全文获取类型
收费全文 | 1975篇 |
免费 | 103篇 |
国内免费 | 11篇 |
专业分类
化学 | 1493篇 |
晶体学 | 9篇 |
力学 | 29篇 |
数学 | 296篇 |
物理学 | 262篇 |
出版年
2023年 | 16篇 |
2022年 | 13篇 |
2021年 | 25篇 |
2020年 | 72篇 |
2019年 | 48篇 |
2018年 | 29篇 |
2017年 | 12篇 |
2016年 | 42篇 |
2015年 | 57篇 |
2014年 | 58篇 |
2013年 | 83篇 |
2012年 | 76篇 |
2011年 | 109篇 |
2010年 | 49篇 |
2009年 | 61篇 |
2008年 | 92篇 |
2007年 | 82篇 |
2006年 | 69篇 |
2005年 | 98篇 |
2004年 | 93篇 |
2003年 | 63篇 |
2002年 | 56篇 |
2001年 | 51篇 |
2000年 | 37篇 |
1999年 | 31篇 |
1998年 | 34篇 |
1997年 | 34篇 |
1996年 | 34篇 |
1995年 | 30篇 |
1994年 | 27篇 |
1993年 | 33篇 |
1992年 | 27篇 |
1991年 | 31篇 |
1990年 | 35篇 |
1989年 | 22篇 |
1988年 | 22篇 |
1987年 | 25篇 |
1986年 | 19篇 |
1985年 | 22篇 |
1984年 | 23篇 |
1983年 | 12篇 |
1982年 | 15篇 |
1981年 | 23篇 |
1980年 | 14篇 |
1979年 | 16篇 |
1978年 | 20篇 |
1977年 | 19篇 |
1976年 | 19篇 |
1974年 | 16篇 |
1973年 | 15篇 |
排序方式: 共有2089条查询结果,搜索用时 21 毫秒
111.
Maximilian Stangier Alexej Scheremetjew Prof. Dr. Lutz Ackermann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201654
Electrochemical fluorinations of C(sp3)−H bonds with a nucleophilic fluoride source have been accomplished in a chemo- and site-selective fashion, avoiding the use of electrophilic F+ sources and stoichiometric oxidants. The introduced metal-free strategy exhibits high functional group tolerance, setting the stage for late-stage fluorinations of biorelevant motifs. The synthetic utility of the C(sp3)−H fluorination was reflected by subsequent one-pot arylation of the generated benzylic fluorides. 相似文献
112.
Emily C. Monkcom Daniël de Bruin Annemiek J. de Vries Dr. Martin Lutz Dr. Shengfa Ye Prof. Dr. Robertus J. M. Klein Gebbink 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(16):5191-5204
We present the synthesis and coordination chemistry of a bulky, tripodal N,N,O ligand, ImPh2NNO t Bu ( L ), designed to model the 2-His-1-carboxylate facial triad (2H1C) by means of two imidazole groups and an anionic 2,4-di-tert-butyl-subtituted phenolate. Reacting K-L with MCl2 (M = Fe, Zn) affords the isostructural, tetrahedral non-heme complexes [Fe(L)(Cl)] ( 1 ) and [Zn(L)(Cl)] ( 2 ) in high yield. The tridentate N,N,O ligand coordination observed in their X-ray crystal structures remains intact and well-defined in MeCN and CH2Cl2 solution. Reacting 2 with NaSPh affords a tetrahedral zinc thiolate complex, [Zn(L)(SPh)] ( 4 ), that is relevant to isopenicillin N synthase (IPNS) biomimicry. Cyclic voltammetry studies demonstrate the ligand's redox non-innocence, where phenolate oxidation is the first electrochemical response observed in K-L , 2 and 4 . However, the first electrochemical oxidation in 1 is iron-centred, the assignment of which is supported by DFT calculations. Overall, ImPh2NNO t Bu provides access to well-defined mononuclear, monoligated, N,N,O-bound metal complexes, enabling more accurate structural modelling of the 2H1C to be achieved. 相似文献
113.
Copper–Boxmi Complexes as Highly Enantioselective Catalysts for Electrophilic Trifluoromethylthiolations 下载免费PDF全文
Dr. Qing‐Hai Deng Christoph Rettenmeier Prof. Dr. Hubert Wadepohl Prof. Dr. Lutz H. Gade 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(1):93-97
The enantioselective trifluoromethylthiolation of β‐ketoesters using chiral copper–boxmi complexes as catalysts is reported. A number of α‐SCF3‐substituted β‐ketoesters have been obtained with up to >99 % enantiomeric excess (ee), and the trifluoromethylthiolated products were then transformed diastereoselectively to α‐SCF3‐β‐hydroxyesters with two adjacent quaternary stereocenters. 相似文献
114.
Precision PEGylated Polymers Obtained by Sequence‐Controlled Copolymerization and Postpolymerization Modification 下载免费PDF全文
Sansanee Srichan Dr. Hatice Mutlu Dr. Nezha Badi Dr. Jean‐François Lutz 《Angewandte Chemie (International ed. in English)》2014,53(35):9231-9235
Copolymers containing water‐soluble poly(ethylene glycol) (PEG) side chains and precisely controlled functional microstructures were synthesized by sequence‐controlled copolymerization of donor and acceptor comonomers, that is, styrene derivatives and N‐substituted maleimides. Two routes were compared for the preparation of these structures: a) the direct use of a PEG–styrene macromonomer as a donor comonomer, and b) the use of an alkyne‐functionalized styrenic comonomer, which was PEGylated by copper‐catalyzed alkyne–azide cycloaddition after polymerization. The latter method was found to be the most versatile and enabled the synthesis of high‐precision copolymers. For example, PEGylated copolymers containing precisely positioned fluorescent (e.g. pyrene), switchable (e.g. azobenzene), and reactive functionalities (e.g. an activated ester) were prepared. 相似文献
115.
Dr. Yann Gloaguen Christophe Rebreyend Dr. Martin Lutz Pravin Kumar Dr. Martina Huber Dr. Ir. Jarl Ivar van der Vlugt Prof. Dr. Sven Schneider Prof. Dr. Bas de Bruin 《Angewandte Chemie (International ed. in English)》2014,53(26):6814-6818
Photochemical activation of [(PNNH)Rh(N3)] (PNNH=6‐di‐(tert‐butyl)phosphinomethyl‐2,2′‐bipyridine) complex 2 produced the paramagnetic (S=1/2), [(PNN)Rh?N.‐Rh(PNN)] complex 3 (PNN?=methylene‐deprotonated PNNH), which could be crystallographically characterized. Spectroscopic investigation of 3 indicates a predominant nitridyl radical (.N2?) character, which was confirmed computationally. Complex 3 reacts selectively with CO, producing two equivalents of [(PNN)RhI(CO)] complex 4 , presumably by nitridyl radical N,N‐coupling. 相似文献
116.
M. Sc. Fanzhi Yang Karsten Rauch M. Sc. Katharina Kettelhoit Prof. Dr. Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2014,53(42):11285-11288
Versatile ruthenium(II) complexes allow for site‐selective C? H oxygenations with weakly‐coordinating aldehydes. The challenging C? H functionalizations proceed with high chemoselectivity by rate‐determining C? H metalation. The new method features an ample substrate scope, which sets the stage for the step‐economical preparation of various bioactive heterocycles. 相似文献
117.
Nickel‐Catalyzed C?H Alkylations: Direct Secondary Alkylations and Trifluoroethylations of Arenes 下载免费PDF全文
Weifeng Song Sebastian Lackner Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2014,53(9):2477-2480
A versatile nickel catalyst allowed for C H alkylations of unactivated arenes with challenging secondary alkyl bromides and chlorides. The high catalytic efficacy also set the stage for direct secondary alkylations of indoles as well as C H trifluoroethylations with ample substrate scope. 相似文献
118.
119.
Long Yang Ralf Steinbock Alexej Scheremetjew Rositha Kuniyil Lars H. Finger Antonis M. Messinis Lutz Ackermann 《Angewandte Chemie (International ed. in English)》2020,59(27):11130-11135
A ruthenium‐catalyzed electrochemical dehydrogenative annulation reaction of imidazoles with alkynes has been established, enabling the preparation of various bridgehead N‐fused [5,6]‐bicyclic heteroarenes through regioselective electrochemical C?H/N?H annulation without chemical metal oxidants. Novel azaruthenabicyclo[3.2.0]heptadienes were fully characterized and identified as key intermediates. Mechanistic studies are suggestive of an oxidatively induced reductive elimination pathway within a ruthenium(II/III) regime. 相似文献
120.