全文获取类型
收费全文 | 322篇 |
免费 | 11篇 |
专业分类
化学 | 198篇 |
晶体学 | 4篇 |
力学 | 4篇 |
数学 | 27篇 |
物理学 | 100篇 |
出版年
2023年 | 1篇 |
2022年 | 7篇 |
2021年 | 11篇 |
2020年 | 4篇 |
2019年 | 5篇 |
2018年 | 9篇 |
2017年 | 5篇 |
2016年 | 26篇 |
2015年 | 7篇 |
2014年 | 17篇 |
2013年 | 31篇 |
2012年 | 17篇 |
2011年 | 21篇 |
2010年 | 18篇 |
2009年 | 22篇 |
2008年 | 21篇 |
2007年 | 29篇 |
2006年 | 13篇 |
2005年 | 12篇 |
2004年 | 14篇 |
2003年 | 8篇 |
2002年 | 8篇 |
2001年 | 6篇 |
2000年 | 4篇 |
1999年 | 1篇 |
1998年 | 3篇 |
1997年 | 4篇 |
1996年 | 1篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1991年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
排序方式: 共有333条查询结果,搜索用时 46 毫秒
251.
Seydou Hebié Mabinty Bayo-Bangoura Karifa Bayo Karine Servat Claudia Morais Teko W. Napporn K. Boniface Kokoh 《Journal of Solid State Electrochemistry》2016,20(4):931-942
Carbon-supported metallophthalocyanine catalysts, composed of a transition central metal M (M = Co, Mn, Ni, Fe) in the phthalocyanine ring, were synthesized in this work. As cathodic reaction in a fuel cell, the oxygen reduction reaction (ORR) was investigated in alkaline medium with linear scanning voltammetry at the surface of these electrocatalysts deposited onto a rotating disk electrode (RDE). It was found that the number of electrons transferred depended on the nature of the metallic cation in the catalyst. Evidences provided with Koutecky-Levich approach showed that iron phthalocyanine (FePc) exhibited the better electrocatalytic ability toward the ORR with four electrons exchanged and low activation overpotential. Among these different as-prepared materials, MnPc and FePc led to a four-electron pathway, while CoPc and NiPc proceeded by a two-electron route. The latter reaction process was also determined with a rotating ring-disk electrode (RRDE), which allowed the determination of hydrogen peroxide formed as O2 reduction intermediate in a small amount, i.e., less than 1.2 %. 相似文献
252.
253.
M. A. V. Ribeiro da Silva V. M. F. Morais M. A. R. Matos C. M. A. Rio C. M. G. S. Piedade 《Structural chemistry》1996,7(5-6):329-336
The standard (p
0 = 0.1 MPa) molar enthalpies of formation for the liquid 2,3-dimethylpyrazine and trimethylpyrazine and the crystalline 2,3-dimethylquinoxaline and tetramethylpyrazine were derived from the standard molar enthalpies of combustion, in oxygen, atT=298.15 K, measured by static-bomb combustion calorimetry. The standard molar enthalpies of vaporization or of sublimation for the same compounds were determined by Calvet microcalorimetry. Ab initio full geometry optimization at the 3-21G and 6-31G* levels were also performed for all the methylpyrazine isomers. MP2/RHF/3-21G//3-21G and DFT energies were also calculated for all the methylpyrazine isomers, thus allowing us to estimate their isodesmic resonance energies. 相似文献
254.
The synthesis of imidazolidin-4-one derivatives of primaquine as potential antimalarial agents is described. The target compounds were synthesized in three steps: (i) condensation of (±)-primaquine with Nα-protected amino acids, (ii) removal of the Nα-protecting group, and (iii) reaction of the N-acylprimaquine with a carbonyl compound: acetone, three cyclic ketones and veratraldehyde. Using 2-formylbenzoic acid in the third step afforded 1H-imidazo[2,1-a]isoindole-2,5(3H,9bH)-diones. All products were isolated in good to excellent yields. Whereas imidazolidin-4-ones were formed as mixtures of all possible diastereomers in equal amounts, 1H-imidazo[2,1-a]isoindole-2,5(3H,9bH)-diones were produced in a stereoselective fashion. The compounds hydrolyse very slowly (t1/2 5-30 d) in pH 7.4 buffer to release primaquine. These primaquine derivatives are being submitted to biological assays, and preliminary results of their antimalarial activity are quite encouraging. 相似文献
255.
W. S. Lopes Crislene R. S. Morais A. G. Souza V. D. Leite B. D. de A. Firmo 《Journal of Thermal Analysis and Calorimetry》2007,87(3):841-845
Isothermal
decomposition kinetic of three lanthanide mixed complexes with the general
formula of Ln(thd)3phen (where Ln=Nd3+,
Sm3+ or Er3+, thd=2,2,6,6-tetramethyl-3,5-heptanodione and phen=1,10-phenanthroline) has been studied in this
work. The powders were characterized by their melting point, elemental analysis,
FTIR spectroscopy and thermogravimetry. The isothermal TG curves have been
recorded under the same conditions at 265–285, 265–285 and 250–270°C
for Nd(thd)3phen, Sm(thd)3phen
and Er(thd)3phen, respectively.
The kinetic
parameters, i.e. activation energy, reaction order and frequency factor were
obtained through the technique of lineal regression using the relation g(α)=kt+g
0. The analysis was done
at decomposed fractions between 0.10–0.90. The values of activation
energy were: 114.10, 114.24 and 115.04 kJ mol–1
for the Nd(thd)3phen, Sm(thd)3phen
and Er(thd)3phen complexes, respectively. The kinetic
models that best described the isothermal decomposition reaction the complexes
were R1 and R2. The values of activation energy suggests the following decreasing
order of stability: Nd(thd)3phen<Sm(thd)3phen<Er(thd)3phen. 相似文献
256.
Garcés-García M Morais S González-Martínez MA Puchades R Maquieira A 《Analytical and bioanalytical chemistry》2004,378(2):484-489
A sensitive, simple and reliable method has been developed for the determination of atrazine in extra virgin olive oil. The analytical procedure involves direct extraction of the target analyte from oil matrix with methanol and a freezing clean-up step (–80 °C) followed by plate or sensor immunoassay determination. A detection limit of 0.7 ng/mL, with a dynamic range from 1.0 to 10.4 ng/mL, was reached. The method was highly selective for atrazine and propazine, showing little or no cross-reactivity to other similar compounds. The excellent recoveries obtained (mean value 91.3%) confirm the potential of this approach to detect atrazine in olive oil for application as screening and complementary method in pesticide regulatory and food safety programs. The proposed method correlates well with the reference gas chromatography (GC-MS) technique. 相似文献
257.
The standard (p(o) = 0.1 MPa) molar energies of combustion in oxygen, at T = 298.15 K, of four liquids: 2-ethylpyridine, 4-ethylpyridine, ethylpyrazine and 2,3-diethylpyrazine were measured by static bomb calorimetry in an oxygen atmosphere. The values of the standard molar enthalpies of vaporization, at T = 298.15 K, were obtained by Calvet microcalorimetry, allowing the calculation of the standard molar enthalpies of formation of the compounds, in the gas phase, at T= 298.15 K: 2-ethylpyridine (79.4 +/- 2.6) kJ mol(-1); 4-ethylpyridine (81.0 +/- 3.4) kJ mol(-1); ethylpyrazine (146.9 +/- 2.8) kJ mol(-1); and 2,3-diethylpyrazine (80.2 +/- 2.9) kJ mol(-1). The most stable geometries of all ethylpyridine and ethylpyrazine isomers were obtained using the density functional theory with the B3LYP functional and two basis sets: 6-31G* and 6-311G**. These calculations were then used to obtain estimates of the enthalpies of formation of all isomers, including those not experimentally studied, through the use of isodesmic reactions. A discussion of the relationship between structure and energetics of the isomers is also presented. 相似文献
258.
Soler MA Lima EC da Silva SW Melo TF Pimenta AC Sinnecker JP Azevedo RB Garg VK Oliveira AC Novak MA Morais PC 《Langmuir : the ACS journal of surfaces and colloids》2007,23(19):9611-9617
In this study, we report on how surface-passivated and nonpassivated cobalt ferrite nanoparticles (8 nm diameter), suspended as ionic magnetic fluids and aged under low pH conditions, revealed different behavior as far as the time evolution of the iron/cobalt cation distribution, crystal quality, coercivity, and saturation magnetization are concerned. Different techniques were used to perform a detailed study regarding the chemical stability, structural stability, and surface and magnetic properties of the suspended nanoparticles as a function of the aging time. Properties of surface-passivated and nonpassivated nanoparticles were investigated by transmission electron microscopy, X-ray diffraction, atomic absorption spectrometry, magnetic measurements, Raman spectroscopy, and M?ssbauer spectroscopy. Our data showed that the employed nanoparticle surface passivation process, besides the formation of an iron-rich surface layer, modifies the nanoparticle core as well, improving the crystal quality while modifying the Fe/Co cation distribution and the nanoparticle dissolution rate profile. Magnetic data showed that the saturation magnetization increases for surface-passivated nanoparticles in comparison to the nonpassivated ones, though coercivity decreases after passivation. These two observations were associated to changes in the cation distribution among the available tetrahedral and octahedral sites. 相似文献
259.
Migowski P Machado G Texeira SR Alves MC Morais J Traverse A Dupont J 《Physical chemistry chemical physics : PCCP》2007,9(34):4814-4821
The diameter and size-distribution of Ni nanoparticles prepared by the decomposition of [bis(1,5-cyclooctadiene)nickel(0)] organometallic precursor dissolved in 1-alkyl-3-methylimidazolium N-bis(trifluoromethanesulfonyl) amide ionic liquids depend on the length of the alkyl side-chain of the imidazolium ring. The increase of the organization range order of the ionic liquid that increases with that of the alkyl side-chain (from n-butyl to n-hexadecyl) induces the formation of nanoparticles with a smaller diameter and size-distribution. The cubic fcc Ni nanoparticles with 4.9 +/- 0.9 to 5.9 +/- 1.4 nm in mean diameter and monomodal size-distribution thus prepared are probably composed of a small cap layer of NiO around a core of Ni metal. The contribution of the oxide layer also depends on the medium i.e. the metal oxide ratio increases in salts containing four to eight carbons on their side-chains and then decreases as the number of carbons increases. The Ni nanoparticles dispersed in the ionic liquids are active catalysts for the hydrogenation of olefins under relatively mild reaction conditions. 相似文献
260.
Graziele P. Ramos Paula M. B. Dias Cláudia B. Morais Pedro E. Fröehlich Miguel Dall’Agnol José A. S. Zuanazzi 《Chromatographia》2008,67(1-2):125-129
Red clover (Trifolium pratense L.) is an important forage plant that contains the isoflavones daidzein, genistein, formononetin, and biochanin A. These
compounds have been studied lately due to their human health benefits. The aim of this study was to develop and validate an
HPLC method with simplified sample preparation to quantify daidzein, genistein, formononetin and biochanin A simultaneously
in red clover leaves. The validation showed that the method is specific, accurate, precise and robust, not to mention that
the sample preparation is easier and faster than those described earlier. The response was linear over a range of 0.01–0.2 μg mL−1 for daidzein, 0.05–0.5 μg mL−1 for genistein, 4–40 μg mL−1 for formononetin and 2–20 μg mL−1 for biochanin A. The range of recoveries was 85.6–101.0%. The RSD for intra- and inter-day precision were <2.54 and <7.22%,
respectively. Five populations of red clover, from the National Plant Germplasm System-USDA were analyzed and the content
of daidzein, genistein, formononetin and biochanin A ranged from 7.87–91.31, 51.60–131.30, 6568.33–23461.82, to 2499.55–10337.33 μg g−1 of dried material, respectively. 相似文献