全文获取类型
收费全文 | 117篇 |
免费 | 5篇 |
专业分类
化学 | 79篇 |
晶体学 | 2篇 |
力学 | 1篇 |
数学 | 17篇 |
物理学 | 23篇 |
出版年
2023年 | 3篇 |
2022年 | 1篇 |
2020年 | 3篇 |
2019年 | 3篇 |
2018年 | 2篇 |
2017年 | 3篇 |
2016年 | 6篇 |
2015年 | 5篇 |
2014年 | 4篇 |
2013年 | 9篇 |
2012年 | 16篇 |
2011年 | 9篇 |
2010年 | 4篇 |
2009年 | 4篇 |
2008年 | 11篇 |
2007年 | 16篇 |
2006年 | 5篇 |
2004年 | 2篇 |
2003年 | 5篇 |
2002年 | 1篇 |
2001年 | 1篇 |
2000年 | 3篇 |
1997年 | 2篇 |
1993年 | 1篇 |
1988年 | 1篇 |
1980年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有122条查询结果,搜索用时 15 毫秒
1.
Maurício Cavicchioli Antonio Carlos Massabni Luciana Rebelo Guilherme Eduardo Ernesto Castellano Armando Paduan-Filho Ana Maria da Costa Ferreira 《Transition Metal Chemistry》2007,32(3):355-361
Structural, electrochemical and spectroscopic data of a new dinuclear copper(II) complex with (±)-2-(p-methoxyphenoxy)propionic acid are reported. The complex {tetra-μ-[(±)-2-(p-methoxyphenoxy)propionato-O,O′]-bis(aqua)dicopper(II)} crystallizes in the monoclinic system, space group P21/n with a = 14.149(1) ?, b = 7.495(1) ?, c = 19.827(1) ?, β = 90.62(1) and Z = 4. X-ray diffraction data show that the two copper(II) ions are held together through four carboxylate bridges, coordinated
as equatorial ligands in square pyramidal geometry. The coordination sphere around each copper ion is completed by two water
molecules as axial ligands. Thermogravimetric data are consistent with such results. The ligand has an “L” type shape due
to the angle formed by the β-carbon of the propionic chain and the linked p-methoxyphenoxy group. This conformation contributes to the occurrence of a peculiar structure of the complex. The complex
retains its dinuclear nature when dissolved in acetonitrile, but it decomposes into the corresponding mononuclear species
if dissolved in ethanol, according to the EPR measurements. Further, cyclic voltammograms of the complex in acetonitrile show
that the dinuclear species maintains the same structure, in agreement with the EPR data in this solvent. The voltammogram
shows two irreversible reduction waves at E
pc = −0.73 and −1.04 V vs. Ag/AgCl assigned to the Cu(II)/Cu(I) and Cu(I)/Cu° redox couples, respectively, and two successive oxidation waves at E
pa =− 0.01 and +1.41 V vs. Ag/AgCl, assigned to the Cu°/Cu(I) and Cu(I)/Cu(II) redox couples, respectively, in addition to the oxidation waves of the
carboxylate ligand. 相似文献
2.
Preconcentration and speciation of chromium in waters using solid-phase extraction and atomic absorption spectrometry 总被引:1,自引:0,他引:1
A method for the preconcentration and speciation of chromium was developed. After formation of an anionic compound with ethylenediaminetetraacetic acid (CrY(-)), Cr (VI) and Cr (III) are retained on a strong anionic phase (SAX) and controlled elution with 0.5 M NaCl permits their speciation. The retention and elution conditions were optimised, and interferences due to the presence of other ions such as Mg(II), Mn(II), Sn(II), Fe(III), Ba(II), Al(III), Ca(II), chloride, iodine, bromide, fluoride, sulphate, phosphate, bicarbonate and nitrate were studied. The detection limits were 0.4 mug l(-1) and 1.1 mug l(-1) for Cr(III) and Cr(VI), respectively, and reproducibility was 9%. The results obtained for speciation of chromium by the proposed method in wastewaters are in agreement with the values obtained by a reference method for a 95% confidence level. 相似文献
3.
Maurício Vieira Kritz 《Bulletin of the Brazilian Mathematical Society》1980,11(2):217-236
In this work the initial value problem for the equation $$u_t + \beta u_x + yf(u)_x - \delta u_{xxt} = g,\forall x \in R, \forall t \in [0,T],$$ with periodic boundary conditions is interpreted in the sense of periodic distributions and studied via fixed point arguments. Weak solutions exist iff∈C 0 (R) andg∈L ∞(L 2(0,1)). Moreover, regularity inf, g and the initial data implies regularity of solutions. 相似文献
4.
Marco Lopez Fabio Sacconi Matthias Auf der Maur Alessandro Pecchia Aldo Di Carlo 《Optical and Quantum Electronics》2012,44(3-5):89-94
In this work electronic and optoelectronic properties of InGaN/GaN nanocolumn quantum disk LEDs have been studied with the multiscale simulation tool tiberCAD. Calculations have been performed with an atomistic tight-binding model. Results shows that emission energies have a minor dependence on the nanocolumn dimension while In concentration in the active region is a critical parameter. 相似文献
5.
Plínio T. Berardo Maurício S. Abrao Maísa L.S. Souza Daniel E. Machado Luiz-Cláudio F. Silva Luiz E. Nasciutti 《Micron (Oxford, England : 1993)》2009,40(5-6):639-645
The composition of sulfated glycosaminoglycans (GAGs) and the tissue distribution of chondroitin sulfate (CS) were analyzed in deeply infiltrating endometriosis (DIE) of rectosigmoid, using metachromatic staining, and biochemical analysis employing electrophoresis before and after specific enzymatic or chemical degradations, and immunostaining with an antibody against CS. The sulfated GAGs were characterized as dermatan sulfate (DS), heparan sulfate (HS) and CS; and DS strongly predominated compared to HS and CS. Immunostaining procedures showed that CS was concentrated in the endometriosis foci, distributed throughout the stroma around the glands. This is the first report describing the composition of sulfated GAGs and the tissue location of CS in DIE by means of histochemical, biochemical and immunohistochemical analyses. These results confirmed that in DIE of rectosigmoid, as in eutopic endometrium [Nasciutti, L.E., Ferrari, R., Berardo, P.T., Souza, M.L.S., Takiya, C.M., Borojevic, R., Abrao, M.S., Silva, L.C.F., 2006. Distribution of chondroitin sulfate in human endometrium. Micron 37, 544–550], CS was the dominant sulfated GAG in stroma of the lesion foci. 相似文献
6.
Giovana de Fátima Menegotto Paulo César Borges Eduardo Mauro do Nascimento Carlos Maurício Lepienski Elaine Cristina Azevedo 《Brazilian Journal of Physics》2011,41(4-6):223-228
The influence of hydrogen loading temperature on the mechanical strength of optical fibers is investigated. Fibers subjected to high-pressure hydrogen loading at different temperatures were submitted to bend tests, and the results compared with those for pristine fibers. The Weibull probability distribution function was used to analyze the data of the mechanical bending strength of the fibers. Fiber strength is reduced by the presence of hydrogen, and this decrease is greater for higher hydrogen loading temperatures. The mechanical properties of the polymers used to coat fibers are affected by the hydrogen loading process and also by the increase in temperature. However, there is no evidence of cracks formation that might allow water to penetrate to the surface of the glass. Observation using scanning electron microscopy revealed that the morphology of fractures in nonhydrogen-loaded fibers have distinct fracture characteristics to that of fibers that are hydrogen loaded at 90°C and 120°C. 相似文献
7.
Scarpellini M Neves A Hörner R Bortoluzzi AJ Szpoganics B Zucco C Nome Silva RA Drago V Mangrich AS Ortiz WA Passos WA de Oliveira MC Terenzi H 《Inorganic chemistry》2003,42(25):8353-8365
The tridentate Schiff base [(2-(imidazol-4-yl)ethyl)(1-methylimidazol-2-yl)methyl)imine (HISMIMI) and its reduced form HISMIMA were synthesized and characterized, as well their mononuclear cis-dihalo copper(II) complexes 1 and 2, respectively. In addition, the dinuclear [CuII(mu-OH)2CuII](2+) complexes (3) and (4) obtained from complexes 1 and 2, respectively, were also isolated and characterized by several physicochemical techniques, including magnetochemistry, electrochemistry, and EPR and UV-vis spectroscopies. The crystal structures of 1 and 2 were determined by X-ray crystallography and revealed two neutral complexes with their tridentate chelate ligands meridionally coordinated. Completing the coordination spheres of the square-pyramidal structures, a chloride ion occupies the apical position and another is bonded in the basal plane. In addition, complexes 1 and 2 were investigated by infrared, electronic, and EPR spectroscopies, cyclic voltammetry, and potentiometric equilibrium studies. The hydrolytic activity on phosphate diester cleavage of 1 and 2 was investigated utilizing 2,4-BDNPP as substrate. These experiments were carried out at 50 degrees C, and the data treatment was based on the Michaelis-Menten approach, giving the following kinetic parameters (complex 1/complex 2): vmax (mol L(-1) s(-1))=16.4x10(-9)/7.02x10(-9); KM (mol L(-1))=17.3x10(-3)/3.03x10(-3); kcat (s(-1))=3.28x10(-4)/1.40x10(-4). Complex 1 effectively promoted the hydrolytic cleavage of double-strand plasmid DNA under anaerobic and aerobic conditions, with a rate constant of 0.28 h(-1) for the decrease of form I, which represents about a 10(7) rate increase compared with the estimated uncatalyzed rate of hydrolysis. 相似文献
8.
M Llobat-Estellés A R Maurí-Aucejo M D López-Catalán 《Fresenius' Journal of Analytical Chemistry》2001,371(3):358-363
A method has been developed for the determination of chromium in presence of V(V), Mo(VI), and Fe(III). The effects of interferences were evaluated by using the apparent content curves method, and their separation was performed by solid-phase extraction with an anionic exchanger. The sample-treatment conditions and the influence of the sample conductivity were studied. Tolerance limits were established, and the proposed procedure was used to determine chromium in certified samples and for speciation of chromium in waste water. Our results were always in agreement with the theoretical content. 相似文献
9.
Maurício Hilgemann Fritz Scholz Heike Kahlert Leandro Machado de Carvalho Marcelo Barcellos da Rosa Ulrike Lindequist Martina Wurster Paulo C. do Nascimento Denise Bohrer 《Electroanalysis》2010,22(4):406-412
A new electrochemical assay has been developed which is based on quantifying the attack of OH. radicals on a self‐assembled thiol monolayer on electrodes in the presence and absence of antioxidants. The OH. radicals were produced in Fenton solutions. The radical scavengers diminish the concentration of the OH. radicals in the Fenton solution, and the extent of thiol layer destruction is monitored with the help of a redox probe in solution, the signal of which is only generated at SAM‐free electrode surface. The results of the electrochemical assay were compared with those of the standard DPPH. assay. In case of each plant extract, an excellent linear correlation was observed between the radical scavenging activity and the concentration of plant extracts; however, the scavenging properties of different plants strongly differ in the electrochemical and the DPPH. assay. Since the proposed new method probes the reactivity of radical scavengers towards OH., one of the most important reactive oxygen radicals in tissues, it is supposed to provide much more relevant information than the DPPH. or other assays. 相似文献
10.
Silva MA Dantelle G Mortier M Monteil A Ribeiro SJ Messaddeq Y Briois V Poulain M 《The Journal of chemical physics》2008,128(24):244516
Erbium L(3)-edge extended x-ray absorption fine structure (EXAFS) measurements were performed on rare earth doped fluorosilicate and fluoroborate glasses and glass ceramics. The well known nucleating effects of erbium ions for the crystallization of cubic lead fluoride (based on x-ray diffraction measurements) and the fact that the rare earth ions are present in the crystalline phase (as indicated by Er(3+) emission spectra) seem in contradiction with the present EXAFS analysis, which indicates a lack of medium range structural ordering around the Er(3+) ions and suggests that the lead fluoride crystallization does not occur in the nearest neighbor distance of the rare earth ion. Molecular dynamics simulations of the devitrification process of a lead fluoride glass doped with Er(3+) ions were performed, and results indicate that Er(3+) ions lower the devitrification temperature of PbF(2), in good agreement with the experimental results. The genuine role of Er(3+) ions in the devitrification process of PbF(2) has been investigated. Although Er(3+) ions could indeed act as seeds for crystallization, as experiments suggest, molecular dynamics simulation results corroborate the experimental EXAFS observation that the devitrification does not occur at its nearest neighbor distance. 相似文献