全文获取类型
收费全文 | 2530篇 |
免费 | 65篇 |
国内免费 | 17篇 |
专业分类
化学 | 2052篇 |
晶体学 | 10篇 |
力学 | 38篇 |
数学 | 256篇 |
物理学 | 256篇 |
出版年
2023年 | 13篇 |
2022年 | 34篇 |
2021年 | 34篇 |
2020年 | 43篇 |
2019年 | 38篇 |
2018年 | 27篇 |
2017年 | 26篇 |
2016年 | 59篇 |
2015年 | 48篇 |
2014年 | 55篇 |
2013年 | 130篇 |
2012年 | 160篇 |
2011年 | 181篇 |
2010年 | 119篇 |
2009年 | 110篇 |
2008年 | 190篇 |
2007年 | 174篇 |
2006年 | 132篇 |
2005年 | 172篇 |
2004年 | 156篇 |
2003年 | 120篇 |
2002年 | 134篇 |
2001年 | 34篇 |
2000年 | 27篇 |
1999年 | 25篇 |
1998年 | 27篇 |
1997年 | 21篇 |
1996年 | 26篇 |
1995年 | 15篇 |
1994年 | 17篇 |
1993年 | 15篇 |
1992年 | 25篇 |
1991年 | 19篇 |
1990年 | 11篇 |
1989年 | 16篇 |
1988年 | 7篇 |
1986年 | 8篇 |
1985年 | 13篇 |
1984年 | 14篇 |
1983年 | 11篇 |
1982年 | 17篇 |
1981年 | 8篇 |
1980年 | 14篇 |
1979年 | 10篇 |
1978年 | 8篇 |
1977年 | 10篇 |
1976年 | 16篇 |
1975年 | 10篇 |
1974年 | 5篇 |
1973年 | 6篇 |
排序方式: 共有2612条查询结果,搜索用时 15 毫秒
41.
Gram‐Scale Enantioselective Formal Synthesis of Morphine through an ortho–para Oxidative Phenolic Coupling Strategy 下载免费PDF全文
Dr. Matthieu Tissot Dr. Robert J. Phipps Dr. Catherine Lucas Dr. Rafael M. Leon Dr. Robert D. M. Pace Dr. Tifelle Ngouansavanh Prof. Matthew J. Gaunt 《Angewandte Chemie (International ed. in English)》2014,53(49):13498-13501
A gram‐scale catalytic enantioselective formal synthesis of morphine is described. The key steps of the synthesis involve an ortho–para oxidative phenolic coupling and a highly diastereoselective “desymmetrization” of the resulting cyclohexadienone that generates three of the four morphinan ring junction stereocenters in one step. The stereochemistry is controlled from a single carbinol center installed through catalytic enantioselective hydrogenation. These transformations enabled the preparation of large quantities of key intermediates and could support a practical and scalable synthesis of morphine and related derivatives. 相似文献
42.
Prachi Vilekar Catherine King Pallavi Lagisetty Vibhudutta Awasthi Shanjana Awasthi 《Applied biochemistry and biotechnology》2014,172(7):3363-3373
Curcumin is well known for its antimicrobial and anti-inflammatory properties. However, since systemic absorption and bioavailability of curcumin from gastrointestinal tract is considerably poor, synthetic curcuminoids are being developed as better alternatives. Two curcumin derivatives: 3,5-bis(benzylidene)-4-piperidone (EF24) and EF24-dimer linked via diethylenetriaminepentacetic acid (EF2DTPA), were included in this study. We investigated the antibacterial activity of EF24 and EF2DTPA against Gram-negative (Escherichia coli) and Gram-positive (Enterococcus faecalis, Staphylococcus aureus) bacteria. We also studied the effects of EF24 and EF2DTPA on uptake and localization of pHrodo-labeled E. coli in the acidic compartments (phagolysosomes) of dendritic cells (DCs) under in vitro conditions. Our results demonstrate that treatment with EF24 and EF2DTPA directly suppresses the bacterial growth. However, these compounds do not affect the bacterial uptake or localization in the DCs. 相似文献
43.
Dr. Antoine Tardy Noémie Gil Dr. Christopher M. Plummer Prof. Didier Siri Dr. Didier Gigmes Dr. Catherine Lefay Dr. Yohann Guillaneuf 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(34):14625-14634
Radical ring-opening polymerization (rROP) of cyclic ketene acetals (CKAs) combines the advantages of both ring-opening polymerization and radical polymerization thereby allowing the robust production of polyesters coupled with the mild polymerization conditions of a radical process. rROP was recently rejuvenated by the possibility to copolymerize CKAs with classic vinyl monomers leading to the insertion of cleavable functionality into a vinyl-based copolymer backbone and thus imparting (bio)degradability. Such materials are suitable for a large scope of applications, particularly within the biomedical field. The competition between the ring-opening and ring-retaining propagation routes is a major complication in the development of efficient CKA monomers, ultimately leading to the use of only four monomers that are known to completely ring-open under all experimental conditions. In this article we investigate the radical ring-opening polymerization of model CKA monomers and demonstrate by the combination of DFT calculations and kinetic modeling using PREDICI software that we are now able to predict in silico the ring-opening ability of CKA monomers. 相似文献
44.
Dr. Julien Gasnot Clément Botella Dr. Sébastien Comesse Dr. Sami Lakhdar Dr. Carole Alayrac Prof. Annie-Claude Gaumont Prof. Vincent Dalla Dr. Catherine Taillier 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(29):11867-11871
Advances in the field of phosphorus chemistry are documented, by revealing the synthetic utility of previously underutilized quaternary phosphiranium salts (QPrS) as three-chain-atom electrophilic building blocks. Notably, control of their challenging C-centered electrophilicity is disclosed with an expedient synthesis of tertiary β-anilino phosphines as a proof-of-concept. 相似文献
45.
Catherine Bessada Aydar Rakhmatullin Anne-Laure Rollet Didier Zanghi 《Journal of fluorine chemistry》2009,130(1):45-52
In situ high temperature nuclear magnetic resonance in molten fluoride mixtures gives some structural picture of the complexes existing in the melt, i.e. of their nature and relative proportion. Thanks to the development of a laser heating system associated with a close crucible in boron nitride, we can describe experimentally the evolution of these complexes from the anions and the cations point of view. By 19F NMR, we have shown the existence of three kinds of fluorine atoms depending on the composition: free fluorine like in pure LiF (non-bonded), bridging fluorine in melts rich in LnF3 in addition with terminal fluorine singly bonded to one rare earth. Data obtained by NMR spectroscopy are also combined with EXAFS measurements, again thanks to a specific development of the sample holder adapted with molten fluorides and high temperature. This study is a part of our systematic investigation of the different Alk-LnF3 systems by NMR and EXAFS spectroscopy. 相似文献
46.
The synthetic investigation of the CuII/maleamate(−1) ion (HL−)/N,N′,N′′-chelate general reaction system has allowed access to compounds [Cu2(HL)2(bppy)2](ClO4)2·H2O (1·H2O), [Cu(HL)(bppy)(ClO4)] (2) and [Cu(HL)(terpy)(H2O)](ClO4) (4) (bppy = 2,6-bis(pyrazol-1-yl)pyridine, terpy = 2,2′;6′,2′′-terpyridine). In the absence of externally added hydroxides, compound [Cu2(L′)2(bppy)2](ClO4)2 (3) was obtained from MeOH solutions; L′− is the monomethyl maleate(−1) ligand which is formed in situ via the CuII-assisted HL− → L′− transformation. In the case of tptz-containing (tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine) reaction systems, the CuII-assisted hydrolysis of tptz to pyridine-2-carboxamide (L1) afforded complex [Cu(L1)2(NO3)2] (5). The crystal structures of 1–5 are stabilized by intermolecular hydrogen bonding and π–π stacking interactions. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the ligands. 相似文献
47.
Mathieu Albini Catherine Taillier Vincent Dalla Jérôme Blanchet Jacques Rouden 《Tetrahedron letters》2014
A dramatic improvement of our previous methodology based on a Suzuki–Miyaura cross-coupling to access 3,3′-disubstituted H8-BINOLs using microwave heating is reported herein. These new conditions represent a large gain in term of atom-economy, reaction time, catalyst loading, and excess of reagents employed. 相似文献
48.
The objective of this paper is to examine causality and feedback relationships between primary commodity prices and US inflation. To this end, the bivariate noisy Mackey–Glass process recently developed by Kyrtsou and Labys [Evidence for chaotic dependence between US inflation and commodity prices, J. Macroecon. 28(1) (2006) 256–266] has been applied to assess this relationship. Results obtained support evidence in favour of causality, which can help to identify the influences of speculative price behaviour on inflation. 相似文献
49.
When a test sound consisting of pure tones with equal intensities is preceded by a precursor sound identical to the test sound except for a reduction in the intensity of one tone, an auditory "enhancement" phenomenon occurs: In the test sound, the tone which was previously softer stands out perceptually. Here, enhancement was investigated using inharmonic sounds made up of five pure tones well resolved in the auditory periphery. It was found that enhancement can be elicited not only by increases in intensity but also by shifts in frequency. In both cases, when the precursor and test sounds are separated by a 500-ms delay, inserting a burst of pink noise during the delay has little effect on enhancement. Presenting the precursor and test sounds to opposite ears rather than to the same ear significantly reduces the enhancement resulting from increases in intensity, but not the enhancement resulting from shifts in frequency. This difference suggests that the mechanisms of enhancement are not identical for the two types of change. For frequency shifts, enhancement may be partly based on the existence of automatic "frequency-shift detectors" [Demany and Ramos, J. Acoust. Soc. Am. 117, 833-841 (2005)]. 相似文献
50.