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81.
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83.
James D. Oliver Adam A. Rosser Christopher M. Fellows Yohann Guillaneuf Jean-Louis Clement Marianne Gaborieau Patrice Castignolles 《Analytica chimica acta》2014
Direct UV detection of carbohydrates in free solution capillary electrophoresis at 270 nm is made possible by a photo-oxidation reaction. Glucose, rhamnose and xylose were shown to have unique UV absorption spectra hypothesizing different UV absorbing intermediates for their respective photo-oxidation. NMR spectroscopy of the photo-oxidation end products proved they consisted of carboxylates and not malondialdehyde as previously theorized and that oxygen thus plays a key role in the photo-oxidation pathway. Adding the photo-initiator Irgacure® 2959 in the background electrolyte increased sensitivity by 40% at an optimum concentration of 1 × 10−4 mM and 1 × 10−8 mM for conventional 50 μm i.d. capillaries and for the corresponding extended light path capillaries, respectively. 相似文献
84.
We report mesoscale simulations of spherical drops to investigate the surface tension and mechanical properties. The Monte Carlo simulations are performed with the multibody potential commonly used in the many-body dissipative particle dynamics simulations. We establish here the calculation of the local normal and transverse components of the pressure tensor via the perturbation volume within the thermodynamic route. The different profiles of these components are compared to those calculated using the mechanical approach. To complete the mesoscale modeling of drops, we investigate the curvature dependence of the surface tension in order to calculate the Tolman's length, which is found to be negative. 相似文献
85.
A complete critical evaluation of all available phase diagram and thermodynamic data has been performed for all condensed phases and relevant gaseous species of the (NaCl + KCl + MgCl2 + CaCl2 + ZnCl2) system, and optimized model parameters have been found. The (NaCl + KCl + MgCl2 + CaCl2) subsystem has been critically evaluated in a previous article. The model parameters obtained for the binary and ternary subsystems can be used to predict thermodynamic properties and phase equilibria for the multicomponent system. The Modified Quasichemical Model for short-range ordering was used for the molten salt phase. 相似文献
86.
Sacré PY Deconinck E Chiap P Crommen J Mansion F Rozet E Courselle P De Beer JO 《Journal of chromatography. A》2011,1218(37):6439-6447
Pharmaceutical counterfeiting is a permanently growing problem. Control laboratories are constantly analysing counterfeit medicines. In industrialised countries, one of the main counterfeited class of medicines are erectile dysfunction drugs. This paper describes the development and validation of a fast method to detect and quantify the three authorised phosphodiesterase type 5 inhibitors and five analogues. The method is based on the use of a sub-2 microns polar-embedded column with a gradient using acetonitrile as organic modifier and 10 mM ammonium formate buffer (pH 3.5) as aqueous component of the mobile phase. The separation was achieved in less than 4.5 min. The method has also been compared to the registered HPLC method for the assay of Viagra® which was considered as the reference method. The method is also compatible with on-line coupling mass spectrometry and will significantly reduce analysis times and solvent consumption. 相似文献
87.
Bourdolle A Allali M Mulatier JC Le Guennic B Zwier JM Baldeck PL Bünzli JC Andraud C Lamarque L Maury O 《Inorganic chemistry》2011,50(11):4987-4999
Two europium complexes with bis(bipyridine) azamacrocyclic ligands featuring pendant arms with or without π-conjugated donor groups are synthesized and fully characterized by theoretical calculations and NMR spectroscopy. Their photophysical properties, including two-photon absorption, are investigated in water and in various organic solvents. The nonfunctionalized ligand gives highly water-stable europium complexes featuring bright luminescence properties but poor two-photon absorption cross sections. On the other hand, the europium complex with an extended conjugated antenna ligand presents a two-photon absorption cross section of 45 GM at 720 nm but is poorly luminescent in water. A detailed solvent-dependent photophysical study indicates that this luminescence quenching is not due to the direct coordination of O-H vibrators to the metal center but to the increase of nonradiative processes in a protic solvent induced by an internal isomerization equilibrium. 相似文献
88.
Pawlowska Z Lietard A Aloïse S Sliwa M Idrissi A Poizat O Buntinx G Delbaere S Perrier A Maurel F Jacques P Abe J 《Physical chemistry chemical physics : PCCP》2011,13(29):13185-13195
This work reports on the solvatochromic properties of a simple heterocyclic betaine pyridinium, 2-(1-pyridinio)benzimidazolate (SBPa), having promising potentialities in non-linear optics. From advanced PCM-TDDFT calculations, the solvatochromism of SBPa was found to be unusual, involving two different electronic states for absorption (S(0)→ S(2)) and emission (S(1)→S'(0)). To account for this behavior, we developed an innovative physical treatment which consists in a non-linear fit of the solvatochromic data using the Bilot-Kawski theoretical model and visualizing the least-square coefficient χ(2) on a 2D map as a function of the solute polarizability and gas phase absorption energy. In parallel, Kamlet-Taft correlations were undertaken to select a propitious set of electrostatic solvents usable in this treatment. Protic solvents that lead to specific interactions and nonpolar solvents that favor dimerization processes were excluded. From a choice of aprotic solvents with sufficiently high polarity, 4 dipole moments μ(g)(S(0)) = +9.1 D, μ(e)(S(2)) = -1.5 D, μ(e)(S(1)) = 0 D and μ(g)(S'(0)) = +3.31 D were determined, the 3 former values being in close agreement with TDDFT values, although the solute polarizability values seem underestimated. Anyhow, disregarding this discrepancy, we evaluated the static hyperpolarizability to β(0) = -64 × 10(-30) esu from the solvatochromic data in close agreement with DFT calculations. 相似文献
89.
Capillary electrophoresis for rapid identification of monoclonal antibodies for routine application in hospital 下载免费PDF全文
Emmanuel Jaccoulet Claire Smadja Patrice Prognon Myriam Taverna 《Electrophoresis》2015,36(17):2050-2056
mAbs are widely used in cancer therapy. Their compounding, performed just before their administration to patients, is executed in a production unit of the hospital. Identification of these drugs, individually prepared in bags for infusion before patient administration, is of paramount importance to detect potential mistakes during compounding stage. A fast and reliable analytical method based on CZE combined to a cationic capillary coating (hexadimethrine bromide) was developed for identification of the most widely used compounded therapeutic for cancer therapy (bevacizumab, cetuximab, rituximab, and trastuzumab). Considering the high structural and physico‐chemical similarities of these mAbs, an extensive optimization of the BGE composition has been performed. The addition of perchlorate ions and polysorbate in the BGE greatly increased the resolution. To validate the method, an internal standard was used and the relative migration times (RTm) were estimated. Very satisfactory RSDs of the RTm for rituximab (0.76%), cetuximab (0.46%), bevacizumab (0.31%), and trastuzumab (0.60%) were obtained. The intraday and interday RSD of the method were less than 0.32 and 1.3%, respectively for RTm. Significant differences between theses RTms have been demonstrated allowing mAbs identification. Finally, accurate mAbs identification has been demonstrated by a blind test. 相似文献
90.
Elizabeth Renaud Christian Robelin Aïmen E. Gheribi Patrice Chartrand 《The Journal of chemical thermodynamics》2011,43(8):1286-1298
A complete critical evaluation of all available phase diagram and thermodynamic data has been performed for all condensed phases of the (LiF + LiCl + NaF + NaCl + KF + KCl + MgF2 + MgCl2 + CaF2 + CaCl2 + SrF2 + SrCl2) system, and optimized model parameters have been found. The (LiCl + NaCl + KCl + MgCl2 + CaCl2 + SrCl2), (LiF + NaF + KF + MgF2 + CaF2 + SrF2), and (LiF + LiCl + NaF + NaCl + KF + KCl + MgF2 + MgCl2 + CaF2 + CaCl2) subsystems have been critically evaluated previously. The model parameters for the common-ion binary, common-anion ternary, and reciprocal ternary subsystems (i.e. systems with two cations and two anions) can be used to predict thermodynamic properties and phase equilibria for the multicomponent reciprocal system. The Modified Quasichemical Model in the Quadruplet Approximation was used for the molten salt phase. This model takes into account both first-nearest-neighbor (cation–anion) and second-nearest-neighbor (cation–cation and anion–anion) short-range ordering, and the coupling between them. Finally, the CaFCl–SrFCl solid solution was modeled using the Compound Energy Formalism. 相似文献