全文获取类型
收费全文 | 2868篇 |
免费 | 124篇 |
国内免费 | 16篇 |
专业分类
化学 | 1725篇 |
晶体学 | 4篇 |
力学 | 133篇 |
数学 | 612篇 |
物理学 | 534篇 |
出版年
2023年 | 30篇 |
2022年 | 25篇 |
2021年 | 110篇 |
2020年 | 77篇 |
2019年 | 91篇 |
2018年 | 69篇 |
2017年 | 54篇 |
2016年 | 115篇 |
2015年 | 110篇 |
2014年 | 126篇 |
2013年 | 196篇 |
2012年 | 227篇 |
2011年 | 251篇 |
2010年 | 149篇 |
2009年 | 109篇 |
2008年 | 204篇 |
2007年 | 175篇 |
2006年 | 162篇 |
2005年 | 167篇 |
2004年 | 114篇 |
2003年 | 104篇 |
2002年 | 81篇 |
2001年 | 37篇 |
2000年 | 23篇 |
1999年 | 18篇 |
1998年 | 11篇 |
1997年 | 22篇 |
1996年 | 19篇 |
1995年 | 16篇 |
1994年 | 15篇 |
1993年 | 12篇 |
1992年 | 6篇 |
1991年 | 2篇 |
1990年 | 8篇 |
1989年 | 6篇 |
1986年 | 4篇 |
1985年 | 6篇 |
1984年 | 8篇 |
1983年 | 9篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 3篇 |
1937年 | 2篇 |
1916年 | 1篇 |
排序方式: 共有3008条查询结果,搜索用时 15 毫秒
31.
ATP-Independent and Cell-Free Biosynthesis of β-Hydroxy Acids Using Vinyl Esters as Smart Substrates
Dr. Alejandro H. Orrego Dr. Maria Grazia Rubanu Idania L. López Daniel Andrés-Sanz Dr. Guillermo García-Marquina Dr. German E. Pieslinger Prof. Luca Salassa Prof. Fernando López-Gallego 《Angewandte Chemie (International ed. in English)》2023,62(13):e202218312
In vitro biosynthetic pathways that condense and reduce molecules through coenzyme A (CoASH) activation demand energy and redox power in the form of ATP and NAD(P)H, respectively. These coenzymes must be orthogonally recycled by ancillary reactions that consume chemicals, electricity, or light, impacting the atom economy and/or the energy consumption of the biosystem. In this work, we have exploited vinyl esters as dual acyl and electron donor substrates to synthesize β-hydroxy acids through a non-decarboxylating Claisen condensation, reduction and hydrolysis stepwise cascade, including a NADH recycling step, catalyzed by a total of 4 enzymes. Herein, the chemical energy to activate the acyl group with CoASH and the redox power for the reduction are embedded into the vinyl esters. Upon optimization, this self-sustaining cascade reached a titer of (S)-3-hydroxy butyrate of 24 mM without requiring ATP and simultaneously recycling CoASH and NADH. This work illustrates the potential of in vitro biocatalysis to transform simple molecules into multi-functional ones. 相似文献
32.
Henri de Maissin Philipp R. Groß Obaid Mohiuddin Dr. Moritz Weigt Luca Nagel Marvin Herzog Zirun Wang Robert Willing Dr. Wilfried Reichardt Dr. Martin Pichotka Dr. Lisa Heß Prof. Dr. Thomas Reinheckel Prof. Dr. Henning J. Jessen Prof. Dr. Robert Zeiser Prof. Dr. Michael Bock Prof. Dominik von Elverfeldt Prof. Dr. Maxim Zaitsev Dr. Sergey Korchak Dr. Stefan Glöggler Prof. Dr. Jan-Bernd Hövener Prof. Dr. Eduard Y. Chekmenev Prof. Dr. Franz Schilling Dr. Stephan Knecht Dr. Andreas B. Schmidt 《Angewandte Chemie (International ed. in English)》2023,62(36):e202306654
33.
Dr. Pradeep Chopra Dr. Tejabhiram Yadavalli Francesco Palmieri Dr. Seino A. K. Jongkees Dr. Luca Unione Prof. Dr. Deepak Shukla Prof. Dr. Geert-Jan Boons 《Angewandte Chemie (International ed. in English)》2023,62(41):e202309838
Herpes simplex virus (HSV-1) employs heparan sulfate (HS) as receptor for cell attachment and entry. During late-stage infection, the virus induces the upregulation of human heparanase (Hpse) to remove cell surface HS allowing viral spread. We hypothesized that inhibition of Hpse will prevent viral release thereby representing a new therapeutic strategy for HSV-1. A range of HS-oligosaccharides was prepared to examine the importance of chain length and 2-O-sulfation of iduronic moieties for Hpse inhibition. It was found that hexa- and octasaccharides potently inhibited the enzyme and that 2-O-sulfation of iduronic acid is tolerated. Computational studies provided a rationale for the observed structure–activity relationship. Treatment of human corneal epithelial cells (HCEs) infected with HSV-1 with the hexa- and octasaccharide blocked viral induced shedding of HS which significantly reduced spread of virions. The compounds also inhibited migration and proliferation of immortalized HCEs thereby providing additional therapeutic properties. 相似文献
34.
Simone Brannetti Serena Gentile Dr. Alejandro Chamorro-Garcia Luca Barbero Dr. Erica Del Grosso Prof. Francesco Ricci 《Angewandte Chemie (International ed. in English)》2023,62(47):e202313243
Here we develop Lateral Flow Assays (LFAs) that employ as functional elements DNA-based structures decorated with reporter tags and recognition elements. We have rationally re-engineered tile-based DNA tubular structures that can act as scaffolds and can be decorated with recognition elements of different nature (i.e. antigens, aptamers or proteins) and with orthogonal fluorescent dyes. As a proof-of-principle we have developed sandwich and competitive multiplex lateral flow platforms for the detection of several targets, ranging from small molecules (digoxigenin, Dig and dinitrophenol, DNP), to antibodies (Anti-Dig, Anti-DNP and Anti-MUC1/EGFR bispecific antibodies) and proteins (thrombin). Coupling the advantages of functional DNA-based scaffolds together with the simplicity of LFAs, our approach offers the opportunity to detect a wide range of targets with nanomolar sensitivity and high specificity. 相似文献
35.
Qiang Liu Hubert Meissel Ilia Sadykov Simon Jones Nick Van Dijk Przemyslaw Rzepka Luca Artiglia Marco Ranocchiari Jeroen A. van Bokhoven 《Helvetica chimica acta》2021,104(7):e2100082
Stability studies on supported metal nanoparticles are essential for gaining insight into the design and optimization of high-performance materials. In this work, the dissolutions of Pt-based catalysts in HBr/Br2 mixture of various concentration regimes were studied and correlated with material structural properties. The dissolution of metal nanoparticles was enhanced by adding Br2 to the HBr solution. Comparing with commercial Pt/C catalyst, the well-alloyed PtIr/C catalyst was observed to exhibit high resistance towards dissolution. In addition, regulating the accessibility of the metal sites to dissolution-inducing species contributed to the marked stability of the nanoparticles in HBr/Br2 solutions, as shown for the surface-modified PtIr/C catalysts with organic diamine molecules. 相似文献
36.
Christoph M. Hendrich Sebastian Senn Lea Haas Marvin T. Hoffmann Dr. Ute Zschieschang Luca C. Greiner Dr. Frank Rominger Dr. Matthias Rudolph Dr. Hagen Klauk Prof. Dr. Andreas Dreuw Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(59):14778-14784
Herein, we describe a gold-catalyzed cascade cyclization of Boc-protected benzylamines bearing two tethered alkyne moieties in a domino reaction initiated by a 6-endo-dig cyclization. The reaction was screened intensively, and the scope was explored, resulting in nine new Boc-protected dihydrobenzo[c]phenanthridines with yields of up to 98 %; even a π-extension and two bidirectional approaches were successful. Furthermore, thermal cleavage of the Boc group and subsequent oxidation gave substituted benzo[c]phenanthridines in up to quantitative yields. Two bidirectional approaches under the optimized conditions were successful, and the resulting π-extended molecules were tested as organic semiconductors in organic thin-film transistors. 相似文献
37.
In this study, the N-dimensional radial Schrodinger equation with an anharmonic sextic potential is solved by the extended Nikirov-Uranov method. We prove that the radial function can be factorised as the product between an exponential function and a polynomial function solution of the biconfluent Heun equation. The approach investigated in this article aims to be an alternative to other known methods of solving, as it has the advantage of dealing with simple, first-order differential and algebraic equations and avoiding numerous and laborious coordinate transformations and series expansions.
相似文献38.
Prof. Gianlorenzo Bussetti Claudia Filoni Prof. Andrea Li Bassi Dr. Alberto Bossi Prof. Marcello Campione Prof. Alessio Orbelli Biroli Prof. Chiara Castiglioni Dr. Silvia Trabattoni Dr. Stefania De Rosa Prof. Luca Tortora Prof. Franco Ciccacci Prof. Lamberto Duò 《ChemistryOpen》2021,10(8):748-755
We have recently discussed how organic nanocrystal dissolution appears in different morphologies and the role of the solution pH in the crystal detriment process. We also highlighted the role of the local molecular chemistry in porphyrin nanocrystals having comparable structures: in water-based acid solutions, protonation of free-base porphyrin molecules is the driving force for crystal dissolution, whereas metal (ZnII) porphyrin nanocrystals remain unperturbed. However, all porphyrin types, having an electron rich π-structure, can be electrochemically oxidized. In this scenario, a key question is: does electrochemistry represent a viable strategy to drive the dissolution of both free-base and metal porphyrin nanocrystals? In this work, by exploiting electrochemical atomic force microscopy (EC-AFM), we monitor in situ and in real time the dissolution of both free-base and metal porphyrin nanocrystals, as soon as molecules reach the oxidation potential, showing different regimes according to the applied EC potential. 相似文献
39.
Lucia De Rosa Rossella Di Stasi Alessandra Romanelli Luca Domenico DAndrea 《Molecules (Basel, Switzerland)》2021,26(12)
Although a plethora of chemistries have been developed to selectively decorate protein molecules, novel strategies continue to be reported with the final aim of improving selectivity and mildness of the reaction conditions, preserve protein integrity, and fulfill all the increasing requirements of the modern applications of protein conjugates. The targeting of the protein N-terminal alpha-amine group appears a convenient solution to the issue, emerging as a useful and unique reactive site universally present in each protein molecule. Herein, we provide an updated overview of the methodologies developed until today to afford the selective modification of proteins through the targeting of the N-terminal alpha-amine. Chemical and enzymatic strategies enabling the selective labeling of the protein N-terminal alpha-amine group are described. 相似文献
40.
The integration of constriction structures such as nanopores and nanochannels into fluidic devices discloses powerful biosensing capabilities that can be tuned to a wide range of analytes through conceptually simple size calibrations. The practical implementation of this tuning requires a nontrivial manipulation of matter at nanoscale with further requirements for low complexity and low-cost procedures that may be adapted to industrial production. Here, we review the recent progress on the fabrication techniques of nanopores and nanochannels, together with the efforts to realize their full biosensing potential by understanding and amending the problems still afflicting the measurement performed during operation. 相似文献