全文获取类型
收费全文 | 1968篇 |
免费 | 56篇 |
国内免费 | 3篇 |
专业分类
化学 | 1360篇 |
晶体学 | 12篇 |
力学 | 38篇 |
数学 | 238篇 |
物理学 | 379篇 |
出版年
2023年 | 17篇 |
2022年 | 71篇 |
2021年 | 63篇 |
2020年 | 40篇 |
2019年 | 35篇 |
2018年 | 54篇 |
2017年 | 47篇 |
2016年 | 66篇 |
2015年 | 53篇 |
2014年 | 77篇 |
2013年 | 115篇 |
2012年 | 110篇 |
2011年 | 134篇 |
2010年 | 109篇 |
2009年 | 90篇 |
2008年 | 103篇 |
2007年 | 105篇 |
2006年 | 103篇 |
2005年 | 69篇 |
2004年 | 82篇 |
2003年 | 51篇 |
2002年 | 50篇 |
2001年 | 39篇 |
2000年 | 18篇 |
1999年 | 32篇 |
1998年 | 20篇 |
1997年 | 21篇 |
1996年 | 18篇 |
1995年 | 24篇 |
1994年 | 17篇 |
1993年 | 14篇 |
1992年 | 8篇 |
1991年 | 10篇 |
1990年 | 16篇 |
1989年 | 15篇 |
1988年 | 10篇 |
1987年 | 11篇 |
1986年 | 4篇 |
1985年 | 8篇 |
1984年 | 12篇 |
1983年 | 8篇 |
1982年 | 11篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 9篇 |
1978年 | 6篇 |
1976年 | 5篇 |
1975年 | 4篇 |
1972年 | 3篇 |
1969年 | 4篇 |
排序方式: 共有2027条查询结果,搜索用时 15 毫秒
111.
Alexandre Carlos Camacho Rodrigues José Luiz Fontes Monteiro 《Journal of Thermal Analysis and Calorimetry》2013,111(2):1297-1302
The effect of the calcination procedure on the decomposition of the [Pt(NH3)4]2+ complex in a cesium-containing NaX zeolite was studied by thermal decomposition accompanied by mass spectrometry and diffuse reflectance spectroscopy, as well as electron paramagnetic resonance and infrared spectroscopy. The decomposition of the complex took place in two steps. Under oxygen, the [Pt(NH3)4]2+ complex was first converted into the [Pt(NH3)2]2+ complex in the first step, with predominant nitrogen release. In the second step, corresponding to the decomposition of the remaining two amine ligands, NO was also formed and adsorbed. Oxygen paramagnetic species were also observed. Under He, the decomposition also occurred in two steps with H2 release. 相似文献
112.
José Roberto dos Santos Politi Paulo Roberto Rodrigues de Matos Maria José Araújo Sales 《Journal of Thermal Analysis and Calorimetry》2013,111(2):1437-1442
Demand for lubricating oils is increasing in the growing Brazilian economy. The use of vegetable bases in exchange of minerals can bring socio-economic and environmental benefits for Brazil. The purpose of this study is to compare the thermal and oxidative stability of vegetable oils related to the bases commonly used as lubricants. In this study, thermogravimetric analysis of castor oil, cotton oil, macauba’s almond oil, passion oil, paraffinic mineral oil, naphthenic oil (NH-140) and synthetic oil (Etro) was performed in inert and oxidative atmosphere to study the thermal and oxidative degradation of the vegetable oils related to the most common lubricants’ oils base. These oils’ oxidation stability were determined by standard procedures (ISO 6886). The use of mineral oil’s additives in these vegetable oils was tested to verify the viability of these additives to improve the oxidative stability of the vegetable oils. The castor oil and the cotton oil presented results of thermal analysis similar to the mineral and synthetic bases values. The castor oil was the only vegetable oil that showed a great oxidative stability. All other vegetable oils had their oxidative stability significantly increased by the additives. 相似文献
113.
Estela de Pieri Troiani Edenir Rodrigues Pereira‐Filho Ronaldo Censi Faria 《Electroanalysis》2013,25(8):1988-1994
A simple and sensitive method for simultaneously measuring dopamine (DA), ascorbic acid (AA), and uric acid (UA) using a poly(1‐aminoanthracene) and carbon nanotubes nanocomposite electrode is presented. The experimental parameters for composite film synthesis as well as the variables related to simultaneous determination of DA, AA, and UA were optimized at the same time using fractional factorial and Doehlert designs. The use of carbon nanotubes and poly(1‐aminoanthracene) in association with a cathodic pretreatment led to three well‐defined oxidation peaks at potentials around ?0.039, 0.180 and 0.351 V (vs. Ag/AgCl) for AA, DA, and UA, respectively. Using differential pulse voltammetry, calibration curves for AA, DA, and UA were obtained over the range of 0.16–3.12×10?3 mol L?1, 3.54–136×10?6 mol L?1, and 0.76–2.92×10?3 mol L?1, with detection limits of 3.95×10?5 mol L?1, 2.90×10?7 mol L?1, and 4.22×10?5 mol L?1, respectively. The proposed method was successfully applied to determine DA, AA, and UA in biological samples with good results. 相似文献
114.
115.
Renata Longhini Traudi Klein Marcos Luciano Bruschi Waldir Veríssimo da Silva Jr Juliana Rodrigues Norberto Peporine Lopes João Carlos Palazzo de Mello 《Journal of separation science》2013,36(7):1247-1254
The phenolic compounds are the main phytochemical constituents of the bark of Trichilia catigua and are commonly used for medicinal purposes. An HPLC method for the simultaneous quantification of phenolic compounds (procyanidin B2 (PB2), epicatechin (EPC), chinchonains Ia, Ib, IIa, IIb, catechin, and chrologenic acid) in T. catigua extract was developed and validated. A suitable chromatographic system was selected, which uses a gradient elution with methanol/ACN (75:25), and water both with 0.05% TFA, as mobile phase, column Luna, 280 nm, and flow 0.4 mL/min. Validation of the analytical method was based on the parameters: linearity, precision, LODs and LOQs, accuracy, robustness, and stability. The method showed linearity for PB2 and EPC, in the range 10–120 μg/mL with good correlation coefficients (>0.996). For precision, the repeatability ranged from 1.89 to 3.23%, and the values for accuracy for PB2 and EPC were 95 and 89%, respectively. The LODs and LOQs for PB2 were 1.36 and 4.12 μg/mL, and for EPC were 2.18 and 6.61 μg/mL, respectively. The method was robust under the conditions employed. The proposed method could be employed for quality assessment of T. catigua, as well as pharmaceutical products. 相似文献
116.
Tiago E. Frizon Daniel S. Rampon Hugo Gallardo Aloir A. Merlo Paulo H. Schneider Oscar E.D. Rodrigues 《Liquid crystals》2013,40(6):769-777
A simple and efficient procedure for the synthesis of a new class of organoselenium liquid crystal compounds was developed. The coupling of aryl bromides with elemental selenium was catalysed using copper oxide nanopowder in the presence of potassium hydroxide employing dimethyl sulfoxide as the solvent. This is the first report of the synthesis and characterisation of liquid crystal-based diselenides. Their mesophases were characterised by polarising optical microscopy and differential scanning calorimetry. Compounds 1, 2 and 4b exhibited the smectic A phase. In addition, these compounds showed weak blue fluorescence in solution (λmax. em. 350–405 nm) and a Stokes shift of around 90 nm. 相似文献
117.
Ariana Borges Souza Monique Rodrigues Moreira Carly Henrique Gambeta Borges Marília Rodrigues Simão Jairo Kenupp Bastos João Paulo Barreto de Sousa Sérgio Ricardo Ambrosio Rodrigo Cassio Sola Veneziani 《Biomedical chromatography : BMC》2013,27(3):280-283
The Copaifera species (Leguminoseae) are popularly known as ‘copaíba’ or ‘copaíva’ and are grown in the states of Amazonas, Pará and Ceará in northern Brazil. The oleoresins obtained from these species have been extensively used owing to their pharmacological potential and their application in cosmetic and pharmaceutical preparations. In the present study, the development and validation of a novel, rapid and efficient RP‐HPLC methodology for the analysis of the diterpene (?)‐copalic acid (CA), pointed out as the only chemical marker of the Copaifera genus, are described. The regression equation (Y = 26,707x ? 29,498) was obtained with good linearity (r2 = 0.9993) and the limits of quantification and detection were 9.182 and 3.032 µg/mL, respectively. The precision and the accuracy of the method were adequate (lower than 4%). Finally, the validation parameters evaluated were satisfactorily met, so the developed method represents a suitable tool for application in the quality control of such natural products. Further studies aiming to develop analytical methodologies for each Copaifera species using a more representative number of chemical markers should be performed. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
118.
The technique of imaging time-of-flight secondary ion mass spectrometry (TOF-SIMS) and dual beam depth profiling has been used to study the composition of the surface of tabular silver halide microcrystals. Analysis of individual microcrystals with a size well below 1 microm from a given emulsion is possible. The method is successfully applied for the characterization of silver halide microcrystals with subpercent global iodide concentrations confined in surface layers with a thickness below 5 nm. The developed TOF-SIMS analytical procedure is explicitly demonstrated for the molecular imaging of adsorbed thiocyanate layers (SCN) at crystal surfaces of individual crystals and for the differentiation of iodide conversion layers synthesized with KI and with AgI micrates (nanocrystals with a size between 10 and 50 nm). It can be concluded that TOF-SIMS as a microanalytical, surface-sensitive technique has some unique properties over other analytical techniques for the study of complex structured surface layers of silver halide microcrystals. This offers valuable information to support the synthesis of future photographic emulsions. 相似文献
119.
Reichard GA Stengone C Paliwal S Mergelsberg I Majmundar S Wang C Tiberi R McPhail AT Piwinski JJ Shih NY 《Organic letters》2003,5(23):4249-4251
[structure: see text] A highly efficient and practical synthesis of 4,4-Disubstituted-2-Imidazolidinones utilizing a "self-reproduction of the center of chirality" strategy is described. 相似文献
120.
Dr. Yanira Méndez Dr. Aldrin V. Vasco Galway Ivey Ana Laura Dias Dr. Peter Gierth Bárbara B. Sousa Dr. Claudio D. Navo Angel Torres-Mozas Dr. Tiago Rodrigues Dr. Gonzalo Jiménez-Osés Prof. Gonçalo J. L. Bernardes 《Angewandte Chemie (International ed. in English)》2023,62(44):e202311186
Multicomponent reactions are of utmost importance at generating a unique, wide, and complex chemical space. Herein we describe a novel multicomponent approach based on the combination of the isonitrile-tetrazine (4+1) cycloaddition and the Ugi four-component reaction to generate pyrazole amide derivatives. The scope of the reaction as well as mechanistic insights governing the 4H-pyrazol-4-imine tautomerization are provided. This multicomponent process provides access to a new chemical space of pyrazole amide derivatives and offers a tool for peptide modification and stapling. 相似文献