全文获取类型
收费全文 | 5215篇 |
免费 | 227篇 |
国内免费 | 4篇 |
专业分类
化学 | 3605篇 |
晶体学 | 42篇 |
力学 | 77篇 |
数学 | 751篇 |
物理学 | 971篇 |
出版年
2023年 | 40篇 |
2022年 | 24篇 |
2021年 | 59篇 |
2020年 | 83篇 |
2019年 | 75篇 |
2018年 | 105篇 |
2017年 | 109篇 |
2016年 | 179篇 |
2015年 | 155篇 |
2014年 | 169篇 |
2013年 | 348篇 |
2012年 | 395篇 |
2011年 | 461篇 |
2010年 | 219篇 |
2009年 | 170篇 |
2008年 | 335篇 |
2007年 | 350篇 |
2006年 | 285篇 |
2005年 | 292篇 |
2004年 | 239篇 |
2003年 | 201篇 |
2002年 | 156篇 |
2001年 | 142篇 |
2000年 | 108篇 |
1999年 | 64篇 |
1998年 | 47篇 |
1997年 | 32篇 |
1996年 | 66篇 |
1995年 | 44篇 |
1994年 | 42篇 |
1993年 | 40篇 |
1992年 | 46篇 |
1991年 | 30篇 |
1990年 | 15篇 |
1989年 | 14篇 |
1988年 | 21篇 |
1987年 | 17篇 |
1986年 | 18篇 |
1985年 | 23篇 |
1984年 | 25篇 |
1983年 | 13篇 |
1982年 | 23篇 |
1981年 | 21篇 |
1980年 | 15篇 |
1979年 | 22篇 |
1978年 | 20篇 |
1976年 | 14篇 |
1975年 | 9篇 |
1974年 | 8篇 |
1973年 | 10篇 |
排序方式: 共有5446条查询结果,搜索用时 0 毫秒
61.
Díez-Barra E García-Martínez JC del Rey R Rodríguez-López J Giacalone F Segura JL Martín N 《The Journal of organic chemistry》2003,68(8):3178-3183
New chiral, soluble binaphthyl derivatives that incorporate stilbenoid dendrons at the 6,6'-positions have been prepared. The synthesis of the new enantiopure dendrimers was performed in a convergent manner by Horner-Wadsworth-Emmons (HWE) reaction of the appropriately functionalized 1,1'-binaphthyl derivative (R)-1 and the appropriate dendrons (R)(2n)G(n)-CHO. Different electroactive units were incorporated in the peripheral positions of the dendrons in order to tune both the optical and electrochemical behavior of these systems. Fluorescence measurements on the chiral dendrimers reveal a strong emission with maxima between 409 and 508 nm depending upon the substitution pattern. Finally, the redox properties of the dendrimers were determined by cyclic voltammetry, showing the influence of the functional groups at the peripheral positions of the dendrimer on the redox behavior of these systems. 相似文献
62.
A simple, sensitive, selective, fast and inexpensive assay for the determination of diquat is proposed. The method is based on the reduction of the herbicide to a strongly fluorescent monocation radical with sodium dithionite. The initial rate of this reaction is directly proportional to the diquat concentration. The stopped-flow mixing technique was used because the kinetic data can be obtained in only 7 s, meaning that the method can be automated. The calibration graph is linear over the range 5-500 ng ml-1 and the precision (RSD) is close to 1.2%. The applicability of the method was demonstrated by determining the herbicide in different kinds of samples. 相似文献
63.
S. Martínez-Gallegos S. Bulbulian 《Journal of Radioanalytical and Nuclear Chemistry》2005,266(2):285-287
Summary Electrophoresis followed by neutron activation analysis was utilized to determine chromium(III) and (VI) in mixed solutions.
These solutions proceeded from Cr(VI) adsorbed hydrotalcites heated at 800 °C to partially immobilize Cr in the Mg-Al oxide
solid solution. Immobilization was studied by Cr lixiviation with NaCl solutions through the heated hydrotalcites. The results
have shown that Cr lixiviated was in the form of CrO42- ions, mainly because some Cr(VI) was not completely reduced to Cr(III) during heating. Chromium lixiviated from HT-Cr sample,
heated at 800 °C and γ-irradiated at 1000 kGys, was found, as well, in the form of CrO42- ions. Although γ-irradiation increases Cr immobilization in the solid, it does not reduce completely all CrO42- ions present in the solid and, therefore, some Cr is lixiviated through the solid in the form of CrO42- ion. 相似文献
64.
Donald G. Fleming Donald J. Arseneau David M. Garner Masayoshi Senba Randall J. Mikula 《Hyperfine Interactions》1984,18(1-4):655-678
The vapor phase fractional polarizations of positive muons thermalizing as the muonium atom (P
M) and in diamagnetic environments (P
D) has been measured in H2O, CH3OH, C6H14, C6H12, CCl4, CHCl3, CH2Cl2 and TMS, in order to compare with the corresponding fractions measured in the condensed phases. There is a marked contrast in every case, with the vapor phase results being largely understandable in terms of a charge exchange/hot atom model. Unlike the situation in the corresponding liquids, there is no permanent lost fraction in the vapor phase in the limit of even moderately high pressures (1 atm); at lower pressures, depolarization is due to hyperfine mixing and is believed to be well understood. For vapor phase CH3OH, C6H14, C6H12, and TMS therelative fractions are found to be pressure dependent, suggesting the importance of termolecular hot atom (or ion) reactions in the slowing down process. For vapor phase H2O and the chloromethanes, the relative fractions are pressure independent. For CCl4,P
M=P
D0.5 in the vapor phase vs.P
D=1.0 in the liquid phase; fast thermal reactions of Mu likely contribute significantly to this difference in the liquid phase. For H2O,P
M 0.9 andP
D0.1 in the vapor phase vs.P
D 0.6 andP
M0.2 in the liquid phase. Water appears to be the one unequivocal case where the basic charge exchange/hot atom model is inappropriate in the condensed phase, suggesting, therefore, that radiation induced spur effects play a major role. 相似文献
65.
Carbonyl 2 + 2 photoaddition occurs selectively to the alkene moiety of 3-(4-methyl-3-pentenoxy)pyridine. Photolysis of alkene containing pyridines in acetophenone gives rise to an oxetane which is obtained with extremely high diastereoselectivity as shown by analysis of the major 2 + 2 photoproduct. A second photoproduct, 2,3-dihydroxy-2,3-diphenylbutane, is obtained as a result of acetophenone coupling. 相似文献
66.
Martín Y 《The Analyst》2000,125(12):2230-2235
A method for the determination of three anabolic hormones (diethylstilbestrol, dienestrol and trenbolone) in calf urine is described. After enzymatic hydrolysis, the samples were cleaned up by C18 solid-phase extraction. Drugs were extracted with hexane and analyzed by isocratic elution on a Discovery RP-Amide C16 5 microns column with photodiode-array detection at 240 and 347 nm. Both retention time and UV spectra were used for identification. Detection limits for the HPLC system were calculated to be 0.3 ng injected for all analytes in the standard mixture. However, for urine samples these limits increased because of the presence of unidentified matrix components. After extraction from urine, the limits of detection for the whole analytical procedure were 5 and 10 ng injected for trenbolone and stilbenes, respectively. The average recoveries of the hormones from spiked samples were in the range 53.1-56.7% with RSD between 11.3 and 14.5% for the whole procedure in the concentration range 25-2.5 ng ml-1. 相似文献
67.
J. L. Martínez Vidal A. Garrido Frenich T. López López I. Martínez Salvador L. Hajjaj el Hassani M. Hassan Benajiba 《Chromatographia》2005,61(3-4):127-131
An analytical method for determining residues of twenty pesticides by liquid chromatography (LC) coupled to electrospray ionisation (ESI) tandem mass spectrometry (MS-MS) in eight commodities, cucumber, tomato, pepper, green bean, eggplant, zucchini, melon and watermelon, has been developed and validated. On one hand, calibration curves prepared in solvent were compared with calibration curves prepared in a blank matrix extract of each target matrix. On the other hand, calibration curves and recoveries for each commodity were compared. Cucumber was selected as potential reference matrix for the target vegetables. 相似文献
68.
Tatsuhiko Nakano A.C. Spinelli A. Martín A. Usubillaga Andrew T. McPhail Kay D. Onan 《Tetrahedron letters》1982,23(35):3627-3630
cleavage of the epoxide () of methyl (-)-kaur-9(11)-en-19-oate () with boron trifluoride-ether in benzene and in acetic anhydride yielded () and (), respectively. On epoxidation with -chloroperbenzoic acid in the presence of -nitrosomethyl urea, () suffered a backbone rearrangement to form (). 相似文献
69.
Román LU Guerra-Ramírez D Morán G Martínez I Hernández JD Cerda-García-Rojas CM Torres-Valencia JM Joseph-Nathan P 《Organic letters》2004,6(2):173-176
[structure: see text] The triterpenes 8,14-seco-oleana-8(26),13-dien-3beta-ol (1) and its acetyl derivative 2 were isolated from Stevia viscida and Stevia eupatoria, respectively. Their structures were elucidated by 2D NMR, including carbon-carbon connectivity experiments, and confirmed by X-ray diffraction analysis of ketone 3. The absolute configuration was determined by NMR analysis of the Mosher esters of 1. The biogenetic implications of the new substances are discussed. 相似文献
70.
C. Martínez R. Cremer D. Neuschütz J. P. Servais D. Loison 《Surface and interface analysis : SIA》2002,34(1):524-526
The formation of oxides at the surface of Fe–1.5%Mn and Fe–0.6%Mn binary alloys was investigated as a function of the conditions of the heat treatments. Both the influence of temperature and the atmosphere under which the experiments were performed were studied. The range of annealing temperatures was adjusted to 800°C. The atmosphere consisted of a mixture of N2–5%H2 and traces of water vapour, with different fixed dew points ranging from −10°C to −30°C. The state of the annealed surfaces was determined using in situ analytical devices attached to the annealing reactor in order to avoid surface contamination or the formation of native oxides after the experiments due to contact with air. The structure and composition of the surfaces were determined by reflection high-energy electron diffraction (RHEED) and electron spectroscopy (XPS, AES). Copyright © 2002 John Wiley & Sons, Ltd. 相似文献