全文获取类型
收费全文 | 3317篇 |
免费 | 78篇 |
国内免费 | 22篇 |
专业分类
化学 | 2064篇 |
晶体学 | 11篇 |
力学 | 145篇 |
数学 | 500篇 |
物理学 | 697篇 |
出版年
2024年 | 4篇 |
2023年 | 35篇 |
2022年 | 78篇 |
2021年 | 114篇 |
2020年 | 100篇 |
2019年 | 80篇 |
2018年 | 58篇 |
2017年 | 45篇 |
2016年 | 129篇 |
2015年 | 91篇 |
2014年 | 134篇 |
2013年 | 168篇 |
2012年 | 222篇 |
2011年 | 253篇 |
2010年 | 142篇 |
2009年 | 124篇 |
2008年 | 200篇 |
2007年 | 194篇 |
2006年 | 207篇 |
2005年 | 192篇 |
2004年 | 149篇 |
2003年 | 127篇 |
2002年 | 126篇 |
2001年 | 50篇 |
2000年 | 24篇 |
1999年 | 29篇 |
1998年 | 34篇 |
1997年 | 40篇 |
1996年 | 36篇 |
1995年 | 21篇 |
1994年 | 23篇 |
1993年 | 18篇 |
1992年 | 8篇 |
1991年 | 16篇 |
1990年 | 9篇 |
1989年 | 10篇 |
1988年 | 12篇 |
1987年 | 9篇 |
1986年 | 12篇 |
1985年 | 9篇 |
1984年 | 10篇 |
1983年 | 9篇 |
1982年 | 12篇 |
1981年 | 14篇 |
1980年 | 7篇 |
1979年 | 10篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 9篇 |
排序方式: 共有3417条查询结果,搜索用时 15 毫秒
71.
72.
Juliana Sih Shyam S. Bansal Stefano Filipini Silvia Ferrati Kunal Raghuwansi Erika Zabre Eugenia Nicolov Daniel Fine Mauro Ferrari Ganesh Palapattu Alessandro Grattoni 《Analytical and bioanalytical chemistry》2013,405(5):1547-1557
Novel drug delivery systems capable of continuous sustained release of therapeutics have been studied extensively for use in the prevention and management of chronic diseases. The use of these systems holds promise as a means to achieve higher patient compliance while improving therapeutic index and reducing systemic toxicity. In this work, an implantable nanochannel drug delivery system (nDS) is characterized and evaluated for the long-term sustained release of atorvastatin (ATS) and trans-resveratrol (t-RES), compounds with a proven role in managing atherogenic dyslipidemia and promoting cardioprotection. The primary mediators of drug release in the nDS are nanofluidic membranes with hundreds of thousands of nanochannels (up to 100,000/mm2) that attain zero-order release kinetics by exploiting nanoconfinement and molecule-to-surface interactions that dominate diffusive transport at the nanoscale. These membranes were characterized using gas flow analysis, acetone diffusion, and scanning and transmission electron microscopy (SEM, TEM). The surface properties of the dielectric materials lining the nanochannels, SiO2 and low-stress silicon nitride, were further investigated using surface charge analysis. Continuous, sustained in vitro release for both ATS and t-RES was established for durations exceeding 1 month. Finally, the influence of the membranes on cell viability was assessed using human microvascular endothelial cells. Morphology changes and adhesion to the surface were analyzed using SEM, while an MTT proliferation assay was used to determine the cell viability. The nanochannel delivery approach, here demonstrated in vitro, not only possesses all requirements for large-scale high-yield industrial fabrication, but also presents the key components for a rapid clinical translation as an implantable delivery system for the sustained administration of cardioprotectants. 相似文献
73.
Laetitia Shintu Stefano Caldarelli Mylène Campredon 《Analytical and bioanalytical chemistry》2013,405(28):9093-9100
In this paper, we present for the first time the use of high-resolution magic angle spinning nuclear magnetic resonance (HRMAS NMR) spectroscopy combined with chemometrics as an alternative tool for the characterization of tobacco products from different commercial international brands as well as for the identification of counterfeits. Although cigarette filling is a very complex chemical mixture, we were able to discriminate between dark, bright, and additive-free cigarette blends belonging to six different filter-cigarette brands, commercially available, using an approach for which no extraction procedure is required. Second, we focused our study on a specific worldwide-distributed brand for which established counterfeits were available. We discriminated those from their genuine counterparts with 100 % accuracy using unsupervised multivariate statistical analysis. The counterfeits that we analyzed showed a higher amount of nicotine and solanesol and a lower content of sugars, all endogenous tobacco leaf metabolites. This preliminary study demonstrates the great potential of HRMAS NMR spectroscopy to help in controlling cigarette authenticity. Figure
Prediction of the authenticity of smuggled B2 cigarettes. All of them were further established as counterfeits 相似文献
74.
Clemente Bretti Concetta De Stefano Claudia Foti Silvio Sammartano 《Journal of solution chemistry》2013,42(7):1452-1471
The protonation constants and solubilities of three complexons [ethylenediamine-N,N′-disuccinic acid (EDDS), ethylene glycol bis(2-aminoethyl ether)-N,N,N′,N′-tetraacetic acid (EGTA) and 1,2-cyclohexanediamine-N,N,N′,N′-tetraacetic acid (CDTA)] are reported in aqueous solutions of NaCl with different ionic strength values (0 ≤ I ≤ 4.8 mol·L?1) and, in the case of CDTA, in (CH3)4NCl (0.1 ≤ I ≤ 2.7 mol·L?1). The dependence on ionic strength of the protonation constants of these three complexons and four other complexons that were previously reported (NTA, EDTA, DTPA and TTHA), is analyzed in NaCl solution; the ionic strength influences quite strongly the protonation constants (as an example for CDTA, log10 K 1 = 10.54 and 9.25 at I = 0.1 and 1 mol·L?1, respectively), while the effect of (CH3)4NCl concentration is lower. Based on the total solubility S T and the protonation constant data at different salt concentrations, the solubility of the neutral species S 0 and the solubility products K S0 are obtained. The Setschenow coefficients k m and the solubility values S 0 0 in pure water are also reported (S 0 0 = 0.55, 0.21 and 0.75 mmol·kg?1 for EDDS, EGTA and CDTA, respectively). The dependence of the protonation constants on ionic strength is also interpreted in terms of ion pair formation, and the formation constants of Na+ species are reported. 相似文献
75.
Joel Malmgren Dr. Stefano Santoro Dr. Nazli Jalalian Prof. Fahmi Himo Prof. Berit Olofsson 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(31):10334-10342
Phenols, anilines, and malonates have been arylated under metal‐free conditions with twelve aryl(phenyl)iodonium salts in a systematic chemoselectivity study. A new “anti‐ortho effect” has been identified in the arylation of malonates. Several “dummy groups” have been found that give complete chemoselectivity in the transfer of the phenyl moiety, irrespective of the nucleophile. An aryl exchange in the diaryliodonium salts has been observed under certain arylation conditions. DFT calculations have been performed to investigate the reaction mechanism and to elucidate the origins of the observed selectivities. These results are expected to facilitate the design of chiral diaryliodonium salts and the development of catalytic arylation reactions that are based on these sustainable and metal‐free reagents. 相似文献
76.
Dr. Antonello Di Crescenzo Dr. Luca Bardini Dr. Bruna Sinjari Dr. Tonino Traini Dr. Lisa Marinelli Dr. Mauro Carraro Prof. Raimondo Germani Dr. Pietro Di Profio Prof. Sergio Caputi Prof. Antonio Di Stefano Prof. Marcella Bonchio Prof. Francesco Paolucci Prof. Antonella Fontana 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(48):16415-16423
Novel hydrogel phases based on positively charged and zwitterionic surfactants, namely, N‐[p‐(n‐dodecyloxybenzyl)]‐N,N,N‐trimethylammonium bromide (pDOTABr) and p‐dodecyloxybenzyldimethylamine oxide (pDOAO), which combine pristine carbon nanotubes (CNTs), were obtained, thus leading to stable dispersions and enhanced cross‐linked networks. The composite hydrogel featuring a well‐defined nanostructured morphology and an overall positively charged surface was shown to efficiently immobilise a polyanionic and redox‐active tetraruthenium‐substituted polyoxometalate (Ru4POM) by complementary charge interactions. The resulting hybrid gel has been characterised by electron microscopy techniques, whereas the electrostatic‐directed assembly has been monitored by means of fluorescence spectroscopy and ζ‐potential tests. This protocol offers a straightforward supramolecular strategy for the design of novel aqueous‐based electrocatalytic soft materials, thereby improving the processability of CNTs while tuning their interfacial decoration with multiple catalytic domains. Electrochemical evidence confirms that the activity of the catalyst is preserved within the gel media. 相似文献
77.
78.
Sergio Mauricio Bonesi Daniele Dondi Stefano Protti Maurizio Fagnoni Angelo Albini 《Tetrahedron letters》2014
Irradiation of triphenylamine (Ph3N) in nitrogen-flushed solution leads to 9-phenylcarbazole and two tetrahydroderivatives (1,2,3,4- and 1,2,7,8-) via disproportionation of the corresponding 4a,4b-dihydrocarbazole. In oxygen-equilibrated solution oxidative cyclization occurs through the intermediacy of a triplet peroxy diradical, which either abstracts a hydrogen atom intramolecularly or (mainly) cleaves back to the reagents. The role of the key intermediates is supported by DFT calculations and by trapping by triarylphosphines (that are thus efficiently oxidized, while preventing the cyclization of Ph3N). The hydroperoxide, on the other hand, causes inefficient co-oxidation of sulfides. 相似文献
79.
Maurizio Sansotera Cristian Gambarotti Antonino Famulari Alberto Baggioli Raffaella Soave Francesco Venturini Stefano V. Meille Ivan Wlassics Walter Navarrini 《Tetrahedron》2014
Perfluoroalkyl radicals, generated by thermal decomposition of perfluorodiacyl peroxides, react selectively with quinone rings of 1,4-naphthoquinones. In the presence of a non-conjugated alkene such as 1-hexene, perfluoroalkyl radicals add to the double bonds of the olefin forming a radical adduct, which selectively adds to the naphthoquinone ring. Several perfluorodiacyl peroxides have been synthesized and used for the direct and alkene-mediated functionalization of naphthoquinones. Geometrical parameters and electron density topology of all perfluorodiacyl peroxides have been calculated by the density functional formalism and quantum theory of atoms in molecules to attempt a rationalization of the experimental reactivity. 相似文献
80.