全文获取类型
收费全文 | 2009篇 |
免费 | 35篇 |
国内免费 | 1篇 |
专业分类
化学 | 1026篇 |
晶体学 | 29篇 |
力学 | 79篇 |
数学 | 538篇 |
物理学 | 373篇 |
出版年
2023年 | 14篇 |
2022年 | 12篇 |
2021年 | 15篇 |
2020年 | 24篇 |
2019年 | 38篇 |
2018年 | 41篇 |
2017年 | 24篇 |
2016年 | 47篇 |
2015年 | 39篇 |
2014年 | 42篇 |
2013年 | 96篇 |
2012年 | 72篇 |
2011年 | 668篇 |
2010年 | 82篇 |
2009年 | 70篇 |
2008年 | 81篇 |
2007年 | 58篇 |
2006年 | 51篇 |
2005年 | 50篇 |
2004年 | 52篇 |
2003年 | 43篇 |
2002年 | 29篇 |
2001年 | 43篇 |
2000年 | 29篇 |
1999年 | 16篇 |
1998年 | 11篇 |
1997年 | 23篇 |
1996年 | 15篇 |
1995年 | 23篇 |
1994年 | 10篇 |
1993年 | 6篇 |
1992年 | 11篇 |
1991年 | 6篇 |
1989年 | 11篇 |
1987年 | 12篇 |
1986年 | 8篇 |
1985年 | 18篇 |
1984年 | 12篇 |
1983年 | 9篇 |
1982年 | 6篇 |
1981年 | 10篇 |
1980年 | 11篇 |
1979年 | 6篇 |
1978年 | 13篇 |
1977年 | 10篇 |
1976年 | 8篇 |
1975年 | 8篇 |
1974年 | 6篇 |
1973年 | 14篇 |
1971年 | 6篇 |
排序方式: 共有2045条查询结果,搜索用时 78 毫秒
31.
For the determination of flouride, chloride and bromide, a suitable metal ion is added in a modified graphite tube atomizer. After drying and ashing, the substances are vaporized and diatomic molecules between the metal and nonmetal are formed. These molecules are excited by a pulsed dye laser and the resulting fluorescence is measured. At constant metal concentration, the fluorescence is proportional to the halide concentration. The diatomic molecules used are MgF, InCl and AlBr. The detection limits are 11 pg of fluoride, 15 pg of chloride and 70 pg of bromide in the 10-μl injections, corresponding to 6 x 10?8 mol l?1 fluoride, 4 x 10?8 mol l?1 chloride and 9 x 10?8 mol l?1 bromides. 相似文献
32.
33.
New complexes {M(CO)4[Ph2P(S)P(S)Ph2]} (M = Cr, Mo and W), (1a)–(3a), [(1a), M = Cr; (2a), M = Mo; (3a), M = W] and {M2(CO)10[-Ph2P(S)P(S)Ph2]} (M = Cr, Mo, W), [(1b)–(3b) [(1b), M = Cr; (2b), M = Mo; (3b), M = W]] have been prepared by the photochemical reaction of M(CO)6 with Ph2P(S)P(S)Ph2 and characterized by elemental analyses, f.t.-i.r. and 31P-(1H)-n.m.r. spectroscopy and by FAB-mass spectrometry. The spectra suggest cis-chelate bidentate coordination of the ligand in {M(CO)4[Ph2P(S)P(S)Ph2]} and cis-bridging bidentate coordination of the ligand between two metals in (M = Cr, Mo and W). 相似文献
34.
Rhodium trichloride supported on Ti-hexagonal mesoporous silica (Ti-HMS), via a bipyridyl group, is an efficient catalyst for the hydroformylation of olefins at 120 °C and 40.8 atm of CO/H2 (CO/H2=2/1). The catalyst is selective leading to high ratios of linear or branched aldehydes from functionalized olefins, and high activity in the case of propene which gave a turnover frequency of 6209 mol/mol(Rh)/h. 相似文献
35.
The first palladium-catalyzed ring-expansion reaction of 2-vinylpyrrolidines with aryl isocyanates to form seven-membered ring heterocycles is described. This regioselective reaction requires 5 mol % of Pd(2)(dba)(3).CHCl(3) and 10 mol % of dppp at 40-60 degrees C in THF and results in the formation of 1,3-diazepin-2-ones in good isolated yields. When Pd(OAc)(2) and PPh(3) were utilized in the reaction, an intramolecular hydrogen migration occurs resulting in the formation of conjugated diene derivatives of urea. 相似文献
36.
Tárkányi G 《Journal of chromatography. A》2002,961(2):257-276
A quantitative NMR approach is proposed for the screening of cyclodextrins with regard to their enantioselectivity as chiral mobile phase additives in column reversed-phase chromatography and capillary electrophoresis. Similarities and differences between the mechanism of enantiomeric peak-separation in NMR and HPLC and CE are interpreted. The affinity of d-norgestrel to bind to (alpha-, beta-, gammay-) cyclodextrins in aqueous solution was quantified and compared by determining the association constants from chemical shift data. The association constant of l-norgestrel was estimated from titration of the racemate. Differences between the apparent association constants of the enantiomerically pure drug and the racemate are discussed from the point of view of enantiomeric competition for the cyclodextrin. The apparent association constants and chiral selectivities determined by 'H NMR for dl-norgestrell/gamma-CD system at various water-methanol ratios are correlated with the corresponding chromatographic results found in the literature. The pitfalls of previously proposed screening methods based on comparison of chemical shift differences with separation parameters are discussed. 相似文献
37.
Preben C. Mrk John Ugelstad Jan Ole Aasen 《Journal of polymer science. Part A, Polymer chemistry》1995,33(11):1759-1765
Expressions for calculating the stationary state distribution of radicals in compartmentalized systems with a constant number of reaction loci containing an oil-soluble initiator are given. Besides pairwise formation of radicals in the particles, desorption and reabsorption, water phase termination, solubility of the initiator in the aqueous phase, and the possibility of formation of a single radical species are taken into consideration. The calculation is based on a probabilistic analysis leading to a third-order recurrence relation solved using confluent, hypergeometric Kummer functions. Some calculated curves illustrating the de-pendence of the average number of radicals per particle on various relevant parameters are included. © 1995 John Wiley & Sons, Inc. 相似文献
38.
Mixed gels of starch and bentonite are investigated in the interval 0.056–0.089 of total solids/water ratio and 0-100% starch in the solids. The bentonite was a sodium calcium bentonite with a Na/Ca ratio of 1.76. In water it forms gels consisting of a network of band-type structures. Starch forms gels through hydrogen bonds between granules and/or amylose and amylopectin present on the external surfaces of granules and/or in fully stretched form. Mixed gels of bentonite and starch were obtained by adding corn starch granules to the already formed bentonite gels and heating the mixture above the Kofler gelatinization temperature. Amylose and amylopectin were adsorbed on strands of band-type structures of mont-morillonite lamellae. Starch gellation, e.g. diffusion of amylose out of the granule, was facilitated in the presence of bentonite. On the other hand, the presence of starch favored delamination of the montmorillonite particle into thinner lamellae. Maximum gelatinization and polymer adsorption were observed for gels with 20% starch and 80% bentonite. Montmorillonite networks formed the continuous phase for 0-80% starch. At higher starch concentrations, montmorillonite flakes were dispersed within the polymer network. Increase in the water content of the gels caused segregation of the bentonite and starch. 相似文献
39.
N. Öztürk T. Akyüz A. Y. Erkol 《Journal of Radioanalytical and Nuclear Chemistry》1995,201(5):439-446
The Eskiehir-Beylikahir district has the largest and richest thorium and rare earth elements deposits in Turkey. The uranium and thorium concentrations of samples taken from four different parts of this area have been determined by the delayed neutron counting technique. The results are compared with those of previous analyses by other techniques and found to be in good agreement. 相似文献
40.
A novel, fast and simple liquid chromatographic method was developed and validated for the simultaneous determination of rosiglitazone and metformin in human plasma. The analysis was performed on a phenyl column (250 mm × 4.6 mm i.d., 5 μm) using a gradient method starting with mobile phase composed of acetonitrile:5 mM acetate buffer pH 5.5 (75:25, v/v). The flow rate was 1 mL min−1. UV detection was performed at 245 nm and verapamil was used as internal standard. The total run time was less than 10 min. Sample preparation included a simple protein precipitation step with acetonitrile. Validation experiments were performed to demonstrate stability, specificity, sensitivity, linearity, accuracy, precision and robustness. The limit of quantification was 100 ng mL−1 for rosiglitazone and 250 ng mL−1 for metformin. The extraction recoveries were 100.02-105.0% for rosiglitazone and 105.64-103.88% for metformin. The method was applied with success to plasma samples obtained from diabetic patients undergoing treatment with rosiglitazone and metformin. 相似文献