全文获取类型
收费全文 | 2774篇 |
免费 | 74篇 |
国内免费 | 18篇 |
专业分类
化学 | 1798篇 |
晶体学 | 11篇 |
力学 | 52篇 |
数学 | 511篇 |
物理学 | 494篇 |
出版年
2023年 | 23篇 |
2022年 | 63篇 |
2021年 | 74篇 |
2020年 | 77篇 |
2019年 | 63篇 |
2018年 | 57篇 |
2017年 | 58篇 |
2016年 | 100篇 |
2015年 | 83篇 |
2014年 | 90篇 |
2013年 | 218篇 |
2012年 | 219篇 |
2011年 | 224篇 |
2010年 | 131篇 |
2009年 | 110篇 |
2008年 | 164篇 |
2007年 | 171篇 |
2006年 | 159篇 |
2005年 | 122篇 |
2004年 | 106篇 |
2003年 | 88篇 |
2002年 | 82篇 |
2001年 | 28篇 |
2000年 | 28篇 |
1999年 | 35篇 |
1998年 | 21篇 |
1997年 | 16篇 |
1996年 | 20篇 |
1995年 | 29篇 |
1994年 | 13篇 |
1993年 | 13篇 |
1992年 | 19篇 |
1991年 | 17篇 |
1990年 | 6篇 |
1989年 | 13篇 |
1988年 | 5篇 |
1987年 | 10篇 |
1986年 | 6篇 |
1985年 | 13篇 |
1984年 | 19篇 |
1983年 | 12篇 |
1982年 | 8篇 |
1981年 | 11篇 |
1979年 | 5篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1976年 | 3篇 |
1975年 | 5篇 |
1974年 | 7篇 |
1973年 | 3篇 |
排序方式: 共有2866条查询结果,搜索用时 0 毫秒
21.
Rodríguez JL Souto RM Fernández-Mérida L Pastor E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(9):2134-2142
Spectroelectrochemical studies on the reactivity of butanol isomers on Pt electrodes in perchloric acid medium led to the observation of structural effects that result from the different arrangements of atoms in the organic molecules. The use of differential electrochemical mass spectrometry (DEMS) to detect volatile products showed that all four isomers react on the electrode, though different product yields were observed for each compound. In spite of the differences in the electrochemical behaviour of the butanol isomers, a series of general processes accounts for the results obtained. The formation of strongly adsorbed residues by a dehydration process leading to the formation of a C=C bond was proposed for all isomers. Electroreduction of the adsorbates produces C(4) and C(3) alkanes, and the latter reveal the existence of a fragmentation process. The C(4) hydrocarbons can be formed by hydrogenation of these residues and by hydrogenolysis of alcohol molecules in the bulk solution which react at the electrode with adsorbed hydrogen. On the other hand, CO(2) is formed during electrooxidation of the adsorbed species. Partial-oxidation products containing a carbonyl group were detected from 0.2 M solutions of 1-butanol, isobutyl alcohol and sec-butyl alcohol. The tertiary alcohol tert-butyl alcohol only reacts in its adsorbed state. 相似文献
22.
The electrophilic α-alkylation of ketones with alcohols was accomplished by a [Ru(DMSO)4]Cl2 catalyzed process, water being the only wasted material. The reaction can be successfully governed to produce either the expected ketones or their related alcohols only by changing the reaction conditions. When 2-aminobenzyl alcohol was used, a cyclization process took place to yield 2,3-disubstituted quinolines. 相似文献
23.
Production of antitumoral retamycin during fed-batch fermentations of Streptomyces olindensis 总被引:1,自引:0,他引:1
Fed-batch runs were performed in order to correlate the production of retamycin, an anthracycline antibiotic produced by Streptomyces olindensis in submerged cultures, with the specific growth rate. Maximum retamycin production was achieved with an exponential feed rate, controlling the specific growth rate at a low value (0.03 h-1, about 10% of the maximum specific growth rate). Control of the specific growth rate at higher values (0.10 and 0.17 h-1) caused a decrease in antibiotic production. Morphology, assessed by image analysis, was shown to be highly relevant in this process. Cell growth mainly in the form of clumps (90% clumps and 10% free filaments) led to better results than growth as clumps (75%) and free filaments (25%). 相似文献
24.
Metz AW Ireland JR Zheng JG Lobo RP Yang Y Ni J Stern CL Dravid VP Bontemps N Kannewurf CR Poeppelmeier KR Marks TJ 《Journal of the American Chemical Society》2004,126(27):8477-8492
A series of low-melting, thermally stable cadmium metal-organic chemical vapor deposition (MOCVD) precursors have been synthesized, structurally and spectroscopically characterized, and implemented in growth of highly conductive and transparent CdO thin films. One member of the series, bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)(N,N-diethyl-N',N'-dimethyl-ethylenediamine)cadmium(II), Cd(hfa)(2)()(N,N-DE-N',N'-DMEDA), represents a particularly significant improvement over previously available Cd precursors, owing to the low melting point and robust thermal stability. High-quality CdO films were grown by MOCVD on glass and single-crystal MgO(100) between 300 and 412 degrees C. Film growth parameters and substrate surface have large effects on microstructure and electron carrier transport properties. Enhanced mobilities observed for highly biaxially textured films grown on MgO(100) vs glass are attributed, on the basis of DC charge transport and microstructure analysis, to a reduction in neutral impurity scattering and/or to a more densely packed grain microstructure. Although single-grained films grown on MgO(100) exhibit greater mobilities than analogues with discrete approximately 100 nm grains and similar texture, this effect is attributed, on the basis of charge transport and Hall effect measurements as well as optical reflectivity analysis, to differences in carrier concentration rather than to reduced grain boundary scattering. Unprecedented conductivities and mobilities as high as 11,000 S/cm and 307 cm(2)/V.s, respectively, are obtained for epitaxial single-grained films (X-ray diffraction parameters: fwhm(omega) = 0.30 degrees, fwhm(phi) = 0.27 degrees ) grown in situ on MgO(100) at a relatively low temperature (400 degrees C). 相似文献
25.
26.
Guimarães KL Castro RH Gouvêa D 《Langmuir : the ACS journal of surfaces and colloids》2005,21(25):11645-11650
The standard methods for obtaining adsorption isotherms on colloidal suspensions are usually very time consuming and involve a large number of steps and assumptions that increase the experimental errors. In this work, an alternative method is proposed to evaluate the adsorption behavior of electrosteric-stabilized systems based on electrokinetic sonic amplitude signal measurements. The new method, entitled "zeta-sorption", is noticeably less time-consuming when compared to conventional procedures but showed great precision and reliability confirmed by comparison with data obtained from conventional routes on alumina-polyacrylate and alumina-citric acid aqueous suspensions. The experimental conditions that restrict the applicability of the new method were identified and justified by discussing the possible ion exchanges. 相似文献
27.
Martínez-Lozano JA Marín MJ Tena F Utrillas MP Sánchez-Muniosguren L González-Frías C Cuevas E Redondas A Lorente J de Cabo X Cachorro V Vergaz R de Frutos A Díaz JP Expósito FJ de la Morena B Vilaplana JM 《Photochemistry and photobiology》2002,76(2):181-187
An analysis is made of experimental ultraviolet erythemal solar radiation data measured during the years 2000 and 2001 by the Spanish UV-B radiation evaluation and prediction network. This network consists of 16 Robertson-Berger type pyranometers for evaluating solar erythemal radiation and five Brewer spectroradiometers for evaluating the stratospheric ozone. On the basis of these data the Ultraviolet Index (UVI) was evaluated for the measuring stations that are located either in coastal regions or in the more densely populated regions inland on the Iberian Peninsula. It has been checked that in most cases the maximum irradiance values corresponded to solar noon, although there were exceptions that could be explained by cloudiness. The maximum experimental values of the UVI were around 9 during the summer, though frequently passing this value at the inland measurement stations. The annual accumulated dose of irradiation on a horizontal plane has also been studied, as well as the evolution through the year in units of energy, standard erythemal doses and minimum erythemal doses, according to different phototypes. 相似文献
28.
Jos Luis Lpez Marcos Mandado Ana M. Graa Ricardo A. Mosquera 《International journal of quantum chemistry》2002,86(2):190-198
The atomic and bond properties of a series of alkanenitriles were calculated in order to analyze the transferability of the CN, methyl, and methylene groups. The calculations were carried out using the atoms in molecules (AIM) theory on RHF/6‐31++G**// RHF/6‐31G** wave functions obtained for compounds CN–R (R ranging from H to C11H23). Linear correlations between L(Ω) and N(Ω) were used to establish N(CH2) and N(CH3) nearly transferable values. Average values and maximum differences to the mean value of several properties were used for classifying the CN group. It shows a transferable behavior along the CN–R series for R>Et. The methyl group presents specific properties when R<Pr. The methylene groups can be classified considering both their position with respect to the end of the chain and the position with respect to the CN group. The atomic energy displays a dependence on the molecular size. Although this behavior does not allow to consider this property as transferable, both the ab initio total electronic molecular energies and the experimental heats of formation can be fitted, by linear regression analysis, as a function of the number of methylene groups. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001 相似文献
29.
Mandado M Mosquera RA Van Alsenoy C 《Physical chemistry chemical physics : PCCP》2005,7(18):3290-3296
The presence of intramolecular hydrogen bond (IHB) in beta-hydroxyethylperoxy and beta-hydroxyethoxy radicals was investigated using the QTAIM topological study on UB3LYP/6-311++G(2d,2p) charge densities. Only one of the two conformers of beta-hydroxyethylperoxy radical which were previously considered to present IHB displays a bond critical point (BCP) associated to an IHB. Furthermore, the atomic energies and electron populations indicate no evidence of IHB in the second conformer. Nevertheless, very small differences in molecular energies were obtained using several one-step and multi-step methods (G3, G3B3) between both conformers. No BCP is found between the hydroxyl hydrogen and the oxygen in the most stable conformer or in the transition state for the dissociation path of beta-hydroxyethoxy radical. However, a BCP is formed in the last steps of this path, thereby yielding H-bonded products. 相似文献
30.
Menezes PH Gonçalves SM Hallwass F Silva RO Bieber LW Simas AM 《Organic letters》2003,5(10):1601-1604
[reaction: see text] Several (77)Se NMR experiments were performed by titrating a sample of selenides with the chiral shift reagent methylbenzylamine (MBA), followed by acquisition of (77)Se NMR spectra. Eventually, we observed the appearance of two anisochronous resonances, with a relatively large separation, from 37 to 56 Hz, corresponding to the formation of the diastereomeric complexes. This methodology avoids derivatization processes, and the studied compound can be easily recovered from the NMR tube. 相似文献