全文获取类型
收费全文 | 2725篇 |
免费 | 96篇 |
国内免费 | 18篇 |
专业分类
化学 | 1922篇 |
晶体学 | 19篇 |
力学 | 41篇 |
数学 | 360篇 |
物理学 | 497篇 |
出版年
2023年 | 17篇 |
2022年 | 28篇 |
2021年 | 46篇 |
2020年 | 44篇 |
2019年 | 41篇 |
2018年 | 33篇 |
2017年 | 34篇 |
2016年 | 73篇 |
2015年 | 69篇 |
2014年 | 67篇 |
2013年 | 116篇 |
2012年 | 181篇 |
2011年 | 212篇 |
2010年 | 119篇 |
2009年 | 133篇 |
2008年 | 190篇 |
2007年 | 196篇 |
2006年 | 194篇 |
2005年 | 140篇 |
2004年 | 97篇 |
2003年 | 104篇 |
2002年 | 95篇 |
2001年 | 50篇 |
2000年 | 58篇 |
1999年 | 36篇 |
1998年 | 30篇 |
1997年 | 31篇 |
1996年 | 43篇 |
1995年 | 33篇 |
1994年 | 20篇 |
1993年 | 19篇 |
1992年 | 19篇 |
1991年 | 17篇 |
1990年 | 18篇 |
1989年 | 10篇 |
1988年 | 10篇 |
1987年 | 10篇 |
1986年 | 11篇 |
1985年 | 13篇 |
1984年 | 20篇 |
1983年 | 10篇 |
1982年 | 13篇 |
1981年 | 6篇 |
1980年 | 14篇 |
1979年 | 10篇 |
1978年 | 11篇 |
1975年 | 7篇 |
1974年 | 7篇 |
1934年 | 6篇 |
1930年 | 6篇 |
排序方式: 共有2839条查询结果,搜索用时 865 毫秒
51.
L. F. Capitán-Vallvey R. Avidad Castañeda M. del Olmo Iruela J. L. Vilchez Quero 《Mikrochimica acta》1993,112(1-4):55-62
Benzo(a)pyrene (BaP) and pyrene (Pyr) are two polycyclic aromatic hydrocarbons (PAHs) showing native fluorescence in solution. Both compounds have been determined in water at trace levels by solid-phase spectrofluorimetry, in which BaP and Pyr are fixed on Sephadex G-25 gel and the relative fluorescence intensity is measured after the system is packed in a 1-mm silica cell. First-derivative synchronous spectra obtained at =38 nm were used to determine BaP and Pyr in the presence of other potentially interferent PAHs. The spectral characteristics of the PAHs-gel system are described, the applicable concentration ranges being 0.4–2.5 ng/ml for BaP and 0.7–4.5 ng/ml for Pyr. The relative standard deviations were 1.1% and 1.4% for BaP and Pyr respectively. The detection limits were 0.04 ng/ml for BaP and 0.1 ng/ml for Pyr. The method was applied to the analysis of both compounds in water at trace levels and a recovery study on tap, natural and sea waters was carried out. 相似文献
52.
Ahmad Al-Alousy Saad Alshehri John Burgess Maria del Mar Graciani Maria-Luisa Moya Ernestina Muñoz Amalia Rodriguez Francisco Sanchez 《Transition Metal Chemistry》1993,18(2):179-181
Summary Dependences of rate constants on pressure (up to 1 kbar) and on added salt concentration (up to 6.0 mol dm–3 LiNO3, NaNO3, NaCl, Na2SO4 or KNO3) have been established for dissociative substitution of pentacyanoferrates(II), [Fe(CN)5L]3– with L = 4-cyanopyridine, 4,4-bipyridyl, 4-phenylpyridine and 4-t-butylpyridine. Activation volumes derived directly from pressure effects, and indirectly from salt effects via surface tension dependences and derived surfaces of activation, are reported, compared and discussed. 相似文献
53.
Alfredo Carrascull Claudia Grzona Daniela Lick Marta Ponzi Esther Ponzi 《Reaction Kinetics and Catalysis Letters》2002,75(1):63-68
The catalytic combustion of particulate material was studied on cobalt catalysts promoted with potassium using different supports for its preparation. Silica, aluminium oxides and hydroxides, zirconium oxide and hydroxide were used as supports. The catalytic activity for combustion depends on the type of support used, the higher activity corresponding to the supported catalyst on zirconium oxide. TPR studies indicate that the interaction metal/support allows to explain the higher activity of the CoK/SiO2 catalyst with respect to the CoK/Al2O3 but the high activity found in CoK/ZrO2is not explained by this interaction. In all cases the Co and K improved the performance of the catalysts. 相似文献
54.
Functionalized keto-enamines 6 were obtained by nucleophilic addition of enol ethers to the imine moiety of 2-azadienes derived from dehydroaspartic esters 4. Reactions of 2-azadiene 4c containing three electron-withdrawing substituents (CO(2)R) with enol ethers 5 in the presence of lithium perchlorate led to the formation of tetrahydropyridine derivatives 7 in a regio- and stereoselective fashion. 2H-[1,3]-oxazines 10 and pyridine derivatives 12 and 13 were obtained by heterocycloaddition reactions of electron-poor azadienes 4d-g containing two electron-withdrawing substituents (4-O(2)N-C(6)H(4), CO(2)R) in positions 1 and 4 with carbonyl derivatives (ethyl glyoxalate 9a and diethyl ketomalonate 9b) and the electron-deficient olefin tetracyanoethylene 11. 相似文献
55.
Churruca F SanMartin R Carril M Urtiaga MK Solans X Tellitu I Domínguez E 《The Journal of organic chemistry》2005,70(8):3178-3187
Novel dibenzo[a,c]phenanthridines are prepared regioselectively by the application of a straightforward synthetic pathway, starting from new 3,4-diaryl- and 3,4-dihydro-3,4-diarylisoquinolines prepared via Ritter-type heterocyclization and the more classical two-step reductive amination/Bischler-Napieralski cyclization of triarylethanones, respectively. A comparative study of nonphenolic oxidative coupling methodologies provides a highly efficient procedure, based on the hypervalent iodine reagent phenyliodine(III) bis(trifluoroacetate) (PIFA), to accomplish the final coupling step. 相似文献
56.
Lainez A del Burgo P Junquera E Aicart E 《Langmuir : the ACS journal of surfaces and colloids》2004,20(14):5745-5752
Speed of sound, density, conductivity, and fluorescence spectroscopy experiments were run to analyze the mixed aggregation process of a nonionic-cationic surfactant system in aqueous media at 298.15 K. The mixed system comprises a nonionic surfactant, n-octyl-beta-D-glucopyranoside (OBG), and a cationic surfactant, tetradecyltrimethylammonium bromide (C14TAB), with 8 and 14 carbon atoms on the hydrophobic tails, respectively. From these data, the total and partial critical micellar concentrations, the total and partial aggregation numbers, apparent molar volumes and isentropic compressibilities, hydration numbers, and the corresponding changes in the latest properties due to the mixed aggregation process were determined. Pure and mixed micelles were analyzed from a geometrical point of view by determining the packing parameter of the aggregates. Furthermore, the experimental characterization of both the monomeric and micellar phases was completed with a theoretical study of the mixed micellization phenomena studied herein, by means of some of the most relevant theoretical models. 相似文献
57.
Determination of rotenone residues in raw honey by solid-phase extraction and high-performance liquid chromatography 总被引:8,自引:0,他引:8
Jiménez JJ Bernal JL del Nozal MJ Novo M Higes M Llorente J 《Journal of chromatography. A》2000,871(1-2):67-73
A method for determining residues of the insecticide rotenone in raw-honey by high-performance liquid chromatography (HPLC) is described. To extract the residues, organic solvents such as ethyl acetate, n-hexane/dichloromethane and solid-phase extraction with octadecylsilane cartridges or Florisil packed columns were tested. Determination was carried out by reversed-phase HPLC using acetonitrile-buffer phosphate (pH 7) (60:40, v/v) as mobile phase and detection at 210 nm. Although the data showed that the two extraction methods were able to isolate the pesticide residues, the extraction on octadecylsilane cartridges was preferred due to its simplicity and higher recovery. Recoveries depended strongly on the fortification level for the two extraction procedures. Practical determination limits of 0.015 mg/kg were obtained. In the analysis of honeys, from beehives treated with rotenone at therapeutical doses for 1 month, residual amounts below 0.2 mg/kg were found. 相似文献
58.
Bulloch EM Jones MA Parker EJ Osborne AP Stephens E Davies GM Coggins JR Abell C 《Journal of the American Chemical Society》2004,126(32):9912-9913
(6S)-6-Fluoroshikimate has antimicrobial activity. The molecular basis of this effect had not been identified, but there was speculation that (6S)-6-fluoroshikimate is first converted in vivo into 2-fluorochorismate, which then could inhibit 4-amino-4-deoxychorismate synthase (ADCS). 2-Fluorochorismate was prepared from E-fluorophosphoenolpyruvate and erythose-4-phosphate by the sequential reactions of DAHP synthase, dehydroquinate synthase, dehydroquinase, shikimate dehydrogenase, EPSP synthase, and chorismate synthase. Inhibition studies on ADCS showed that it was inhibited rapidly and irreversibly by 2-fluorochorismate. Electrospray mass spectrometry of the inactivated enzyme showed an additional mass of 198 +/- 10 Da. A novel peptide of 1087.6 Da was identified in the HPLC trace for the tryptic digest of 2-fluorochorismate-inactivated ADCS. Sequencing of this peptide by MS/MS showed that the peptide corresponded to residues 272-279 with a modification of 206.1 Da on Lys-274. This observation is particularly exciting in the context of a recent proposal for the catalytic mechanism of ADCS. 相似文献
59.
R. Roque-Malherbe A. Berazain J. A. del Rosario 《Journal of Thermal Analysis and Calorimetry》1987,32(3):949-951
The ionexchange heats of homoionic heulandite and mordenite were measured with a microcalorimeter. In the case of K, NH4, Na, Mg and Ca, the selectivity of the zeolite is determined by the heat of hydration.We are very grateful to Dr. Ingemar Wadso from the Division of Thermochemistry of the University of Lund, Sweden, and to Dr. R. Ohlen from LKB, Sweden, for their advice, and to Ing. Valentina Zelenenko and Lic. Jose Sosa for providing homoionic samples. 相似文献
60.
[reaction: see text] A new route to oxcarbazepine (Trileptal), the most widely prescribed antiepileptic drug, starting from commercially available 2'-aminoacetophenone and 1,2-dibromobenzene, is reported. The sequentially accomplished key steps are palladium-catalyzed intermolecular alpha-arylation of ketone enolates and intramolecular N-arylation reactions. After several experiments to establish the best conditions for both arylation processes, the target oxcarbazepine is obtained in a satisfactory overall yield, minimizing the number of steps and employing scalable catalytic procedures developed in partially aqueous media. 相似文献