全文获取类型
收费全文 | 2731篇 |
免费 | 108篇 |
国内免费 | 9篇 |
专业分类
化学 | 2464篇 |
晶体学 | 7篇 |
力学 | 17篇 |
数学 | 212篇 |
物理学 | 148篇 |
出版年
2023年 | 13篇 |
2022年 | 38篇 |
2021年 | 80篇 |
2020年 | 37篇 |
2019年 | 48篇 |
2018年 | 29篇 |
2017年 | 41篇 |
2016年 | 68篇 |
2015年 | 93篇 |
2014年 | 83篇 |
2013年 | 166篇 |
2012年 | 202篇 |
2011年 | 212篇 |
2010年 | 106篇 |
2009年 | 131篇 |
2008年 | 169篇 |
2007年 | 180篇 |
2006年 | 206篇 |
2005年 | 205篇 |
2004年 | 149篇 |
2003年 | 132篇 |
2002年 | 121篇 |
2001年 | 26篇 |
2000年 | 25篇 |
1999年 | 18篇 |
1998年 | 20篇 |
1997年 | 29篇 |
1996年 | 22篇 |
1995年 | 20篇 |
1994年 | 11篇 |
1993年 | 12篇 |
1992年 | 16篇 |
1991年 | 15篇 |
1990年 | 14篇 |
1989年 | 10篇 |
1988年 | 3篇 |
1987年 | 12篇 |
1986年 | 12篇 |
1985年 | 14篇 |
1984年 | 12篇 |
1983年 | 5篇 |
1982年 | 10篇 |
1980年 | 6篇 |
1979年 | 6篇 |
1978年 | 3篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1974年 | 2篇 |
1970年 | 2篇 |
1927年 | 2篇 |
排序方式: 共有2848条查询结果,搜索用时 31 毫秒
281.
M. Carmen Morán M. Pilar Vinardell M. Rosa Infante M. Graça Miguel Björn Lindman 《Advances in colloid and interface science》2014
A general understanding of interactions between DNA and oppositely charged compounds forms the basis for developing novel DNA-based materials, including gel particles. The association strength, which is altered by varying the chemical structure of the cationic cosolute, determines the spatial homogeneity of the gelation process, creating DNA reservoir devices and DNA matrix devices that can be designed to release either single- (ssDNA) or double-stranded (dsDNA) DNA. This review covers recent developments on the topic of DNA gel particles formed in water–water emulsion-type interfaces. The degree of DNA entrapment, particle morphology, swelling/dissolution behavior and DNA release responses are discussed as functions of the nature of the cationic agent used. On the basis of designing DNA gel particles for therapeutic purposes, recent studies on the determination of the surface hydrophobicity and the hemolytic and the cytotoxic assessments of the obtained DNA gel particles have been also reported. 相似文献
282.
This paper reports the synthesis, passivation and functionalization of luminescent carbon dots (CDs) possessing surface thiol ending groups. A simple procedure involving amidation of passivated carbon dots (p-CDs) with cysteamine boosts their photoluminescent properties and enables their use as easily controlled fluorescent nanosensors for determining citrate–gold nanoparticles (AuNPs). The mechanism behind the quenching phenomenon was established from fluorescence measurements at high temperatures and lifetime tests, and found to involve static quenching leading to the formation of CD–AuNP nanohybrids. A method for determining AuNPs in complex matrices was developed and validated by application to spiked drinking water and mussel tissues. The limits of detection and quantitation for AuNPs thus obtained were 0.20 and 0.66 nmol L–1, respectively. 相似文献
283.
In the present work, we study the approximation of a distributed optimal control problem for a linear heat equation with model order reduction based on Proper Orthogonal Decomposition (POD-MOR). We show that snapshot location for control problems is crucial in model reduction. For the determination of the time instances (snapshot locations) we utilize an a-posteriori error control concept which is based on a reformulation of the optimality system of the underlying optimal control problem as a second order in time and fourth order in space elliptic system. Finally, we present a numerical test to illustrate our approach. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
284.
A computational strategy to analyze Cu-O(2) adducts based on the use of difference-dedicated configuration interaction (DDCI) calculations is presented. The electronic structure, vertical gaps and nature of the metal-O(2) interaction, and the extension of the charge transfer between both fragments have been investigated. Relative stabilities between isomers are determined from triplet states CCSD(T) calculations. The key point of the here proposed strategy rests on the use of a rationally designed active space, containing only those orbitals, which optimize the interaction pathways between LCu and O(2) fragments. The procedure has been tested on a broad set of model and synthetic biomimetic systems, the results compared with previous theoretical evaluations and/or available experimental data. Our study indicates that this strategy can be considered as an alternative approach to multireference second-order perturbation theory methods to deal with this type of systems with remarkable biradical nature. 相似文献
285.
Cornelia Ratiu Florica Manea Carmen Lazau Corina Orha Georgeta Burtica Ioan Grozescu Joop Schoonman 《Chemical Papers》2011,65(3):289-298
This paper reports the results of an investigation into enhancement of the electrochemical oxidation of p-aminophenol (4-AP) in an aqueous solution with a boron-doped diamond (BDD) electrode, assisted by photocatalysis using a
zeolite-supported TiO2 (Z-TiO2) catalyst. The BDD electrode was characterised in 0.1 M Na2SO4-supporting electrolyte and the presence of 4-AP by open-circuit potential behaviour (OCP) and cyclic voltammetry (CV). The
electrode behaviour was investigated in the dark and following UV irradiation and in the absence/presence of the Z-TiO2 catalyst. The electro-oxidation process was carried out using chronoamperometry (CA) and multiple-pulsed amperometry (MPA)
at the selected potential under potentiostatic conditions. The electrochemical degradation process of 4-AP on the BDD electrode
was improved by the application of a pulsed potential, which allowed both in-situ electrochemical cleaning of the electrode
and indirect oxidation of 4-AP by oxygen evolution. The application of photocatalysis using Z-TiO2 in the 4-AP electrochemical degradation exhibited an enhanced effect when the anodic potential was set at +1.25 V vs. Ag/AgCl
in the water stability region, close to the oxygen evolution potential. 相似文献
286.
Gimenez-Lopez Mdel C Räisänen MT Chamberlain TW Weber U Lebedeva M Rance GA Briggs GA Pettifor D Burlakov V Buck M Khlobystov AN 《Langmuir : the ACS journal of surfaces and colloids》2011,27(17):10977-10985
Anisotropy of intermolecular and molecule-substrate interactions holds the key to controlling the arrangement of fullerenes into 2D self-assembled monolayers (SAMs). The chemical reactivity of fullerenes allows functionalization of the carbon cages with sulfur-containing groups, thiols and thioethers, which facilitates the reliable adsorption of these molecules on gold substrates. A series of structurally related molecules, eight of which are new fullerene compounds, allows systematic investigation of the structural and functional parameters defining the geometry of fullerene SAMs. Scanning tunnelling microscopy (STM) measurements reveal that the chemical nature of the anchoring group appears to be crucial for the long-range order in fullerenes: the assembly of thiol-functionalized fullerenes is governed by strong molecule-surface interactions, which prohibit formation of ordered molecular arrays, while thioether-functionalized fullerenes, which have a weaker interaction with the surface than the thiols, form a variety of ordered 2D molecular arrays owing to noncovalent intermolecular interactions. A linear row of fullerene molecules is a recurring structural feature of the ordered SAMs, but the relative alignment and the spacing between the fullerene rows is strongly dependent on the size and shape of the spacer group linking the fullerene cage and the anchoring group. Careful control of the chemical functionality on the carbon cages enables positioning of fullerenes into at least four different packing arrangements, none of which have been observed before. Our new strategy for the controlled arrangement of fullerenes on surfaces at the molecular level will advance the development of practical applications for these nanomaterials. 相似文献
287.
Abel Zúñiga-Moreno Carmen M. Reza-San Germán Oscar G. Rojas-Valencia Elizabeth P. Juárez-Camacho 《Journal of solution chemistry》2011,40(4):621-631
Densities of the binary mixture of nonane with decane were measured at temperatures from 283.15 to 353.15 K at atmospheric
pressure (0.7 atm). Measurements have been made over the full range of compositions and for the pure compounds by using a
vibrating-tube densimeter (VTD). Excess molar volumes have been obtained from these experimental results and were fitted to
a Redlich–Kister type expansion. The excess molar volumes exhibit small positive and small negative deviations from ideal
behavior in the temperature interval studied. Partial molar volumes and partial molar volumes at infinite dilution have been
determined for each component. 相似文献
288.
Study of the effects of operational parameters on multiresidue pesticide analysis by LC-MS/MS 总被引:2,自引:0,他引:2
In this paper, the influence of several operational parameters on a well established multiresidue LC-MS/MS method has been studied in relation to the analysis of 150 pesticides commonly present in vegetable samples. The operational parameters investigated are: (i) the influence of different modifiers (0.1% formic acid; 5 mM ammonium formiate; 5 mM ammonium acetate in aqueous phase) - both on the retention time and on the analytical response of the studied compounds; (ii) the effect of the analytical column's temperature on the retention time and on the analytical response of the pesticides investigated; (iii) the effects of co-elution in mixture containing 150 pesticides and, additionally, (iv) the carrying out of a study about the common transitions obtained by LC-MS/MS. Various common transitions were found among the 150 pesticides, but there were only two problematic cases, the pairs diuron-fluometuron and prometryn-terbutryn, which have common scanned transitions and have very close retention times. The use of ammonium salts as modifier instead of formic acid reports enhancement or suppression of the response depending on the pesticides. No great influence on the retention time or on the response of the pesticides and commodities studied was observed with relation to the column temperature. Two different columns: an HPLC (5 μm particle size) and an UHPLC analytical column (1.8 μm particle size) have been used. As was expected, shorter run times and lower peak width was achieved with the UHPLC column.In this paper, the effect of the compounds on each other in the MS analysis when the number of co-eluting compounds is quite high is also described. Mainly small suppression or enhancement co-elution effect was observed, but some particular pesticides presented high sensitivity (>±60% effect) when they elute together with others. This is an important factor and it has to be taken into account when performing multiresidue pesticide analysis. 相似文献
289.
Martín-Rodríguez M Nájera C Sansano JM de Cózar A Cossío FP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(50):14224-14233
The 1,3-dipolar cycloaddition between azomethine ylides and alkenes is efficiently catalysed by [{(S(a))-Binap-Au(tfa)}(2)] (Binap=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl; tfa=trifluoroacetyl). Maleimides, 1,2-bis(phenylsulfonyl)ethylene, chalcone and nitrostyrene were suitable dipolarophiles even when using sterically hindered 1,3-dipole precursors. The results obtained in these transformations improve the analogous ones obtained in the same reactions catalysed by [Binap-Ag(tfa)]. In addition, computational studies have also been carried out to demonstrate both the high enantioselectivity exhibited by the chiral gold(I) complex, and the non-linear effect observed in this transformation. 相似文献
290.
Martín C Molina F Alvarez E Belderrain TR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(52):14885-14895
The Pd(0) complexes [(NHC)PdL(n)] (NHC=N-heterocyclic carbene ligand; L=styrene for n=2 or PR(3) for n=1) efficiently catalyse olefin cyclopropanation by using ethyl diazoacetate (EDA) as the carbene source with activities that improve on previously described catalytic systems based on this metal. Mechanistic studies have shown that all of these catalyst precursors deliver the same catalytic species in solution, that is, [(IPr)Pd(sty)], a 14e(-) unsaturated intermediate that further reacts with EDA to afford [(IPr)Pd(=CHCO(2)Et)(sty)], from which the cyclopropane is formed. 相似文献