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51.
We describe a density functional theory approach to solvation in molecular solvents. The solvation free energy of a complex solute can be obtained by direct minimization of a density functional, instead of the thermodynamic integration scheme necessary when using atomistic simulations. In the homogeneous reference fluid approximation, the expression of the free-energy functional relies on the knowledge of the direct correlation function of the pure solvent. After discussing general molecular solvents, we present a generic density functional describing a dipolar solvent and we show how it can be reduced to the conventional implicit solvent models when the solvent microscopic structure is neglected. With respect to those models, the functional includes additional effects such as the microscopic structure of the solvent, the dipolar saturation effect, and the nonlocal character of the dielectric constant. We also show how this functional can be minimized numerically on a three-dimensional grid around a solute of complex shape to provide, in a single shot, both the average solvent structure and the absolute solvation free energy. 相似文献
52.
Laloup M Ramirez Fernandez Mdel M Wood M De Boeck G Henquet C Maes V Samyn N 《Journal of chromatography. A》2005,1082(1):15-24
A rapid and sensitive method for the analysis of delta9-tetrahydrocannabinol (THC) in preserved oral fluid was developed and fully validated. Oral fluid was collected with the Intercept, a Food and Drug Administration (FDA) approved sampling device that is used on a large scale in the U.S. for workplace drug testing. The method comprised a simple liquid-liquid extraction with hexane, followed by liquid chromatography-tandem mass spectrometry (LC-MS-MS) analysis. Chromatographic separation was achieved using a XTerra MS C18 column, eluted isocratically with 1 mM ammonium formate-methanol (10:90, v/v). Selectivity of the method was achieved by a combination of retention time, and two precursor-product ion transitions. The use of the liquid-liquid extraction was demonstrated to be highly effective and led to significant decreases in the interferences present in the matrix. Validation of the method was performed using both 100 and 500 MicroL of oral fluid. The method was linear over the range investigated (0.5-100 ng/mL and 0. 1-10 ng/mL when 100 and 500 microL, respectively, of oral fluid were used) with an excellent intra-assay and inter-assay precision (relative standard deviations, RSD <6%) for quality control samples spiked at a concentration of 2.5 and 25 ng/mL and 0.5 and 2.5 ng/mL, respectively. Limits of quantification were 0.5 and 0.1 ng/mL when using 100 and 500 microL, respectively. In contrast to existing GC-MS methods, no extensive sample clean-up and time-consuming derivatisation steps were needed. The method was subsequently applied to Intercept samples collected at the roadside and collected during a controlled study with cannabis. 相似文献
53.
54.
An experimental study has been conducted to assess the structural refinement of magnesium and its alloys by ultrasonic irradiation during solidification. It is shown that (i) ultrasonic irradiation leads to significant refinement only in the presence of adequate solute, which is alloy dependent; (ii) the attendant grain density increases linearly with increase in solute content at a given irradiation level; (iii) increasing the solute content at a low irradiation level above the cavitation threshold is more effective than substantially increasing the irradiation intensity; and (iv) the difference in the grain size between two ultrasonicated magnesium alloys is mainly determined by the solute content rather than the irradiation intensity. In view of these, the effect of ultrasonic irradiation on solute redistribution in a solidifying magnesium alloy seems rather limited even at a substantial intensity level such as 1700 W cm−2. The implications of these findings are discussed and a mechanism is proposed to account for the experimental observations. 相似文献
55.
Jose Luis Castro Maria Rosa Lopez‐Ramirez Juan Francisco Arenas Juan Carlos Otero 《Journal of Raman spectroscopy : JRS》2012,43(7):857-862
The Surface‐enhanced Raman scattering of benzenesulfonamide and sulfanilamide adsorbed on silver sols was studied. On the basis of the noticeable shifts observed for wavenumbers of the νs(OSO), ν(CS), and ν(SN) vibrations with respect to the Raman spectra of the solids and the ionic solutions, we conclude that these molecules are adsorbed on silver nanoclusters at pH ≥ 7 with the aminosulfonyl groups partially deprotonated. The benzenesulfonamide links to the metal through the nitrogen atom of the corresponding azanion, while the sulfanilamide interacts in turn through the nitrogen atoms of the –NH2 and –SO2NH– groups in the para‐position. Additionally, it was found that the most enhanced surface‐enhanced Raman scattering bands, especially the 8a;νring mode, are related to the presence of the charge transfer mechanism. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
56.
Manuel Vásquez-Montoya Juan F.Montoya Daniel Ramirez Franklin Jaramillo 《Journal of Energy Chemistry》2021,(6):386-391
Upscaling perovskite solar cell fabrication is one of the key challenges in the pathway for commercialization.The slow evaporation of frequently used solvents (... 相似文献
57.
58.
Balbina P. García-Aguilar Antonio Avalos Ramirez J. Peter Jones Michèle Heitz 《Chemical Papers》2011,65(3):373-379
The emissions of methane (CH4), a powerful greenhouse gas (GES), contribute to the increase in GES concentration level in the atmosphere. For this reason,
the importance of controlling CH4 emissions of anthropogenic origin has increased over the last decades. Physicochemical and biological processes are available
for treating CH4. For this reason, such properties as the solubility of CH4 in aqueous solutions and organic solvents are of great relevance in different applications in environmental engineering and
biotechnology. In this study, the solubility of CH4 was determined at 298 K and 101.3 kPa in organic solvents, such as polyoxyethylenesorbates (Tween 20, Tween 40, and Tween
60), and linear alcohols (methanol, ethanol, and butan-1-ol) alone and in their admixtures. Admixtures of methanol with butan-1-ol
exhibited the highest solubility of CH4, of around 0.49 g m−3 of solvent, whereas the solubility of CH4 in linear alcohols varied from 0.167 g m−3 to 0.41 g m−3 of solvent. In the case of Tweens, CH4 solubility decreased with the hydrophilic-lipophilic balance (HLB) number. 相似文献
59.
Kim YA Ramirez DM Costain WJ Johnston LJ Bittman R 《Chemical communications (Cambridge, England)》2011,47(32):9236-9238
The bioactivity of natural, long-chain ceramides has until now been studied after its delivery to cells in organic solvent mixtures containing dodecane. We have synthesized ceramides conjugated to a (6-bromo-7-hydroxycoumarin-4-yl)methyl group. The photocaged ceramide is efficiently released with 350 nm light in aqueous solution at neutral pH, thus providing a promising new tool to study ceramide's properties. 相似文献
60.
Rolando Ramirez Carlos Eduardo Schnorr Jordana Georgin Matias Schadeck Netto Dison S. P. Franco Elvis Carissimi Delmira Wolff Luis F. O. Silva Guilherme Luiz Dotto 《Molecules (Basel, Switzerland)》2022,27(22)
Brazil’s production and consumption of açai pulp (Euterpe oleracea) occur on a large scale. Most of the fruit is formed by the pit, which generates countless tons of residual biomass. A new purpose for this biomass, making its consumption highly sustainable, was presented in this study, where activated carbon (AC) was produced with zinc chloride for later use as an adsorbent. AC carbon formed by carbon and with a yield of 28 % was satisfactorily used as an adsorbent in removing the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Removal efficiency was due to the highly porous surface (Vp = 0.467 cm3 g−1; Dp = 1.126 nm) and good surface área (SBET = 920.56 m2 g−1). The equilibrium data fit the Sips heterogeneous and homogeneous surface model better. It was observed that the increase in temperature favored adsorption, reaching a maximum experimental capacity of 218 mg g−1 at 328 K. The thermodynamic behavior indicated a spontaneous, favorable, and endothermic behavior. The magnitude of the enthalpy of adsorption was in agreement with the physical adsorption. Regardless of the herbicide concentration, the adsorbent displayed fast kinetics, reaching equilibrium within 120 min. The linear driving force (LDF) model provided a strong statistical match to the kinetic curves. AC with zinc chloride (ZnCl2), created from leftover açai biomass, is a potential alternative as an adsorbent for treating effluents containing 2,4-D. 相似文献