全文获取类型
收费全文 | 1339篇 |
免费 | 70篇 |
国内免费 | 5篇 |
专业分类
化学 | 1075篇 |
晶体学 | 1篇 |
力学 | 14篇 |
数学 | 150篇 |
物理学 | 174篇 |
出版年
2023年 | 10篇 |
2022年 | 9篇 |
2021年 | 17篇 |
2020年 | 35篇 |
2019年 | 27篇 |
2018年 | 10篇 |
2017年 | 9篇 |
2016年 | 62篇 |
2015年 | 45篇 |
2014年 | 59篇 |
2013年 | 70篇 |
2012年 | 114篇 |
2011年 | 103篇 |
2010年 | 64篇 |
2009年 | 51篇 |
2008年 | 94篇 |
2007年 | 77篇 |
2006年 | 94篇 |
2005年 | 69篇 |
2004年 | 83篇 |
2003年 | 66篇 |
2002年 | 49篇 |
2001年 | 31篇 |
2000年 | 15篇 |
1999年 | 16篇 |
1998年 | 14篇 |
1997年 | 12篇 |
1996年 | 21篇 |
1995年 | 16篇 |
1994年 | 20篇 |
1993年 | 3篇 |
1992年 | 6篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1986年 | 3篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1976年 | 3篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1967年 | 1篇 |
1965年 | 1篇 |
1964年 | 2篇 |
1963年 | 1篇 |
1962年 | 1篇 |
排序方式: 共有1414条查询结果,搜索用时 9 毫秒
61.
Manuel Plaza Christian Jandl Thorsten Bach 《Angewandte Chemie (International ed. in English)》2020,59(31):12785-12788
Trisubstituted allenes with a 3‐(1′‐alkenylidene)‐pyrrolidin‐2‐one motif were successfully deracemized (13 examples, 86–98 % ee) employing visible light (λ=420 nm) and a chiral triplet sensitizer as the catalyst (2.5 mol %). The photocatalyst likely operates by selective recognition of one allene enantiomer via hydrogen bonds and by a triplet‐sensitized racemization process. Even a tetrasubstituted allene (45 % ee) and a seven‐membered 3‐(1′‐alkenylidene)‐azepan‐2‐one (62 % ee) could be enantiomerically enriched under the chosen conditions. It was shown that the axial chirality of the allenes can be converted into point chirality by a Diels–Alder (94–97 % ee) or a bromination reaction (91 % ee). Ring opening of the five‐membered pyrrolidin‐2‐one was achieved without significantly compromising the integrity of the chirality axis (92 % ee). 相似文献
62.
Thomas Rigotti Daniel P. Schwinger Raphaela Graßl Christian Jandl Thorsten Bach 《Chemical science》2022,13(8):2378
In intramolecular [2+2] photocycloaddition reactions, the two tethered olefins can approach each other in a straight or in a crossed fashion. Despite the fact that the latter reaction mode leads to intriguing, otherwise inaccessible bridged skeletons, there has so far not been any enantioselective variants thereof. This study concerned the crossed [2+2]-photocycloaddition of 2-(alkenyloxy)cyclohex-2-enones to bridged cyclobutanes. It was found that the reaction could be performed with high enantioselectivity (80–94% ee) under visible light conditions when employing a chiral rhodium Lewis acid as a catalyst (2 mol%).An enantioselective crossed [2+2] photocycloaddition is presented which proceeds under visible light irradiation in the presence of a chiral Lewis acidic metal complex. Chelation of two oxygen atoms to the metal centre accounts for the observed enantioface differentiation. 相似文献
63.
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
64.
A membrane-assisted solvent extraction (MASE) method is presented for the extraction of several non-ionic organophosphorus chemicals from wastewaters samples followed by LC-MS/MS determination. The method was developed for a variety of chlorinated phosphates (trichloroethyl, tichloropropyl) and non-chlorinated phosphates (triphenyl, tributyl) used as flame retardants and for plasticizers such as triethylhexyl and tris-butoxyethyl phosphate. Parameters such as extracting solvent, sample volume and ionic strength, extraction temperature and time were optimized. The final method provides good quantification limits (1-25 ng L(-1)) and linearity (R2>0.9978). Method precision was also good at high concentrations (5% mean RSD at the 500 ng L(-1) level) but decreased at lower concentrations (20% mean RSD at the 20 ng L(-1) level). MASE yields lower matrix effects than SPE in a successive LC-MS/MS analysis of these compounds, avoiding the need for standard addition for quantification. When applied to wastewater samples comparable results were obtained using either MASE with internal standard calibration or SPE with standard addition. 相似文献
65.
The Ideal Ionic Liquid Salt Bridge for the Direct Determination of Gibbs Energies of Transfer of Single Ions,Part I: The Concept 下载免费PDF全文
Dr. Valentin Radtke Andreas Ermantraut Dr. Daniel Himmel Prof. Thorsten Koslowski Prof. Ivo Leito Prof. Ingo Krossing 《Angewandte Chemie (International ed. in English)》2018,57(9):2344-2347
Described is a procedure for the thermodynamically rigorous, experimental determination of the Gibbs energy of transfer of single ions between solvents. The method is based on potential difference measurements between two electrochemical half cells with different solvents connected by an ideal ionic liquid salt bridge (ILSB). Discussed are the specific requirements for the IL with regard to the procedure, thus ensuring that the liquid junction potentials (LJP) at both ends of the ILSB are mostly canceled. The remaining parts of the LJPs can be determined by separate electromotive force measurements. No extra‐thermodynamic assumptions are necessary for this procedure. The accuracy of the measurements depends, amongst others, on the ideality of the IL used, as shown in our companion paper Part II. 相似文献
66.
Lukas Fritz Dr. Sebastian Wienhold Sabrina Hackl Prof. Dr. Thorsten Bach 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(3):e202104064
A synthetic route to the pulvomycin class of natural products is presented, which culminated in the first synthesis of a pulvomycin, pulvomycin D. Key elements of the strategy include a pivotal aldol reaction which led to bond formation between the C24-C40 and the C8-C23 fragment. The remaining C1-C7 fragment was attached by a Yamaguchi esterification completing the assembly of the 40 carbon atoms within the main skeleton. Ring closure to the 22-membered lactone ring was achieved in the final stages of the synthesis by a Heck reaction. The completion of the synthesis required the removal of six silyl protecting groups in combination with olefin formation at C26-C27 by a Peterson elimination. 相似文献
67.
68.
69.
Instruments for surgical and dental application based on oscillatory mechanics submit unwanted vibrations to the operator’s hand. Frequently the weight of the instrument’s body is increased to dampen its vibration. Based on recent research regarding the optimization of granular damping we developed a prototype granular damper that attenuates the vibrations of an oscillatory saw twice as efficiently as a comparable solid mass. 相似文献
70.