全文获取类型
收费全文 | 3128篇 |
免费 | 156篇 |
国内免费 | 2篇 |
专业分类
化学 | 2316篇 |
晶体学 | 45篇 |
力学 | 85篇 |
数学 | 408篇 |
物理学 | 432篇 |
出版年
2023年 | 26篇 |
2022年 | 23篇 |
2021年 | 38篇 |
2020年 | 54篇 |
2019年 | 54篇 |
2018年 | 58篇 |
2017年 | 55篇 |
2016年 | 114篇 |
2015年 | 82篇 |
2014年 | 94篇 |
2013年 | 216篇 |
2012年 | 264篇 |
2011年 | 272篇 |
2010年 | 148篇 |
2009年 | 130篇 |
2008年 | 226篇 |
2007年 | 218篇 |
2006年 | 170篇 |
2005年 | 169篇 |
2004年 | 155篇 |
2003年 | 111篇 |
2002年 | 109篇 |
2001年 | 76篇 |
2000年 | 85篇 |
1999年 | 52篇 |
1998年 | 42篇 |
1997年 | 23篇 |
1996年 | 33篇 |
1995年 | 17篇 |
1994年 | 23篇 |
1993年 | 15篇 |
1992年 | 18篇 |
1991年 | 14篇 |
1990年 | 9篇 |
1989年 | 12篇 |
1988年 | 12篇 |
1987年 | 6篇 |
1986年 | 9篇 |
1985年 | 11篇 |
1984年 | 9篇 |
1983年 | 8篇 |
1982年 | 4篇 |
1980年 | 4篇 |
1978年 | 1篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1973年 | 4篇 |
1969年 | 1篇 |
1925年 | 1篇 |
排序方式: 共有3286条查询结果,搜索用时 765 毫秒
21.
Optimization of a microwave-assisted extraction method for the analysis of polychlorinated biphenyls in ash samples 总被引:2,自引:0,他引:2
Ramil Criado M Rodríguez Pereiro I Cela Torrijos R 《Journal of chromatography. A》2003,985(1-2):137-145
An alternative method for the extraction of polychlorinated biphenyls (PCBs) in ash samples, which is less time and solvent consuming than Soxhlet extraction, is presented. A study was carried out to evaluate the possibilities of microwave-assisted extraction (MAE) to determine exactly which parameters affect the efficiency of the process, since direct extrapolation of extraction conditions for PCBs in other solid matrices, failed when applied to coplanar congeners in ash samples. Influence of the organic solvent on the yield of the extraction was first evaluated using two ash samples with different percentages of carbon. Once the extraction solvent was fixed, the effects of solvent volume, extraction temperature and extraction time were investigated using an experimental design. It was found that the volume of organic solvent played a more important role in the extraction efficiency than the other factors. In the optimal conditions microwave extractions were performed at 110 degrees C. for 10 min and using 30 ml of toluene. Recoveries higher than 80% were obtained for all the highly chlorinated congeners. including coplanar species, in a spiked ash sample containing a relatively high concentration of carbon. The proposed method was also applied to the determination of PCBs in a reference material of urban dust. Recoveries were similar to those obtained for spiked ash samples. 相似文献
22.
del Mar Graciani M Rodríguez A Muñoz M Moyá ML 《Langmuir : the ACS journal of surfaces and colloids》2005,21(16):7161-7169
Micellization in water-ethylene glycol (EG) N-dodecyl, N-tetradecyl, and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (SB3-12, SB3-14, and SB3-16, respectively) micellar solutions, with the weight percent of EG changing within the range 0-40, was studied by means of surface tension measurements. Information about the influence of the added EG on the aggregation number of the sulfobetaine micelles and on the polarity of the interfacial region of micelles was obtained through fluorescence and spectroscopic measurements. Surface tension measurements also provide information about the dependence of the surface excess concentration, the minimum area per surfactant molecule, the surface pressure at the cmc, and the standard Gibbs energy of adsorption on the added weight percent of the organic solvent. The Gordon parameter of the water-EG mixtures was also estimated by means of surface tension measurements. The thermodynamic and structural changes originated by the presence of EG control the micellar kinetic effects observed in the reaction methyl 4-nitrobenzenesulfonate + Br(-) occurring in the water-EG sulfobetaine micellar solutions. Information about the distribution of bromide ions between the bulk and micellar pseudophases was obtained through conductivity measurements. The kinetic micellar effects were quantitatively explained by using the pseudophase kinetic model. 相似文献
23.
Ruiz E Rodríguez-Fortea A Cano J Alvarez S Alemany P 《Journal of computational chemistry》2003,24(8):982-989
The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data. 相似文献
24.
J. L. Gascón M. Rodríguez J. A. Suárez Del Rey 《Journal of Radioanalytical and Nuclear Chemistry》1996,207(1):63-69
The determination of Am and Cm in typical waste streams from nuclear power plants using anion exchange chromatography has some drawbacks like the contamination by Pu and Po. This improved procedure solves these problems, and it has been applied with success to the analysis of Am and Cm in nuclear waste samples: ion exchange resins, ion exchange resins solidified with cement and evaporator concentrates. 相似文献
25.
A. Caubet A. Labarta R. Rodríguez A. Fernandez E. Molins V. Moreno J. Tejada 《Hyperfine Interactions》1986,28(1-4):773-776
By means of57Co Mössbauer emission spectroscopy and magnetic susceptibility measurements, the local symmetries and electronic structure of the Co(II) ions in the Co-5IMO and Co-5GMP complexes in the hydrated and dehydrated forms have been determined. 相似文献
26.
27.
Francisco García-Montelongo María J. Sánchez Miguel A. Rodríguez 《Mikrochimica acta》1989,98(4-6):259-265
A spectrophotometric method for cyanide based on its inhibition of the colour formation reaction between nickel(II) and 3-(4,5-dimethyl-2-thiazolylazo)-2,6-dihydroxybenzoic acid has been developed, and allows the determination of down to 0.1 g of cyanide. Most of the interferences can be avoided by displacement of the hydrogen cyanide using an arsine generator. 相似文献
28.
Pablo Ríos Javier Borge Francisco Fernndez de Crdova Giuseppe Sciortino Agustí Lleds Amor Rodríguez 《Chemical science》2021,12(7):2540
The concept of metal–ligand cooperation opens new avenues for the design of catalytic systems that may offer alternative reactivity patterns to the existing ones. Investigations of this concept with ligands bearing a boron center in their skeleton established mechanistic pathways for the activation of small molecules in which the boron atom usually performs as an electrophile. Here, we show how this electrophilic behavior can be modified by the ligand trans to the boron center, evincing its ambiphilic nature. Treatment of diphosphinoboryl (PBP) nickel–methyl complex 1 with bis(catecholato)diboron (B2Cat2) allows for the synthesis of nickel(ii) bis-boryl complex 3 that promotes the clean and reversible heterolytic cleavage of dihydrogen leading to the formation of dihydroborate nickel complex 4. Density functional theory analysis of this reaction revealed that the heterolytic activation of H2 is facilitated by the cooperation of both boryl moieties and the metal atom in a concerted mechanism that involves a Ni(ii)/Ni(0)/Ni(ii) process. Contrary to 1, the boron atom from the PBP ligand in 3 behaves as a nucleophile, accepting a formally protic hydrogen, whereas the catecholboryl moiety acts as an electrophile, receiving the attack from the hydride-like fragment. This manifests the dramatic change in the electronic properties of a ligand by tuning the substituent trans to it and constitutes an unprecedented cooperative mechanism that involves two boryl ligands in the same molecule operating differently, one as a Lewis acid and the other one as a Lewis base, in cooperation with the metal. In addition, reactivity towards different nucleophiles such as amines or ammonia confirmed the electrophilic nature of the Bcat moiety, allowing the formation of aminoboranes.A bis(boryl)nickel complex promotes the facile and reversible activation of H2 through a cooperative mechanism that involves the metal and both boryl moieties in a concerted five-center process. 相似文献
29.
Methodology based on the cloud-point phenomenon was applied to the comparative study of 3 different polyoxyethylene nonionic surfactants in order to extract and preconcentrate a group of phenolic derivatives in water samples; these phenolic compounds, which were determined by liquid chromatography with UV detection, included 11 pollutants given priority by the U.S. Environmental Protection Agency. The optimum conditions for the extraction and preconcentration of phenolic compounds were established for each surfactant. The surfactant that gave the best extraction and preconcentration of the analytes under study was polyoxyethylene 6 lauryl ether (C12E6) with detection limits of <3.5 microg/L for all the phenolic compounds tested. The method was applied to seawater and depurated wastewater samples. 相似文献
30.
Rodríguez AD Ramírez C Rodríguez II Barnes CL 《The Journal of organic chemistry》2000,65(5):1390-1398
Four diterpenes and a nor-diterpenoid, all of which possess unusual carbocyclic skeletons, were isolated from the hexane solubles of the West Indian gorgonian Pseudopterogorgia elisabethae. The structures and relative configurations of novel metabolites elisabethin D (2), elisabethin D acetate (3), 3-epi-elisabanolide (5), elisapterosin A (6), and elisapterosin B (7) were elucidated by interpretation of overall spectral data, which included 2D NMR correlation methods, IR, UV, and accurate mass measurements (HREI-MS and HRFAB-MS), chemical reactions, and X-ray diffraction analyses. The tetracyclic carbon skeleton of the elisapterosins is undescribed and constitutes a new class of C(20) rearranged diterpenes. Elisapterosin B displays strong in vitro anti-tuberculosis activity. 相似文献