全文获取类型
收费全文 | 1869篇 |
免费 | 57篇 |
国内免费 | 10篇 |
专业分类
化学 | 991篇 |
晶体学 | 16篇 |
力学 | 35篇 |
数学 | 200篇 |
物理学 | 694篇 |
出版年
2021年 | 11篇 |
2020年 | 15篇 |
2019年 | 27篇 |
2017年 | 13篇 |
2016年 | 40篇 |
2015年 | 42篇 |
2014年 | 32篇 |
2013年 | 57篇 |
2012年 | 74篇 |
2011年 | 83篇 |
2010年 | 39篇 |
2009年 | 53篇 |
2008年 | 74篇 |
2007年 | 79篇 |
2006年 | 62篇 |
2005年 | 63篇 |
2004年 | 75篇 |
2003年 | 34篇 |
2002年 | 55篇 |
2001年 | 34篇 |
2000年 | 36篇 |
1999年 | 24篇 |
1998年 | 19篇 |
1997年 | 26篇 |
1996年 | 31篇 |
1995年 | 29篇 |
1994年 | 37篇 |
1993年 | 31篇 |
1992年 | 22篇 |
1991年 | 32篇 |
1990年 | 36篇 |
1989年 | 16篇 |
1988年 | 40篇 |
1987年 | 41篇 |
1986年 | 17篇 |
1985年 | 40篇 |
1984年 | 29篇 |
1983年 | 24篇 |
1982年 | 24篇 |
1981年 | 38篇 |
1980年 | 31篇 |
1979年 | 27篇 |
1978年 | 22篇 |
1977年 | 14篇 |
1976年 | 20篇 |
1975年 | 19篇 |
1974年 | 16篇 |
1973年 | 16篇 |
1972年 | 10篇 |
1938年 | 9篇 |
排序方式: 共有1936条查询结果,搜索用时 31 毫秒
1.
Julia Holz Camilla Pfeffer Hualiang Zuo Dennis Beierlein Gunther Richter Elias Klemm Ren Peters 《Angewandte Chemie (International ed. in English)》2019,58(30):10330-10334
Gold nanoparticle catalysts are important in many industrial production processes. Nevertheless, for traditional C ?C cross‐coupling reactions they have been rarely used and Pd catalysts usually give a superior performance. Herein we report that in situ formed gold metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form C ?C bonds. Turnover numbers up to 29 000 could be achieved in the presence of active carbon as solid support, which allowed for convenient catalyst recovery and reuse. The present study is a rare case where a gold metal catalyst is superior to Pd catalysts in a cross‐coupling reaction of an organic halide and an organometallic reagent. 相似文献
2.
3.
Da Wang Dr. Christian Richter Andreas Rühling Dr. Patrick Drücker Daniel Siegmund Prof. Dr. Nils Metzler‐Nolte Prof. Dr. Frank Glorius Prof. Dr. Hans‐Joachim Galla 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(43):15123-15126
A series of imidazolium salts bearing two alkyl chains in the backbone of the imidazolium core were synthesized, resembling the structure of lipids. Their antibacterial activity and cytotoxicity were evaluated using Gram‐positive and Gram‐negative bacteria and eukaryotic cell lines including tumor cells. It is shown that the length of alkyl chains in the backbone is vital for the antibiofilm activities of these lipid‐mimicking components. In addition to their biological activity, their surface activity and their membrane interactions are shown by film balance and quartz crystal microbalance (QCM) measurements. The structure–activity relationship indicates that the distinctive chemical structure contributes considerably to the biological activities of this novel class of lipids. 相似文献
4.
Olivia Schimming Dr. Victoria L. Challinor Dr. Nicholas J. Tobias Dr. Hélène Adihou Peter Grün Laura Pöschel Dr. Christian Richter Prof. Dr. Harald Schwalbe Prof. Dr. Helge B. Bode 《Angewandte Chemie (International ed. in English)》2015,54(43):12702-12705
Pyrrolizidine alkaloids (PAs) are widespread plant natural products with potent toxicity and bioactivity. Herein, the identification of bacterial PAs from entomopathogenic bacteria using differential analysis by 2D NMR spectroscopy (DANS) and mass spectrometry is described. Their biosynthesis was elucidated to involve a non‐ribosomal peptide synthetase. The occurrence of these biosynthesis gene clusters in Gram‐negative and Gram‐positive bacteria indicates an important biological function in bacteria. 相似文献
5.
Production of the Bengamide Class of Marine Natural Products in Myxobacteria: Biosynthesis and Structure–Activity Relationships 下载免费PDF全文
Dr. Silke C. Wenzel Dr. Holger Hoffmann Dr. Jidong Zhang Dr. Laurent Debussche Dr. Sabine Haag‐Richter Dr. Michael Kurz Dr. Frederico Nardi Dr. Peer Lukat Irene Kochems Dr. Heiko Tietgen Prof. Dr. Dietmar Schummer Jean‐Paul Nicolas Dr. Loreley Calvet Dr. Valerie Czepczor Dr. Patricia Vrignaud Dr. Agnes Mühlenweg Priv.‐Doz. Dr. Stefan Pelzer Prof. Dr. Rolf Müller Prof. Dr. Mark Brönstrup 《Angewandte Chemie (International ed. in English)》2015,54(51):15560-15564
The bengamides, sponge‐derived natural products that have been characterized as inhibitors of methionine aminopeptidases (MetAPs), have been intensively investigated as anticancer compounds. We embarked on a multidisciplinary project to supply bengamides by fermentation of the terrestrial myxobacterium M. virescens, decipher their biosynthesis, and optimize their properties as drug leads. The characterization of the biosynthetic pathway revealed that bacterial resistance to bengamides is conferred by Leu 154 of the myxobacterial MetAP protein, and enabled transfer of the entire gene cluster into the more suitable production host M. xanthus DK1622. A combination of semisynthesis of microbially derived bengamides and total synthesis resulted in an optimized derivative that combined high cellular potency in the nanomolar range with high metabolic stability, which translated to an improved half‐life in mice and antitumor efficacy in a melanoma mouse model. 相似文献
6.
Silke C. Wenzel Holger Hoffmann Jidong Zhang Laurent Debussche Sabine Haag‐Richter Michael Kurz Frederico Nardi Peer Lukat Irene Kochems Heiko Tietgen Dietmar Schummer Jean‐Paul Nicolas Loreley Calvet Valerie Czepczor Patricia Vrignaud Agnes Mühlenweg Stefan Pelzer Rolf Müller Mark Brnstrup 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(51):15781-15785
7.
Gas‐Phase Infrared Spectra of Three Compounds of Astrochemical Interest: Vinyl,Allenyl, and Propargyl Isocyanides 下载免费PDF全文
Dr. Abdessamad Benidar Prof. Dr. Didier Bégué Dr. Falk Richter Prof. Dr. Claude Pouchan Prof. Dr. Mohammed Lahcini Dr. Jean‐Claude Guillemin 《Chemphyschem》2015,16(4):848-854
Isocyanides, isomers of the cyanides detected in the interstellar medium, are also possible components of this medium. The infrared spectra (5000–500 cm?1) of gaseous vinyl isocyanide, allenyl isocyanide, and propargyl isocyanide have been recorded at 0.1 cm?1 resolution. When prepared on a gram scale to produce a partial pressure of 10 mbar after evaporation in the cell, these three isocyanides, which have previously been reported to be kinetically unstable, do not display any sign of decomposition when recording the spectra. Geometry optimizations and harmonic and anharmonic vibrational frequencies were calculated using the LCCSD(T) method with the cc‐pVTZ basis set. Anharmonic frequencies of fundamental, overtone, and combination transitions were calculated using a variational approach implemented in the P Anhar.v2.0 code, to assign the experimental data for each compound. These results improve our knowledge of these under‐investigated compounds and pave the way for other physicochemical studies on functionalized isocyanides. 相似文献
8.
9.
10.
Kwan Ho Au-Yeung Tim Kühne Daniel Becker Dr. Marcus Richter Dr. Dmitry A. Ryndyk Prof. Dr. Gianaurelio Cuniberti Prof. Dr. Thomas Heine Prof. Dr. Xinliang Feng Dr. Francesca Moresco 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(69):17336-17340
The rapid development of on-surface synthesis provides a unique approach toward the formation of carbon-based nanostructures with designed properties. Herein, we present the on-surface formation of CN-substituted phenylene vinylene chains on the Au(111) surface, thermally induced by annealing the substrate stepwise at temperatures between 220 °C and 240 °C. The reaction is investigated by scanning tunneling microscopy and density functional theory. Supported by the calculated reaction pathway, we assign the observed chain formation to a Knoevenagel condensation between an aldehyde and a methylene nitrile substituent. 相似文献