全文获取类型
收费全文 | 1093篇 |
免费 | 57篇 |
国内免费 | 1篇 |
专业分类
化学 | 727篇 |
晶体学 | 2篇 |
力学 | 53篇 |
数学 | 153篇 |
物理学 | 216篇 |
出版年
2024年 | 4篇 |
2023年 | 12篇 |
2022年 | 45篇 |
2021年 | 50篇 |
2020年 | 39篇 |
2019年 | 27篇 |
2018年 | 28篇 |
2017年 | 20篇 |
2016年 | 71篇 |
2015年 | 40篇 |
2014年 | 42篇 |
2013年 | 72篇 |
2012年 | 83篇 |
2011年 | 115篇 |
2010年 | 57篇 |
2009年 | 37篇 |
2008年 | 55篇 |
2007年 | 63篇 |
2006年 | 57篇 |
2005年 | 59篇 |
2004年 | 31篇 |
2003年 | 33篇 |
2002年 | 24篇 |
2001年 | 6篇 |
2000年 | 12篇 |
1999年 | 6篇 |
1997年 | 2篇 |
1996年 | 9篇 |
1995年 | 6篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1987年 | 2篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1970年 | 1篇 |
1966年 | 1篇 |
1961年 | 1篇 |
1948年 | 1篇 |
1938年 | 1篇 |
1937年 | 1篇 |
1918年 | 1篇 |
1916年 | 1篇 |
排序方式: 共有1151条查询结果,搜索用时 12 毫秒
11.
A series of 3-(N-substituted)-aminoquinolin-2(1H)-ones have been synthesized by the palladium-catalyzed C-N coupling reaction starting from 3-bromoquinolin-2-(1H)-ones. Various nucleophiles including amines, amides, sulfonamides, carbamates and ureas have been used successfully. In all the cases, the reactions take place rapidly in 1,4-dioxane and proceed in good to excellent yield using palladium acetate as a catalyst, Xantphos as a ligand and Cs2CO3 as a base. 相似文献
12.
This paper presents some new data on nitrophenol formation from phenol under illumination, and reviews the studies performed on phenol photonitration, from its discovery in 1988 to the very recent elucidation of its reaction pathway by the authors. Recent experimental results account for the pH effect on phenol photonitration. The nitrogen sources so far investigated are nitrate and nitrite, which undergo photolysis upon absorption of near-UV light. These studies have given a relevant information on the role of both nitrate and nitrite as environmental factors. Such processes can take place both in natural waters and in atmospheric hydrometeors. 相似文献
13.
Binding and condensation of plasmid DNA onto functionalized carbon nanotubes: toward the construction of nanotube-based gene delivery vectors 总被引:10,自引:0,他引:10
Singh R Pantarotto D McCarthy D Chaloin O Hoebeke J Partidos CD Briand JP Prato M Bianco A Kostarelos K 《Journal of the American Chemical Society》2005,127(12):4388-4396
Carbon nanotubes (CNTs) constitute a class of nanomaterials that possess characteristics suitable for a variety of possible applications. Their compatibility with aqueous environments has been made possible by the chemical functionalization of their surface, allowing for exploration of their interactions with biological components including mammalian cells. Functionalized CNTs (f-CNTs) are being intensively explored in advanced biotechnological applications ranging from molecular biosensors to cellular growth substrates. We have been exploring the potential of f-CNTs as delivery vehicles of biologically active molecules in view of possible biomedical applications, including vaccination and gene delivery. Recently we reported the capability of ammonium-functionalized single-walled CNTs to penetrate human and murine cells and facilitate the delivery of plasmid DNA leading to expression of marker genes. To optimize f-CNTs as gene delivery vehicles, it is essential to characterize their interactions with DNA. In the present report, we study the interactions of three types of f-CNTs, ammonium-functionalized single-walled and multiwalled carbon nanotubes (SWNT-NH3+; MWNT-NH3+), and lysine-functionalized single-walled carbon nanotubes (SWNT-Lys-NH3+), with plasmid DNA. Nanotube-DNA complexes were analyzed by scanning electron microscopy, surface plasmon resonance, PicoGreen dye exclusion, and agarose gel shift assay. The results indicate that all three types of cationic carbon nanotubes are able to condense DNA to varying degrees, indicating that both nanotube surface area and charge density are critical parameters that determine the interaction and electrostatic complex formation between f-CNTs with DNA. All three different f-CNT types in this study exhibited upregulation of marker gene expression over naked DNA using a mammalian (human) cell line. Differences in the levels of gene expression were correlated with the structural and biophysical data obtained for the f-CNT:DNA complexes to suggest that large surface area leading to very efficient DNA condensation is not necessary for effective gene transfer. However, it will require further investigation to determine whether the degree of binding and tight association between DNA and nanotubes is a desirable trait to increase gene expression efficiency in vitro or in vivo. This study constitutes the first thorough investigation into the physicochemical interactions between cationic functionalized carbon nanotubes and DNA toward construction of carbon nanotube-based gene transfer vector systems. 相似文献
14.
Co(II) sulfate reacts with the flexible ligand 1,4-bis(imidazol-1-ylmethyl)benzene (bix) to yield the coordination network [Co(bix)2(H2O)2](SO4).7H2O, containing polymeric ribbons of rings which penetrate and catenate a 3D single frame of the CdSO4 topology, to produce an open-channel entangled architecture with nanoporous behaviour. 相似文献
15.
Polycyclic aromatic hydrocarbons in the atmosphere: monitoring, sources, sinks and fate. II: Sinks and fate 总被引:1,自引:0,他引:1
Vione D Barra S De Gennaro G De Rienzo M Gilardoni S Perrone MG Pozzoli L 《Annali di chimica》2004,94(4):257-268
This paper reviews the transformation processes that polycyclic aromatic hydrocarbons (PAHs) undergo in the atmosphere. These processes can take place both in the gas phase and in the particulate/aerosol one. Among the gas-phase processes, the most important ones are the daytime reaction with *OH and the nighttime reaction with *NO3. The relative importance of the two processes depends on the particular PAH molecule. For instance, gaseous naphthalene is mainly removed from the atmosphere upon reaction with *OH, while gaseous phenanthrene is mainly removed by reaction with *NO3. Oxy-, hydroxy-, and nitro-PAHs are the main transformation intermediates. Reaction with ozone and photolysis play a secondary role in the transformation of gaseous PAHs. The particle-associated processes are usually slower than the gas-phase ones, thus the gas-phase PAHs usually have shorter atmospheric lifetimes than those found on particulate. Due to the higher residence time on particulate when compared with the gas phase, direct or assisted photolysis plays a relevant role in the transformation of particle-associated PAHs. Among the other processes taking place in the condensed phase, nitration plays a very important role due to the health impact of nitro-PAHs, some of them being the most powerful mutagens found so far in atmospheric particulate extracts. 相似文献
16.
Alemani D Chopard B Galceran J Buffle J 《Physical chemistry chemical physics : PCCP》2005,7(18):3331-3341
A new approach to numerically solve a reaction-diffusion system is given, specifically developed for complex systems including many reacting/diffusing species with broad ranges of rate constants and diffusion coefficients, as well as complicated geometry of reacting interfaces. The approach combines a Lattice Boltzmann (LB) method with a splitting time technique. In the present work, the proposed approach is tested by focusing on the typical reaction process between a metal ion M and a ligand L, to form a complex ML with M being consumed at an electrode. The aim of the paper is to systematically study the convergence conditions of the associated numerical scheme. We find that the combination of LB with the time splitting method allows us to solve the problem for any value of association and dissociation rate constant of the reaction process. Also, the method can be extended to a mixture of ligands. We stress two main points: (1) the LB approach is particularly convenient for the flux computation of M and (2) the splitting time procedure is very well suited for reaction processes involving association-dissociation rate constants varying on many orders of magnitude. 相似文献
17.
18.
Davide Carlo Demaria 《Milan Journal of Mathematics》1976,46(1):139-161
Given a metric compact spaceS and a finite graphG we show that:
Hence it follows that in each class of regularn-dimensional homotopy ofG can always be chosen as representative an almost constant path in respect of a suitable triangulation ofn-cubeI
n. 相似文献
a) | each regular function ofS inG is regularly homotopic to a strongly regular function; |
b) | each regular function ofS inG is regularly homotopic to an almost constant function in respect of an appropriate partition ofS. |
19.
Eleni Georgiou Davide Spinnato Kang Chen Paolo Melchiorre Kilian Muiz 《Chemical science》2022,13(27):8060
We report a photocatalytic strategy for the chemodivergent radical benzylation of 4-cyanopyridines. The chemistry uses a single photoredox catalyst to generate benzyl radicals upon N–F bond activation of 2-alkyl N-fluorobenzamides. The judicious choice of different photocatalyst quenchers allowed us to select at will between mechanistically divergent processes. The two reaction manifolds, an ipso-substitution path proceeding via radical coupling and a Minisci-type addition, enabled selective access to regioisomeric C4 or C2 benzylated pyridines, respectively. Mechanistic investigations shed light on the origin of the chemoselectivity switch.We report a photocatalytic strategy for the chemodivergent radical benzylation of 4-cyanopyridines. The chemistry uses a single photoredox catalyst to generate benzyl radicals upon N–F bond activation of 2-alkyl N-fluorobenzamides. 相似文献
20.
Valentina Noemi Madia Walter Toscanelli Daniela De Vita Marta De Angelis Antonella Messore Davide Ialongo Luigi Scipione Valeria Tudino Felicia Diodata DAuria Roberto Di Santo Stefania Garzoli Annarita Stringaro Marisa Colone Magda Marchetti Fabiana Superti Lucia Nencioni Roberta Costi 《Molecules (Basel, Switzerland)》2022,27(12)
Influenza viruses are transmitted from human to human via airborne droplets and can be transferred through contaminated environmental surfaces. Some works have demonstrated the efficacy of essential oils (EOs) as antimicrobial and antiviral agents, but most of them examined the liquid phases, which are generally toxic for oral applications. In our study, we describe the antiviral activity of Citrus bergamia, Melaleuca alternifolia, Illicium verum and Eucalyptus globulus vapor EOs against influenza virus type A. In the vapor phase, C. bergamia and M. alternifolia strongly reduced viral cytopathic effect without exerting any cytotoxicity. The E. globulus vapor EO reduced viral infection by 78% with no cytotoxicity, while I. verum was not effective. Furthermore, we characterized the EOs and their vapor phase by the head-space gas chromatography–mass spectrometry technique, observing that the major component found in each liquid EO is the same one of the corresponding vapor phases, with the exception of M. alternifolia. To deepen the mechanism of action, the morphological integrity of virus particles was checked by negative staining transmission electron microscopy, showing that they interfere with the lipid bilayer of the viral envelope, leading to the decomposition of membranes. We speculated that the most abundant components of the vapor EOs might directly interfere with influenza virus envelope structures or mask viral structures important for early steps of viral infection. 相似文献