全文获取类型
收费全文 | 466篇 |
免费 | 12篇 |
国内免费 | 2篇 |
专业分类
化学 | 329篇 |
力学 | 12篇 |
数学 | 70篇 |
物理学 | 69篇 |
出版年
2023年 | 2篇 |
2022年 | 17篇 |
2021年 | 22篇 |
2020年 | 11篇 |
2019年 | 8篇 |
2018年 | 6篇 |
2017年 | 4篇 |
2016年 | 8篇 |
2015年 | 15篇 |
2014年 | 10篇 |
2013年 | 36篇 |
2012年 | 26篇 |
2011年 | 33篇 |
2010年 | 14篇 |
2009年 | 27篇 |
2008年 | 25篇 |
2007年 | 28篇 |
2006年 | 25篇 |
2005年 | 33篇 |
2004年 | 21篇 |
2003年 | 11篇 |
2002年 | 15篇 |
2001年 | 5篇 |
2000年 | 4篇 |
1999年 | 7篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 7篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1987年 | 4篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 4篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1972年 | 3篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1923年 | 1篇 |
排序方式: 共有480条查询结果,搜索用时 31 毫秒
31.
Stefani Gamboa-Ramirez Dr. Bruno Faure Dr. Marius Réglier Dr. A. Jalila Simaan Dr. Maylis Orio 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(66):e202202206
The stereoselective copper-mediated hydroxylation of intramolecular C−H bonds from tridentate ligands is reinvestigated using DFT calculations. The computational study aims at deciphering the mechanism of C−H hydroxylation obtained after reaction of Cu(I) precursors with dioxygen, using ligands bearing either activated ( L1 ) or non-activated ( L2 ) C−H bonds. Configurational analysis allows rationalization of the experimentally observed regio- and stereoselectivity. The computed mechanism involves the formation of a side-on peroxide species ( P ) in equilibrium with the key intermediate bis-(μ-oxo) isomer ( O ) responsible for the C−H activation step. The P/O equilibrium yields the same activation barrier for the two complexes. However, the main difference between the two model complexes is observed during the C−H activation step, where the complex bearing the non-activated C−H bonds yields a higher energy barrier, accounting for the experimental lack of reactivity of this complex under those conditions. 相似文献
32.
Eric Mayer-Santos Tatjana Maravic Allegra Comba Patricia Moreira Freitas Giovanna Bueno Marinho Claudia Mazzitelli Edoardo Mancuso Nicola Scotti Federica Florenzano Lorenzo Breschi Annalisa Mazzoni 《Molecules (Basel, Switzerland)》2022,27(5)
This study aimed to investigate matrix metalloproteinase (MMP) activity in human dentin using in-situ and gelatin zymography, after at-home and in-office bleaching, related to their clinical exposure times. Dentin specimens (n = 5) were treated with 35% hydrogen peroxide (50 min per session/4 sessions), 10% carbamide peroxide (180 min/21 sessions), or no treatment. All were subjected to in-situ zymography. Dentin slices were, subsequently, obtained, covered with fluorescein-conjugated gelatin, and examined with confocal laser-scanning microscopy. The fluorescence intensity was quantified and statistically analyzed using one-way ANOVA and Bonferroni tests (α = 0.05). Furthermore, gelatin zymography was performed on protein extracts obtained from dentin powder (N = 8 teeth), treated with hydrogen peroxide or carbamide peroxide, with different exposure times (10/50 min for hydrogen peroxide; 252/1260 min for carbamide peroxide). The results of the in-situ zymography showed no statistical differences between the bleached specimens and the control group, with a medium level of gelatinolytic activity expressed in the dentin tubules. The results of gelatin zymography showed an increased expression of pro-MMP-9 in carbamide peroxide groups. The expression of pro-MMP-2 decreased in all the experimental groups. The bleaching treatments performed on the enamel of sound teeth do not influence dentinal enzymatic activity. However, when unprotected dentin tissue is bleached, matrix metalloproteinases are more expressed, particularly when carbamide peroxide is used, proportional to the exposure time. 相似文献
33.
34.
The first measurement of the absolute (e, 2e) five times differential cross section in coplanar symmetric conditions on He are reported. Incident energy is varied from 200 to 4000 eV in order to test different theoretical models. 相似文献
35.
36.
The effectiveness of electrochemical reactors for industrial wastewater treatment has been improved since three-dimensional electrodes have been introduced; in fact, limitations of mass transfer can arise, due to the low concentrations of pollutants which may be involved in the process. Three-dimensional electrodes offer a very high electrode area per unit electrode volume and they can act as turbulence promoters or give rise to high linear electrolyte velocity, resulting in high values of mass transport coefficient. However, careful selection of operative parameters is needed in order to obtain high performance. This paper examines the results obtained in our laboratory on the cathodic reduction of copper at RVC electrodes; in particular the interference of dissolved oxygen is studied during the removal of copper from extremely diluted solutions (C < 10 ppm). Some results are also discussed on the removal of organic pollutants by electrochemical oxidation at three-dimensional anode consisting of a fixed bed of carbon pellets. 相似文献
37.
Gailitis A Lielausis O Dement'ev S Platacis E Cifersons A Gerbeth G Gundrum T Stefani F Christen M Hanel H Will G 《Physical review letters》2000,84(19):4365-4368
In a closed volume of molten sodium an intense single-vortex-like helical flow has been produced by an outside powered propeller. At a flow rate of 0.67 m(3)/s a slowly growing magnetic field eigenmode was detected. For a slightly lower flow, additional measurements showed a slow decay of this mode. The measured results correspond satisfactorily with numerical predictions for the growth rates and frequencies. 相似文献
38.
39.
Marcio W. Paixão Minéia Weber Juliano B. de Azeredo Hélio A. Stefani 《Tetrahedron letters》2008,49(15):2366-2370
The copper-catalyzed dimerization of alkynyltrifluoroborates proceeds readily with good yields. The homo-coupling reaction can be effected in DMSO, in the open air, using Cu(OAc)2 as catalyst in the absence of any other additives. A variety of functional groups are tolerated. 相似文献
40.
Annalisa Bertoli Lidia Fanfoni Fulvia Felluga Giuliana Pitacco Ennio Valentin 《Tetrahedron: Asymmetry》2009,20(19):2305-2310
Three α-methylene-γ-carbomethoxy-γ-butyrolactams (methyl α-methylene-pyroglutamates) 11, 12 and 13, differing in the substitution at the heterocyclic nitrogen, as well as the structurally related γ-lactones 14 and 15 were synthesised and resolved enzymatically by hydrolysis of their ester function, mediated by commercially available hydrolytic enzymes. In particular, the α-chymotrypsin proved to be active to all the substrates examined, displaying a different degree of activity and enantioselectivity, this latter increasing significantly towards the substrate with an aromatic substituent at the nitrogen. 相似文献