–π stacking between the IM rings are presented. The predicted electronic properties confirm the photoluminescence emissions in the correct spectral domain. 相似文献
107.
Simone Manzini Dr. Albert Poater Dr. David J. Nelson Prof. Dr. Luigi Cavallo Prof. Dr. Alexandra M. Z. Slawin Prof. Dr. Steven P. Nolan 《Angewandte Chemie (International ed. in English)》2014,53(34):8995-8999
The decomposition of a series of benzylidene, methylidene, and 3‐phenylindenylidene complexes has been probed in alcohol solution in the presence of base. Tricyclohexylphosphane‐containing precatalysts are shown to yield [RuCl(H)(H2)(PCy3)2] in isopropyl alcohol solutions, while 3‐phenylindenylidene complexes lead to η5‐(3‐phenyl)indenyl products. The potential‐energy surfaces for the formation of the latter species have been probed using density functional theory studies. 相似文献
108.
Prof. Li Chen Genevieve E. Mullen Myriam Le Roch Cody G. Cassity Prof. Nicolas Gouault Prof. Henry Y. Fadamiro Prof. Robert E. Barletta Prof. Richard A. O'Brien Prof. Richard E. Sykora Prof. Alexandra C. Stenson Prof. Kevin N. West Howard E. Horne Jeffrey M. Hendrich Kang Rui Xiang Prof. James H. Davis Jr. 《Angewandte Chemie (International ed. in English)》2014,53(44):11762-11765
The practical utility of ionic liquids (ILs) makes the absence (heretofore) of reported examples from nature quite puzzling, given the facility with which nature produces many other types of exotic but utilitarian substances. In that vein, we report here the identification and characterization of a naturally occurring protic IL. It can be formed during confrontations between the ants S. invicta and N. fulva. After being sprayed with alkaloid‐based S. invicta venom, N. fulva detoxifies by grooming with its own venom, formic acid. The mixture is a viscous liquid manifestly different from either of the constituents. Further, we find that the change results as a consequence of formic acid protonation of the N centers of the S. invicta venom alkaloids. The resulting mixed‐cation ammonium formate milieu has properties consistent with its classification as a protic IL. 相似文献
109.
Tetracyanoquinodimethane Reduction by Complexed Guanidinyl‐Functionalized Aromatic Compounds
下载免费PDF全文
![点击此处可从《Chemphyschem》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Hendrik Herrmann Alexandra Ziesak Ute Wild Simone Leingang David Schrempp Norbert Wagner Prof. Dr. Johannes Beck Dr. Elisabeth Kaifer Prof. Dr. Hubert Wadepohl Prof. Dr. Hans‐Jörg Himmel 《Chemphyschem》2014,15(2):351-365
In this work, we report on the reduction of tetracyanoquinodimethane (TCNQ) with dicationic complexes of guanidinyl‐functionalized aromatic (GFA) electron donors. In contrast to reduction with free GFAs, milder reduction conditions were achieved, and this led to semiconducting materials with extended TCNQ π stacking. The charge on the TCNQ units was estimated from the structural data obtained by single‐crystal X‐ray diffraction analysis and from IR spectroscopic data. The electrical conductivity was studied and the activation energy of the semiconducting materials was estimated from the temperature dependence of the conductivity. 相似文献
110.
Laura Sinatra Jan J. Bandolik Dr. Martin Roatsch Melf Sönnichsen Dr. Clara T. Schoeder Dr. Alexandra Hamacher Andrea Schöler Prof. Dr. Arndt Borkhardt Prof. Dr. Jens Meiler Dr. Sanil Bhatia Prof. Dr. Matthias U. Kassack Prof. Dr. Finn K. Hansen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(50):22681-22687