全文获取类型
收费全文 | 1298篇 |
免费 | 66篇 |
国内免费 | 7篇 |
专业分类
化学 | 1007篇 |
晶体学 | 24篇 |
力学 | 27篇 |
数学 | 186篇 |
物理学 | 127篇 |
出版年
2022年 | 14篇 |
2021年 | 21篇 |
2020年 | 38篇 |
2019年 | 35篇 |
2018年 | 19篇 |
2017年 | 20篇 |
2016年 | 45篇 |
2015年 | 41篇 |
2014年 | 44篇 |
2013年 | 75篇 |
2012年 | 72篇 |
2011年 | 73篇 |
2010年 | 55篇 |
2009年 | 26篇 |
2008年 | 93篇 |
2007年 | 66篇 |
2006年 | 67篇 |
2005年 | 54篇 |
2004年 | 36篇 |
2003年 | 42篇 |
2002年 | 40篇 |
2001年 | 20篇 |
2000年 | 27篇 |
1999年 | 20篇 |
1998年 | 8篇 |
1997年 | 18篇 |
1996年 | 17篇 |
1995年 | 13篇 |
1994年 | 19篇 |
1993年 | 11篇 |
1992年 | 9篇 |
1990年 | 10篇 |
1989年 | 11篇 |
1988年 | 17篇 |
1987年 | 9篇 |
1986年 | 7篇 |
1985年 | 8篇 |
1983年 | 11篇 |
1981年 | 8篇 |
1980年 | 8篇 |
1979年 | 8篇 |
1978年 | 5篇 |
1977年 | 6篇 |
1976年 | 6篇 |
1975年 | 7篇 |
1974年 | 8篇 |
1972年 | 7篇 |
1969年 | 7篇 |
1967年 | 5篇 |
1966年 | 8篇 |
排序方式: 共有1371条查询结果,搜索用时 31 毫秒
71.
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
72.
Hendrik Gruß Prof. Dr. Norbert Sewald 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(24):5328-5340
Pd-mediated reactions have emerged as a powerful tool for the site-selective and bioorthogonal late-stage diversification of amino acids, peptides and related compounds. Indole moieties of tryptophan derivatives are susceptible to C2H-activation, whereas halogenated aromatic amino acids such as halophenylalanines or halotryptophans provide a broad spectrum of different functionalisations. The compatibility of transition-metal-catalysed cross-couplings with functional groups in peptides, other biologically active compounds and even proteins has been demonstrated. This Review primarily compiles the application of different cross-coupling reactions to modify halotryptophans, halotryptophan containing peptides or halogenated, biologically active compounds derived from tryptophan. Modern approaches use regio- and stereoselective biocatalytic strategies to generate halotryptophans and derivatives on a preparative scale. The combination of bio- and chemocatalysis in cascade reactions is given by the biocompatibility and bioorthogonality of Pd-mediated reactions. 相似文献
73.
Moritz Balkenhohl Harish Jangra Ilya S. Makarov Shu‐Mei Yang Hendrik Zipse Paul Knochel 《Angewandte Chemie (International ed. in English)》2020,59(35):14992-14999
The development of a predictive model towards site‐selective deprotometalation reactions using TMPZnCl?LiCl is reported (TMP=2,2,6,6‐tetramethylpiperidinyl). The pKa values of functionalized N‐, S‐, and O‐heterocycles, arenes, alkenes, or alkanes were calculated and compared to the experimental deprotonation sites. Large overlap (>80 %) between the calculated and empirical deprotonation sites was observed, showing that thermodynamic factors strongly govern the metalation regioselectivity. In the case of olefins, calculated frozen state energies of the deprotonated substrates allowed a more accurate prediction. Additionally, various new N‐heterocycles were analyzed and the metalation regioselectivities rationalized using the predictive model. 相似文献
74.
Rhodium PCcarbeneP complexes 1‐L {L=PPh3, PPh2(C6F5)} react with isothiocyanate, carbodiimide and disulphide to enable C?S, C?N and S?S bond cleavage. The cleaved molecules are sequestered by the metal center and the pincer alkylidene linkage, forming η2‐coordinated sulfide or imide centered pincer complexes. When a C?S or S?S bond is cleaved, the resulting complexes can bridge two rhodium centers through sulphur forming dimeric complexes and eliminating a monodentate phosphine ligand. 相似文献
75.
Sarath P. Gunasekera Sofia Kokkaliari Ranjala Ratnayake Thomas Sauvage Larissa A. H. dos Santos Hendrik Luesch Valerie J. Paul 《Molecules (Basel, Switzerland)》2022,27(5)
Dysidazirine carboxylic acid (1) was isolated from the lipophilic extract of a collection of the benthic marine cyanobacterium Caldora sp. from reefs near Fort Lauderdale, Florida. The planar structure of this new compound was determined by spectroscopic methods and comparisons between HRMS and NMR data with its reported methyl ester. The absolute configuration of the single chiral center was determined by the conversion of 1 to the methyl ester and the comparison of its specific rotation data with the two known methyl ester isomers, 2 and 3. Molecular sequencing with 16S rDNA indicated that this cyanobacterium differs from Caldora penicillata (Oscillatoriales) and represents a previously undocumented and novel Caldora species. Dysidazirine (2) showed weak cytotoxicity against HCT116 colorectal cancer cells (IC50 9.1 µM), while dysidazirine carboxylic acid (1) was non-cytotoxic. Similar cell viability patterns were observed in RAW264.7 cells with dysidazirine only (2), displaying cytotoxicity at the highest concentration tested (50 µM). The non-cytotoxic dysidazirine carboxylic acid (1) demonstrated anti-inflammatory activity in RAW264.7 cells stimulated with LPS. After 24 h, 1 inhibited the production of NO by almost 50% at 50 µM, without inducing cytotoxicity. Compound 1 rapidly decreased gene expression of the pro-inflammatory gene iNOS after 3 h post-LPS treatment and in a dose-dependent manner (IC50 ~1 µM); the downregulation of iNOS persisted at least until 12 h. 相似文献
76.
Room- and high-temperature micro-indentation experiments have been performed to answer the question if, concerning a material with very low stacking-fault energy like CdTe, deformation induced twinning occurs in these substances during or shortly after growth. Micro-twins appear in consequence of room-temperature deformation only, whereas microindentation at 565°C does not produce any twins, but leads to widely expanded dislocation glide-figures, due to dislocation climbing and/or cross-gliding. 相似文献
77.
78.
Reaction between O,O-diethyl-S-phenyl phosphorothiolate and lithium dialkylamides results in the displacement of the PhS substituent by the R2N group. With Grignard reagents, the same substrate gives products of the nucleophilic substitution at both the phosphorus and the sulfur atom. 相似文献
79.
The Vickers indentation hardness of Hg1−xCdxTe has been measured as a function of composition x using monocrystalline samples of Bridgman and THM crystals and polycrystalline starting material at room temperature. The microhardness varied between 220 MPa (x=0) and 440 MPa (x=1), showing a maximum of 850 MPa at x ∼ 0.75, and was different between monocrystalline and polycrystalline samples. The “hardening rate” dH/dx is strongly dependent on the composition range and is discussed in context with solid solution hardening due to elastic interactions of solute atoms with gliding dislocations and ordering effects. 相似文献
80.
Im Rahmen des Graduiertenkollegs “Hochreaktive Mehrfachbindungssysteme” hatten G. Erker und J. Grobe vom 16. bis 18. November 1994 schon zum zweiten Mal nach Münster eingeladen. “Organic and Inorganic Chemistry of Reactive C=X π-Systems” waren diesmal das Thema. 相似文献