全文获取类型
收费全文 | 302篇 |
免费 | 7篇 |
国内免费 | 2篇 |
专业分类
化学 | 265篇 |
晶体学 | 2篇 |
数学 | 5篇 |
物理学 | 39篇 |
出版年
2023年 | 1篇 |
2022年 | 4篇 |
2021年 | 8篇 |
2020年 | 5篇 |
2019年 | 9篇 |
2018年 | 7篇 |
2017年 | 4篇 |
2016年 | 2篇 |
2015年 | 5篇 |
2014年 | 7篇 |
2013年 | 14篇 |
2012年 | 14篇 |
2011年 | 17篇 |
2010年 | 10篇 |
2009年 | 15篇 |
2008年 | 14篇 |
2007年 | 23篇 |
2006年 | 24篇 |
2005年 | 22篇 |
2004年 | 19篇 |
2003年 | 5篇 |
2002年 | 11篇 |
2001年 | 5篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 4篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1991年 | 2篇 |
1990年 | 5篇 |
1989年 | 7篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1977年 | 3篇 |
1914年 | 1篇 |
1908年 | 1篇 |
排序方式: 共有311条查询结果,搜索用时 125 毫秒
11.
Mrcia Sousa Bispo Maria das Graas Andrade Korn Elane Santos da Boa Morte Leonardo Sena Gomes Teixeira 《Spectrochimica Acta Part B: Atomic Spectroscopy》2002,57(12):2175-2180
An analytical method for separation and pre-concentration of lead in seawater for determination by inductively coupled plasma optical emission spectrometry has been investigated. Lead was retained in the solid phase (0.5 g) composed of co-precipitated naphthalene and alizarin red. The solid phase quantitatively sorbs Pb(II) at pH 8–9, and the metal was eluted using 5.0 ml of 2 mol l−1 nitric acid. The effect of NaCl, KCl, BaCl2, CaCl2, Na2SO4, MgCl2 and Na3PO4 on the sorption of Pb(II) in the solid phase was studied. A set of solutions containing varying amounts of electrolytes (0.5; 1.0; 3.0 and 5.0% m/v) with Pb (50 μg) was prepared and the recommended procedure applied. The Na3PO4 was found to interfere; the other electrolytes did not interfere up to 5% m/v. A pre-concentration factor of 40 was obtained in this analytical procedure. The limit of detection and limit of quantification for Pb(II) were 53 and 176 μg l−1, respectively. Lead was determined in seawater samples collected in Salvador city, Bahia, Brazil. The precision, expressed as R.S.D., was 1.8–4.6%, and the recovery of lead added to seawater samples was 95–97%. 相似文献
12.
The parameters that influence the conformation of poly(propylene imine) dendrimers were investigated by molecular simulations using molecular mechanics and simulated annealing methods. Dendrimers with two types of peripheral units able to communicate via hydrogen bonding-amine and amide moieties-were considered in order to study the role that secondary interactions among the end groups have in the spatial organization of the dendritic branches. Radial atomic density profiles and radial atomic probability distributions were used to extract global properties, such as the degree of packing of the branches, the distribution of the monomers throughout the molecular volume, and the extent and characteristics of the surface region. Information was also obtained about the nature, location, and extent of formation of the hydrogen bonds, as well as their evolution with dendrimer generation and their assembly into networks. The analyses were supported by a detailed investigation of the first two generations, with an emphasis on the relationship between hydrogen bonding and the compactness and stability of the molecules; this allowed us to account for the generational evolution of hydrogen bonding that is experimentally observed in several poly(propylene imine) dendrimers. 相似文献
13.
Two series of monoionic (M) kaolinites (M = H(+), Ca(2+), Cu(2+), Zn(2+), Al(3+), and Fe(3+)) were prepared from a natural Brazilian clay (S?o Sim?o clay, SP): series A, dried under vacuum at 25 degrees C, and series B, dried under vacuum at 25 degrees C. The natural clay was characterized by elemental analysis, cation exchange capacity, X-ray diffractometry, differential thermal analysis, and surface area measurements (BET). The interactions of M,M-dimethylacetamide and pyridine with these (M) kaolinites were studied by adsorption isotherms, titration calorimetry, and infrared spectroscopy (for pyridine only). The results indicated a coordinative interaction between M,M-dimethylacetamide and (M) kaolinites. For the interactions between pyridine and (M) kaolinites, the formation of hydrogen bonds (M = Al(3+), Fe(3+)), hydrogen and coordinative bonds (M = Cu(2+), Zn(2+)), and ionic pairs (M = H(+), Ca(2+)) was observed. For the pyridine-(Cu) kaolinite system, a substitution of water coordinated to Cu(2+) by pyridine was established. 相似文献
14.
The equilibrium constants and molar absorptivities for the fast formation of a 1:3 complex between cadmium(II) (Cd(II)) and dithizonate anion, in the presence of cationic and non-ionic surfactants, allowed a simple and fast spectrophotometric determination of total cadmium. Indeed, the molar absorptivities of the Cd(II)-dithizone (Dz) complex formed in the presence of the neutral Triton X-100 and cationic cetyltrimethylammonium bromide (CTAB) surfactants are almost twice the value observed in the standard method and the maxima of absorption are shifted by about 40 nm when compared with the standard method. Clearly, the use of neutral and cationic surfactants promotes a higher value of the molar absorptivities of the complex, resulting in an increase in the sensitivity of the method. Application of the method to the desorption of Cd(II) ions from clays is illustrated. 相似文献
15.
Jones SC Coropceanu V Barlow S Kinnibrugh T Timofeeva T Brédas JL Marder SR 《Journal of the American Chemical Society》2004,126(38):11782-11783
A complex featuring two triarylamine redox centers bridged by Pt, trans-bis(triethylphosphine)-bis{4-[bis(4-methoxyphenyl)amino]phenylethynyl} platinum(II), has been synthesized as a model system for pi-conjugated Pt-containing polymers. Analysis of the intervalence charge-transfer band displayed by its mixed-valence monocation affords a quantitative assessment of electronic delocalization through the Pt bridge; this is found to be only slightly smaller than that determined for a benzene-bridged analogue. These results are supported by density functional theory calculations, which show that the active orbitals involved in the electron-transfer process in both cases have similar delocalization through the bridging unit. 相似文献
16.
Denilson S.S. dos Santos Alete P. Teixeira José T.P. Barbosa Sérgio L.C. Ferreira Maria das Graças A. Korn Leonardo S.G. Teixeira 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007
In this work, the use of cetyltrimethylammonium bromide as surfactant for the preparation of oil-in-water emulsions for the determination of Cu and Cr in gasoline by electrothermal atomic absorption spectrometry (ET AAS) was evaluated. The surfactant amount was tested in the range of 25 to 300 mg, added to 2 ml of gasoline, and completed to 10 mL with 0.1% (v/v) nitric acid solution. 150 mg of surfactant was found optimum, and a sonication time of 10 min sufficient to form an oil-in-water emulsion that was stable for several hours. The ET AAS temperature program was established based on pyrolysis and atomization curves. The pyrolysis temperatures were set at 700 and 1300 °C for Cu and Cr, respectively and the selected atomization temperatures were 2400 and 2500 °C. The time and temperature of the drying stage and the atomization time were experimentally tested to provide optimum conditions. The limits of detection were found to be 5 μg L− 1 and 1.5 μg L− 1 for Cu and Cr, respectively in the original gasoline samples. The relative standard deviation (RSD) ranged from 4 to 9% in oil-in-water emulsions spiked with 5 μg L− 1 and 15 μg L− 1 of each metal, respectively. Recoveries varied from 90 to 98%. The accuracy of the proposed method was tested by an alternate procedure using complete evaporation of the gasoline sample. The method was adequate for the determination of Cu and Cr in gasoline samples collected from different gas stations in Salvador, BA, Brazil. 相似文献
17.
Reduction of sugar methoximes with sodium cyanoborohydride followed by permethylation with CH3SOCH2?/ICH3 affords the corresponding deoxy(methylmethoxylamino)alditol O-methyl ethers, which are amenable to capillary gas chromatography. Derivatization proceeds under mild conditions with high yields. Only a single derivative is formed for each reducing sugar. All aldose derivatives can be separated in a single chromatographic run on glass capillaries coated with Carbowax 20 M or Superox 0.1. Good linearity was found. The introduction of the nitrogen atom in the sugar molecule makes these derivatives suitable for selective detection by the NPD. The El-mass spectra contain intense characteristics ions at m/z 74 for aldoses and at m/z 280 for reducing disaccharides, together with a (M - 15)+ion. These fragments are very suitable for highly sensitive GC-MS analysis by selective single ion monitoring. 相似文献
18.
19.
Gatto Claudia C. Chagas Marcio A. S. Lima Iariane J. Mello Andrade Francyelli Silva Hugo D. Abrantes Gabrielly R. Lacerda Elisângela P. S. 《Transition Metal Chemistry》2019,44(4):329-340
Transition Metal Chemistry - The present study reports the synthesis and crystal structures of Cu(II) complexes with pyridoxal S-allyldithiocarbazate (H2L1) and pyridoxal thiosemicarbazones... 相似文献
20.