全文获取类型
收费全文 | 1283篇 |
免费 | 53篇 |
国内免费 | 5篇 |
专业分类
化学 | 1082篇 |
晶体学 | 1篇 |
力学 | 14篇 |
数学 | 167篇 |
物理学 | 77篇 |
出版年
2023年 | 12篇 |
2022年 | 11篇 |
2021年 | 38篇 |
2020年 | 28篇 |
2019年 | 19篇 |
2018年 | 18篇 |
2017年 | 18篇 |
2016年 | 47篇 |
2015年 | 36篇 |
2014年 | 34篇 |
2013年 | 59篇 |
2012年 | 83篇 |
2011年 | 90篇 |
2010年 | 50篇 |
2009年 | 53篇 |
2008年 | 77篇 |
2007年 | 79篇 |
2006年 | 78篇 |
2005年 | 74篇 |
2004年 | 64篇 |
2003年 | 66篇 |
2002年 | 47篇 |
2001年 | 16篇 |
2000年 | 17篇 |
1999年 | 10篇 |
1998年 | 18篇 |
1997年 | 9篇 |
1996年 | 12篇 |
1995年 | 14篇 |
1994年 | 10篇 |
1993年 | 12篇 |
1992年 | 9篇 |
1991年 | 7篇 |
1990年 | 7篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 6篇 |
1985年 | 4篇 |
1984年 | 8篇 |
1983年 | 4篇 |
1982年 | 8篇 |
1981年 | 5篇 |
1980年 | 12篇 |
1979年 | 11篇 |
1978年 | 7篇 |
1977年 | 7篇 |
1976年 | 11篇 |
1975年 | 6篇 |
1973年 | 3篇 |
排序方式: 共有1341条查询结果,搜索用时 187 毫秒
101.
An eco-friendly tandem tosylation/Ferrier N-glycosylation of amines catalyzed by Er(OTf)3 in 2-MeTHF
Monica Nardi Natividad Herrera Cano Antonio De Nino Maria Luisa Di Gioia Loredana Maiuolo Manuela Oliverio Ana Santiago Diletta Sorrentino Antonio Procopio 《Tetrahedron letters》2017,58(18):1721-1726
Er(OTf)3 in 2-MeTHF provides a new and eco-friendly process for Ferrier glycosylation of sulfonamides and amino acids with various N-nucleophiles.The stereoselective synthesis of 2,3-unsaturated-N-pseudoglycals was carried out with 3,4,6-tri-O-acetyl-d-glucal and different nucleophiles affording good results in a short time. 相似文献
102.
José A. Murillo Pulgarín Luisa F. García Bermejo Armando Carrasquero Durán 《Analytical letters》2017,50(1):186-196
This study reports a simple and rapid method for the determination of the antioxidant activity of the phenolics present in plants of the Hibiscus genus. The protocol is based on the ability of the phenolic compounds to inhibit luminol chemiluminescence through the inactivation of free radicals in a flow injection system. Using the optimized operational conditions, the antioxidant activities of several phenolics were measured. The results were explained on the basis of structure–reactivity relationships. The antioxidant activities of dried flowers of Hibiscus rosa-sinensis and Hibiscus sabdariffa were evaluated. The protocol was validated by the 2,2-diphenyl-1-picrylhydrazyl-hydrate free radical assay. The differences in the antiradical activities were explained based on the concentrations of total polyphenol and flavonoid concentrations determined by spectrophotometric methods. It was concluded that the chemiluminescence method was complementary for the evaluation of hydrophilic antioxidants in plants. 相似文献
103.
Luisa Célia Melo Djenaine De Souza Pedro de Lima‐Neto Adriana Nunes Correia 《Electroanalysis》2010,22(21):2502-2510
The highly boron‐doped diamond electrode (HBDD) combined with square wave voltammetry (SWV) was used in the development of an analytical procedure for diquat determination in potato and sugar cane samples and lemon, orange, tangerine and pineapple juices. Preliminary experiments realised in a medium of 0.05 mol L?1 Na2B4O7 showed the presence of two voltammetric peaks around ?0.6 V and around ?1.0 V vs. Ag/AgCl/Cl? 3.0 mol L?1, where the first peak could be successfully used for analytical proposes due the facility in the electrode surface renovation. After the experimental and voltammetric optimisation, the calculated detection and quantification limits were 1.6×10?10 mol L?1 and 5.3×10?10 mol L?1 (0.057 µg L?1 and 0.192 µg L?1, respectively), which are lower than the maximum residue limit established for fresh food samples by the Brazilian Sanitary Vigilance Agency. The proposed methodology was used to determine diquat residues in potato and sugar cane samples and lemon, orange, tangerine and pineapple juices and the calculated recovery efficiencies indicated that the proposed procedure presents higher robustness, stability and sensitivity, good reproducibility, and is very adequate for diquat determination in complex samples. 相似文献
104.
Sara Luisa Rodríguez De Luna Luis Ángel GarzaSylvain Bernès Perla ElizondoBlanca Nájera Nancy Pérez 《Polyhedron》2010
A series of mononuclear complexes based on lanthanide ions has been synthesized and X-ray characterized. The compounds [LnIIIL2(NO3)3(H2O)2] (Ln = La, Ce, Pr, Nd, Sm, Gd and Tm; L = 2,6-bis(2-formylphenoxymethyl)pyridine) are found to be isomorphous and isostructural. Ligand L systematically coordinates through one carbonyl functionality, and the resulting complexes are placed on a twofold axis in crystals belonging to C2/c space-group. Emission spectra for Ln = La, Pr, Nd revealed a correlation between the Ln–O coordination bond length and the photoluminescent properties of the complexes, in line with a Förster–Dexter mechanism for intramolecular energy transfer. Ligand L is therefore a suitable sensitizer for lanthanide ions. 相似文献
105.
Luís Santos Pascal Martin Jalal Ghilane Pierre-Camille Lacaze Hyacinthe Randriamahazaka Luisa Maria Abrantes Jean-Christophe Lacroix 《Electrochemistry communications》2010,12(7):872-875
The electrodeposition of poly(3,4-ethylenedioxythiophene) (PEDOT) films from aqueous surfactant solution through a two-dimensional poly(styrene) (PS) template onto indium tin oxide (ITO) substrate has been investigated. The polymer grows in the interstitial spaces of the self-assembled PS spheres which were subsequently removed by dissolution in tetrahydrofuran (THF). Surface characterization by scanning electron microscopy (SEM) and atomic force microscopy (AFM) reveals that two-dimensional nanoporous honeycomb PEDOT structures can easily be obtained by using PS spheres of different sizes. Gold electrodeposition onto the nanostructured PEDOT electrode was investigated and SEM images show preferential formation of nanoparticles (NP) on the wall and the rim of the PEDOT film but metal clusters inside the pores are also observed. 相似文献
106.
Danilo Sciarrone Luisa Schipilliti Carla Ragonese Peter Quinto Tranchida Paola Dugo Giovanni Dugo Luigi Mondello 《Journal of chromatography. A》2010,1217(7):1101-1105
The present research is focused on the determination of the enantiomeric distribution of chiral compounds, contained in mandarin essential oils, by means of conventional chiral gas chromatography with flame ionization detection (enantio-GC-FID); the results attained were compared with those derived from heart-cutting multidimensional GC-mass spectrometry (MDGC/MS), to evaluate the reliability of the monodimensional technique as a tool for quality control. The Deans-switch MDGC system was equipped with two GC ovens, which were connected via a heated transfer line, a flame ionization detector (FID1) in the first dimension and a quadrupole MS as second-dimension detector. The a priori knowledge of potential co-elutions concerning target compounds (an enantiomer and an interfering compound), when using enantio-GC-FID, could enable the use of corrected enantiomer excess values. Correction factors could be calculated through a preliminary GC-FID analysis (using an apolar column), considering the peak areas of the known interferences. The method used for the calculation of a so-called “coelution correction factor” is described, along with some examples. 相似文献
107.
Fernando de la Peña Moreno Gracia Patricia BlanchGema Flores Maria Luisa Ruiz del Castillo 《Journal of chromatography. A》2010,1217(7):1083-1088
A method based on the use of the through oven transfer adsorption–desorption (TOTAD) interface in on-line coupling between reversed phase liquid chromatography and gas chromatography (RPLC–GC) for the determination of chiral volatile compounds was developed. In particular, the method was applied to the study of the influence of methyl jasmonate (MJ) treatment on the production and enantiomeric composition of selected aroma compounds in strawberry. The compounds studied were ethyl 2-methylbutanoate, linalool and 4-hydroxy-2,5-dimethyl-3(2H)-furanone (i.e. furaneol), which were examined on days 3, 6 and 9 after treatment. The method developed resulted in relative standard deviations (RSDs) of 21.6%, 8.1% and 9.8% and limits of detection (LD) of 0.04, 0.07 and 0.02 mg/l for ethyl 2-methylbutanoate, linalool and furaneol, respectively. The application of the RPLC–TOTAD–GC method allowed higher levels of ethyl 2-methylbutanoate, linalool and furaneol to be detected, particularly after 9 days of treatment. Besides, MJ demonstrated to affect the enantiomeric distribution of ethyl 2-methylbutanoate. On the contrary, the enantiomeric composition of linalool and furaneol kept constant in both control and MJ-treated strawberries throughout the study. These results are discussed. 相似文献
108.
Ana Belén Martínez-Girón Antonio L. Crego Maria José González Maria Luisa Marina 《Journal of chromatography. A》2010,1217(7):1157-1165
The enantiomeric separation of four chiral polycyclic musks (Galaxolide, Tonalide, Traseolide and Phantolide) using CE was achieved for the first time in this work. Two chiral methodologies were developed by CD-MEKC using SDS as surfactant in a CHES buffer (pH 9.0). One methodology enabled the fast enantiomeric separation of individual polycyclic musks with analysis times lower than 10 min for Tonalide, 13 min for Traseolide and Phantolide, and 17 min for Galaxolide. Enantiomeric resolutions obtained were higher than 1.5 using different separation media for each compound. A second methodology was also developed enabling the simultaneous enantioseparation of the four musks. In this case, the use of a dual CD system containing two neutral CDs was necessary to achieve the separation of all enantiomers from three out of four musks in 45 min. Although a coelution between Galaxolide and Phantolide was observed, the use of different UV absorption wavelengths allowed the simultaneous analysis of both musks. In addition, a sweeping strategy was performed in order to increase the sensitivity of the method. Appropriate analytical characteristics (linearity, LOD and LOQ, precision and absence of matrix interferences) were obtained for conventional and sweeping methodologies. Finally, the usefulness of the method was demonstrated in the determination of the enantiomers of the polycyclic musks in personal care products as perfumes. 相似文献
109.
Fremlin (Ill J Math 38:471–479, 1994) proved that a Banach space valued function is McShane integrable if and only if it is Henstock and Pettis integrable. In this paper we prove that the result remains valid also in case of multifunctions with compact convex values being subsets of an arbitrary Banach space (see Theorem 3.4). Di Piazza and Musia? (Monatsh Math 148:119–126, 2006) proved that if $X$ is a separable Banach space, then each Henstock integrable multifunction which takes as its values convex compact subsets of $X$ is a sum of a McShane integrable multifunction and a Henstock integrable function. Here we show that such a decomposition is true also in case of an arbitrary Banach space (see Theorem 3.3). We prove also that Henstock and McShane integrable multifunctions possess Henstock and McShane (respectively) integrable selections (see Theorem 3.1). 相似文献
110.
Alfonso Miranda-Molina Agustín López-Munguía María Luisa San Román Jaime Escalante Marco Antonio Leyva Ana María Puebla Edmundo Castillo Laura Álvarez 《Tetrahedron: Asymmetry》2010,21(1):43-50
The monoglucosyl-inositols α-d-glucopyranosyl-(1→4)-4d-myo-inositol 3 and α-d-glucopyranosyl-(1→1)-1d-myo-inositol 4 were synthesized by a combined enzymatic transglucosylation and hydrolysis strategy, using cyclodextrin glucosyl transferase (CGTase) from Thermoanaerobacter sp., followed by hydrolysis with Aspergillus niger glucoamylase. The glucosides were separated by preparative HPLC and fully characterized by extensive 1D and 2D NMR studies. The structure of the regioisomer 4 was confirmed by X-ray crystallography of its perbenzoylated derivative 4a. Both isomers demonstrated in vivo anti-inflammatory activity at comparative levels to corticosterone on mouse ear oedema induced by 12-O-tetradecanoylphorbol-13-acetate (TPA) and in rat hind paw oedema induced by carrageenan. 相似文献