全文获取类型
收费全文 | 1023篇 |
免费 | 46篇 |
国内免费 | 3篇 |
专业分类
化学 | 718篇 |
晶体学 | 6篇 |
力学 | 34篇 |
数学 | 171篇 |
物理学 | 143篇 |
出版年
2023年 | 11篇 |
2022年 | 9篇 |
2021年 | 18篇 |
2020年 | 17篇 |
2019年 | 20篇 |
2018年 | 17篇 |
2017年 | 13篇 |
2016年 | 30篇 |
2015年 | 22篇 |
2014年 | 35篇 |
2013年 | 48篇 |
2012年 | 87篇 |
2011年 | 117篇 |
2010年 | 76篇 |
2009年 | 54篇 |
2008年 | 82篇 |
2007年 | 58篇 |
2006年 | 70篇 |
2005年 | 50篇 |
2004年 | 53篇 |
2003年 | 47篇 |
2002年 | 36篇 |
2001年 | 9篇 |
2000年 | 5篇 |
1999年 | 5篇 |
1998年 | 6篇 |
1997年 | 8篇 |
1996年 | 10篇 |
1995年 | 4篇 |
1994年 | 5篇 |
1993年 | 5篇 |
1992年 | 6篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1976年 | 5篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1971年 | 1篇 |
排序方式: 共有1072条查询结果,搜索用时 15 毫秒
1.
Dr. Sabin Llona‐Minguez Dr. Matthieu Desroses Artin Ghassemian Dr. Sylvain A. Jacques Dr. Lars Eriksson Rebecka Isacksson Tobias Koolmeister Dr. Pål Stenmark Dr. Martin Scobie Prof. Thomas Helleday 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(20):7394-7398
A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif. 相似文献
2.
3.
Theodore Flack Thibaut Constantin Sylvain Penasse Dr. Jérôme Dejeu Béatrice Gennaro Dr. Muriel Jourdan Aurélien Laguerre Marc Pirrotta Dr. David Monchaud Dr. Nicolas Spinelli Prof. Eric Defrancq 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(5):1760-1767
A water‐soluble template‐assembled synthetic G‐quartet (TASQ) based on the use of a macrocyclodecapeptide scaffold was designed to display stable intramolecular folds alone in solution. The preformation of the guanine quartet, demonstrated by NMR and CD investigations, results in enhanced peroxidase‐type biocatalytic activities and improved quadruplex‐interacting properties. Comparison of its DNAzyme‐boosting properties with the ones of previously published TASQ revealed that, nowadays, it is the best DNAzyme‐boosting agent. 相似文献
4.
Dr. Sébastien Lemouzy Florian Cuminet Dimitri Berne Dr. Sylvain Caillol Dr. Vincent Ladmiral Prof. Rinaldo Poli Dr. Eric Leclerc 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(48):e202201135
Vitrimers are a third class of polymers gathering the mechanical properties and solvent resistance of 3D thermosets and the reprocessability of thermoplastics. This unique behaviour is due to the triggering of certain covalent exchange reactions that allow the network to rearrange upon application of a stimulus. The constitutive feature of vitrimers is the adoption of a glass-like viscosity during the rearrangement of the network, often due to an associative mechanism for the exchange reaction. Transesterification networks are one of the most studied type of vitrimers that usually require the incorporation of a catalyst, implying the associated drawbacks. Following up on a recent report on catalyst-free transesterification vitrimers in which the ester functions are particularly reactive thanks to the presence of fluorine atoms in α- or β-position, parallel DFT calculations and an experimental kinetic study on model molecules are presented in order to quantitatively assess the effect of neighbouring fluorinated groups on the transesterification reaction rate. 相似文献
5.
Sylvain Sudan Damien W. Chen Cesare Berton Farzaneh Fadaei-Tirani Kay Severin 《Angewandte Chemie (International ed. in English)》2023,62(9):e202218072
A water-soluble coordination cage was obtained by reaction of Pd(NO3)2 with a 1,3-di(pyridin-3-yl)benzene ligand featuring a short PEG chain. The cavity of the metal-organic cage contains one nitrate anion, which is readily replaced by chloride. The apparent association constant for chloride binding in buffered aqueous solution is Ka=1.8(±0.1)×105 M−1. This value is significantly higher than what has been reported for other macrocyclic chloride receptors. The heavier halides Br− and I− compete with binding or self-assembly, but the receptor displays very good selectivity over common anions such as phosphate, acetate, carbonate, and sulfate. A further increase of the chloride binding affinity by a factor of 3 was achieved using a fluorinated dipyridyl ligand. 相似文献
6.
Competitive Gold‐Promoted Meyer–Schuster and oxy‐Cope Rearrangements of 3‐Acyloxy‐1,5‐enynes: Selective Catalysis for the Synthesis of (+)‐(S)‐γ‐Ionone and (−)‐(2S,6 R)‐cis‐γ‐Irone 下载免费PDF全文
Dr. Serena Bugoni Dr. Valentina Merlini Dr. Alessio Porta Dr. Sylvain Gaillard Prof. Giuseppe Zanoni Prof. Dr. Steven P. Nolan Prof. Giovanni Vidari 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(40):14068-14074
We report a simple, highly stereoselective synthesis of (+)‐(S)‐γ‐ionone and (‐)‐(2S,6R)‐cis‐γ‐irone, two characteristic and precious odorants; the latter compound is a constituent of the essential oil obtained from iris rhizomes. Of general interest in this approach are the photoisomerization of an endo trisubstituted cyclohexene double bond to an exo vinyl group and the installation of the enone side chain through a [(NHC)AuI]‐catalyzed Meyer–Schuster‐like rearrangement. This required a careful investigation of the mechanism of the gold‐catalyzed reaction and a judicious selection of reaction conditions. In fact, it was found that the Meyer–Schuster reaction may compete with the oxy‐Cope rearrangement. Gold‐based catalytic systems can promote either reaction selectively. In the present system, the mononuclear gold complex [Au(IPr)Cl], in combination with the silver salt AgSbF6 in 100:1 butan‐2‐one/H2O, proved to efficiently promote the Meyer–Schuster rearrangement of propargylic benzoates, whereas the digold catalyst [{Au(IPr)}2(μ‐OH)][BF4] in anhydrous dichloromethane selectively promoted the oxy‐Cope rearrangement of propargylic alcohols. 相似文献
7.
Dr. Kimiaka C. Guérard Vincent Hamel Dr. Amandine Guérinot Cloé Bouchard‐Aubin Prof. Sylvain Canesi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(50):18068-18071
A rapid route to 5,5‐ and 5,6‐ bicyclic systems is provided by an 1,3‐alkyl‐shift process mediated by a hypervalent iodine reagent on aromatics. The structures obtained contain several unsaturations with different behaviors and reactivities. Such diversity allows further elaborations for the rapid formation of compact systems present in a variety of natural products. The potential for further transformations has been demonstrated by performing a double Michael addition. This cyclization process is regio‐ and stereoselective due to the presence of a former benzylic substituent. Furthermore, an extension of this approach has been accomplished on indole derivatives. 相似文献
8.
Computational Studies on Intramolecular Cycloadditions of Azidoenynes and Azidobutenenitriles to Give 6H‐Pyrrolo[1,2‐c][1,2,3]triazoles and 5H‐Pyrrolo[1,2‐d]tetrazoles 下载免费PDF全文
Gérard Audran Paul Brémond Douniazad El Abed Sylvain R. A. Marque Didier Siri Maurice Santelli 《Helvetica chimica acta》2015,98(7):1018-1027
Energetics of intramolecular cycloadditions of azidoenynes and azidobutenenitriles to give 6H‐pyrrolo[1,2‐c][1,2,3]triazoles and 5H‐pyrrolo[1,2‐d]tetrazoles have been calculated at the B3LYP/6.311++G(3df,3pd) level of theory in ideal gas and in H2O as solvent. Stabilities of the corresponding anions, tautomers, and isomers are discussed. Transition states of the cyclization of parent compounds are determined at the same level of theory. 相似文献
9.
Maria D. Manrique-Juarez Dr. Fabrice Mathieu Dr. Victoria Shalabaeva Dr. Jean Cacheux Sylvain Rat Dr. Liviu Nicu Dr. Thierry Leïchlé Dr. Lionel Salmon Dr. Gábor Molnár Dr. Azzedine Bousseksou 《Angewandte Chemie (International ed. in English)》2017,56(28):8074-8078
We report on a bistable MEMS device actuated by spin-crossover molecules. The device consists of a freestanding silicon microcantilever with an integrated piezoresistive detection system, which was coated with a 140 nm thick film of the [Fe(HB(tz)3)2] (tz=1,2,4-triazol-1-yl) molecular spin-crossover complex. Switching from the low-spin to the high-spin state of the ferrous ions at 338 K led to a reversible upward bending of the cantilever in agreement with the change in the lattice parameters of the complex. The strong mechanical coupling was also evidenced by the decrease of approximately 66 Hz in the resonance frequency in the high-spin state as well as by the drop in the quality factor around the spin transition. 相似文献
10.
The development of a user-friendly reusable laboratory equipment for the delivery of sensitive reagents and catalysts is described. The tightness of these Teflon Magnetic Stirring Capsules (TMSC) is ensured by the magnetic force and release of the reagent inside the solution is triggered by adjusting the stirring rate so that the centrifuge force exceeds the magnetic force. They can be loaded with several chemicals at the same time and do operate across a broad range of temperatures. The inertness of Teflon facilitates reaction purification. 相似文献