全文获取类型
收费全文 | 4468篇 |
免费 | 154篇 |
国内免费 | 19篇 |
专业分类
化学 | 3252篇 |
晶体学 | 36篇 |
力学 | 90篇 |
数学 | 601篇 |
物理学 | 662篇 |
出版年
2024年 | 4篇 |
2023年 | 29篇 |
2022年 | 83篇 |
2021年 | 112篇 |
2020年 | 78篇 |
2019年 | 69篇 |
2018年 | 62篇 |
2017年 | 65篇 |
2016年 | 165篇 |
2015年 | 109篇 |
2014年 | 124篇 |
2013年 | 267篇 |
2012年 | 340篇 |
2011年 | 370篇 |
2010年 | 201篇 |
2009年 | 154篇 |
2008年 | 317篇 |
2007年 | 295篇 |
2006年 | 246篇 |
2005年 | 288篇 |
2004年 | 215篇 |
2003年 | 187篇 |
2002年 | 157篇 |
2001年 | 57篇 |
2000年 | 53篇 |
1999年 | 32篇 |
1998年 | 41篇 |
1997年 | 30篇 |
1996年 | 66篇 |
1995年 | 27篇 |
1994年 | 30篇 |
1993年 | 39篇 |
1992年 | 21篇 |
1991年 | 29篇 |
1990年 | 35篇 |
1989年 | 24篇 |
1988年 | 25篇 |
1987年 | 29篇 |
1986年 | 15篇 |
1985年 | 28篇 |
1984年 | 19篇 |
1983年 | 12篇 |
1982年 | 17篇 |
1981年 | 11篇 |
1980年 | 13篇 |
1979年 | 14篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1976年 | 3篇 |
1974年 | 6篇 |
排序方式: 共有4641条查询结果,搜索用时 31 毫秒
31.
Patricia Cava-Montesinos Agustin Pastor Miguel de la Guardia 《Analytica chimica acta》2003,481(2):291-300
A sensitive procedure has been developed for selenium and tellurium determination in milk by hydride generation atomic fluorescence spectrometry (HG-AFS) after microwave-assisted sample digestion. The method provides sensitivity values of 1591 and 997 fluorescence units ng−1 ml−1 with detection limits of 0.005 and 0.015 ng ml−1 for Se and Te, respectively. The application of the developed methodology to the analysis of cow milk samples of the Spanish market evidenced the presence of concentration ranges from 11.1 to 26.0 ng ml−1 for Se, and from 1.04 to 9.7 ng ml−1 for Te having found a good comparability with data obtained after dry-ashing of samples. 相似文献
32.
A direct and reagent free procedure has been developed to monitor the fermentation process of pine apple nectar using Attenuated Total Reflectance Fourier-transform mid-infrared spectrometry (FT-IR) and multivariate analysis. A classical 42 design for standards was employed for calibration using the information in the spectral range from 907 to 1531 cm−1 of the first order derivative spectra after mean centering of infrared data. The root mean square error of calibration (RMSEC) of 0.040, 0.021, 0.063 and 0.074% w/w were obtained for glucose, fructose, saccharose and ethanol, respectively, and a mean relative validation error of 2.9, 2.1, 2.6 and 3.6% was achieved for glucose, fructose, saccharose and ethanol. Results obtained by the proposed procedure for the alcohol content at different fermentation levels were statistically comparable with those obtained by a reference spectrometric method. So, FT-IR spectrometry provides a fast alternative to long and tedious classical procedures to ethanol determination and sugar enzymatic analysis. 相似文献
33.
A novel Cu(II)-Mn(II) hexanuclear complex of formula [[MnCuL](3)(tma)](ClO(4))(3).8H(2)O [H(2)L = macrocyclic Robson proligand; H(3)tma = trimesic acid] has been obtained by connecting three heterobinuclear [Cu(II)Mn(II)L](2+) cationic species through the trimesate anion. The complex exhibits a C(3) rotational symmetry, imposed by the geometry of the bridging ligand. The interaction within each Mn(II)-Cu(II) pair is antiferromagnetic (J = -16.7 cm(-1)). A weak ferromagnetic coupling among the three S = 2 resulting spins through the tricarboxylato bridge leads to a S = 6 ground spin state, for which the spin polarization mechanism is responsible. 相似文献
34.
35.
Pérez-Prieto J Galian RE Miranda MA Catalina F Martín-Vargas N López-Ortiz F 《Organic letters》2004,6(4):561-564
[reaction: see text] Several benzo[d]-1,2-oxaphosphole 2-oxides were examined as potential precursors of stabilized C-centered radicals. The transient absorption spectra obtained after laser flash photolysis in the presence of di-tert-butyl peroxide showed the features of benzylic radicals with formation and decay kinetics not significantly influenced by the presence of oxygen. In the case of compounds with two possible diastereomeric forms, the C-H bond of the trans-isomers [corrected] is more reactive toward hydrogen abstraction. 相似文献
36.
Triflate abstraction from the complex [Re(OTf)(CO)(3)(bipy)] (1) using the salt NaBAr'(4) (Ar' = 3,5-bis(trifluoromethyl)phenyl) in dichloromethane solution in the presence of L = PPh(3), NCMe, NCPh, imines, ketones, Et(2)O, THF, MeOH, and MeI affords cationic complexes [Re(L)(CO)(3)(bipy)](+) as their BAr'(4)(-) salts. The new complexes have been characterized spectroscopically and, for [Re(eta(1)-O=C(Me)R)(CO)(3)(bipy)]BAr'(4) (R = CH(3), 6a; R = Ph, 6b), and [Re(THF)(CO)(3)(bipy)]BAr'(4) (9), also by single-crystal X-ray diffraction. Compared with conventional methodologies, the route reported here allows the coordination of a broader range of weakly coordinating ligands and requires considerably milder conditions. On the other hand, the reactions of lithium acetylides with [Re(THF)(CO)(3)(bipy)]BAr'(4) (9) can be used for the high-yield syntheses of rhenium alkynyls [Re(Ctbd1;CR)(CO)(3)(bipy)] (R = Ph, 12; R = SiMe(3), 13). Complex 9 was found to catalyze the aziridination of benzylideneaniline with ethyl diazoacetate. 相似文献
37.
Francisco García-Montelongo María J. Sánchez Miguel A. Rodríguez 《Mikrochimica acta》1989,98(4-6):259-265
A spectrophotometric method for cyanide based on its inhibition of the colour formation reaction between nickel(II) and 3-(4,5-dimethyl-2-thiazolylazo)-2,6-dihydroxybenzoic acid has been developed, and allows the determination of down to 0.1 g of cyanide. Most of the interferences can be avoided by displacement of the hydrogen cyanide using an arsine generator. 相似文献
38.
Carlos Cativiela Maria D. Diaz De Villegas Jos A. Mayoral Alberto Avenoza Miguel A. Roy 《Journal of heterocyclic chemistry》1988,25(3):851-855
3(5)-Carbomethoxy-4-hetarylpyrazoles 3 can be obtained by the aromatization of the corresponding cis-3-benzamido-3-carbomethoxy-4-hetaryl-Δ1-pyrazolines 2 obtained by 1,3-dipolar cycloaddition of diazo-methane with methyl Z-2-benzamido-3-hetarylpropenoates 1. An explanation, based on FMO theory, for the different reactivity of the dipolarophiles with diazomethane is given. 相似文献
39.
Manuel Urbano Cuadrado Gonzalo Cerruela García Irene Luque Ruiz Miguel Ángel Gómez-Nieto 《Journal of mathematical chemistry》2006,40(1):15-27
A method for the treatment of long-dimensional chemical data arrays is presented in this work with the aim of maximising classification models. The method is based on the construction of fingerprints and the subsequent generation of a similarity matrix. The similarity calculation has been modified through a scaling process to take into account different significance shown by the variables. The method was applied to spectral measurements of wines and several aspects were studied, namely: threshold considered in the construction of fingerprints and patterns, weighting factor used for scaling, normalisation method, etc. The application of both Principal Components Analysis and Soft-Independent Modelling of Class Analogies to the similarity matrices gave better classifications of the information than those obtained using original data. 相似文献
40.
Basurto S García S Neo AG Torroba T Marcos CF Miguel D Barberá J Ros MB de la Fuente MR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(18):5362-5376
Several new liquid-crystalline indene and pseudoazulene systems are reported. These molecules give rise to either columnar hexagonal mesophases and/or columnar plastic phases. The unique nature of these compounds stems from their non-classical discotic structure. Although the molecules have rigid aromatic cores, they lack terminal tails and instead the polarizable atoms (S, halogens) or polar groups (CN, CO) act as unusual soft parts. On the basis of many structurally related materials, we conclude that for this type of compound molecular stacking in the solid state is a prerequisite for the appearance of a columnar mesophase, although other intermolecular interactions within the layers are also important in establishing liquid-crystalline order. The behavior reported for these mesomorphic molecules opens up new possibilities in the search for related molecular interactions that might be useful for the construction of supramolecular architectures with particular properties. 相似文献