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671.
Ljubica Svilar Vesna Stankov‐Jovanovic Denis Lesage Héloïse Dossmann Jean‐Claude Tabet 《Journal of mass spectrometry : JMS》2012,47(8):969-977
Azaphilones represent numerous groups of wild fungal secondary metabolites that exhibit exceptional tendency to bind to nitrogen atoms in various molecules, especially those containing the amine group. Nitrogenized analogues of mitorubrin azaphilones, natural secondary metabolites of Hypoxylon fragiforme fungus, have been detected in the fungal methanol extract in very low concentrations. Positive electrospray ionization interfaced with high‐resolution mass spectrometry was applied for confirmation of the elemental composition of protonated species. Collision‐induced dissociation (CID) experiments have been performed, and fragmentation mechanisms have been proposed. Additional information regarding both secondary metabolite analogue families has been reached by application of gas‐phase proton/deuterium (H/D) exchanges performed in the collision cell of a triple quadrupole mass spectrometer. An incomplete H/D exchange with one proton less than expected was observed for both protonated mitorubrin azaphilones and their nitrogenized analogues. By means of the density functional theory, an appropriate explanation of this behavior was provided, and it revealed some information concerning gas‐phase H/D exchange mechanism and protonation sites. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
672.
Pablo Martínez-Lozano Sinues Rosa M. Alonso-Salces Lorenzo Zingaro Alessandro Finiguerra Margaret V. Holland Claude Guillou Simone Cristoni 《Analytica chimica acta》2012
A new analytical strategy based on mass spectrometry fingerprinting combined with the NIST-MS search program for pattern recognition is evaluated and validated. A case study dealing with the tracing of the geographical origin of virgin olive oils (VOOs) proves the capabilities of mass spectrometry fingerprinting coupled with NIST-MS search program for classification. The volatile profiles of 220 VOOs from Liguria and other Mediterranean regions were analysed by secondary electrospray ionization-mass spectrometry (SESI-MS). MS spectra of VOOs were classified according to their origin by the freeware NIST-MS search v 2.0. The NIST classification results were compared to well-known pattern recognition techniques, such as linear discriminant analysis (LDA), partial least-squares discriminant analysis (PLS-DA), k-nearest neighbours (kNN), and counter-propagation artificial neural networks (CP-ANN). The NIST-MS search program predicted correctly 96% of the Ligurian VOOs and 92% of the non-Ligurian ones of an external independent data set; outperforming the traditional chemometric techniques (prediction abilities in the external validation achieved by kNN were 88% and 84% for the Ligurian and non-Ligurian categories respectively). This proves that the NIST-MS search software is a useful classification tool. 相似文献
673.
《Analytical letters》2012,45(15):3049-3058
ABSTRACT Waxy (essentially amylose-free) maize starch was chemically modified to varying degrees by treatment with 3-chloro-2-hydroxypropyltrimethyl ammonium chloride (CHPTAC), and the degree of cationic modification was determined by a standard wet chemistry method. FT-Raman spectra of the modified starches were taken, and a characteristic Raman band ~761 cm?1 was found. This 761 cm?1 Raman band's intensity depended on the level of cationic modification of the starch. The ratio of intensity of the ~761 cm?1 band to a ~715 cm?1 C-C stretch Raman band (used as an internal standard) was plotted versus the amount of cationic modification derived by titration analysis, and a linear fit was obtained with a correlation of 0.998. The FT-Raman spectroscopy method presented here demonstrates a rapid non-destructive way to determine the level of cationic modification of waxy maize starch, and should be suitable for use with cationic modified starches of any amylose content. 相似文献
674.
《Analytical letters》2012,45(7):1401-1410
Abstract A Fourier transform infrared (FT‐IR) spectrometric method was developed for the rapid, direct measurement of chromium (tris) picolinate [Cr(pic)3] in different pharmaceutical products. Conventional KBr potassium bromine spectra were compared for best determination of active substance in drug preparations. Lambert‐Beer's law and two chemometric approaches, partial least squares (PLS) and principal component regression (PCR+) methods, were used in data processing. 相似文献
675.
Joanna Hetmaczyk ukasz Hetmaczyk Anna Migda‐Mikuli Edward Mikuli Aleksandra Weseucha‐Birczyska 《Journal of Raman spectroscopy : JRS》2012,43(8):1118-1125
[Ba(H2O)3](ClO4)2 between 90 and 300 K possesses two solid phases. One phase transition of the first‐order type at: = 211.3 K (on heating) and = 204.6 K (on cooling) was determined by differential scanning calorimetry. The entropy change value (ΔS ≈ 15 Jmol–1 K–1), associated with the observed phase transition, indicates a moderate degree of molecular dynamical disorder. Both, vibrational and reorientational motions of H2O ligands and ClO4– anions, in the high‐temperature and low‐temperature phases, were investigated by Fourier transform far‐infrared and middle‐infrared and Raman light scattering spectroscopies. The temperature dependences of the full‐width at half‐maximum values of the bands associated with ρw(H2O) mode, in both infrared (~570 cm–1) and Raman light scattering (~535 cm–1) spectra, suggest that the observed phase transition is not associated with a sudden change of a speed of the H2O reorientational motions. Ligands reorient fast, with correlation time of the order of several picoseconds, with a mean activation energy value Ea = 5.1 kJ mol–1 in both high and low temperature phases. On the other hand, measurements of temperature dependences of full‐width at half‐maximum values of the infrared band at ~460 cm–1, associated with δd(OClO)E mode, and Raman band at ~1105 cm–1, associated with νas(ClO)F2 mode, revealed the existence of a fast ClO4– reorientation in phase I and in phase II, with the Ea(I) and Ea(II) values equal to 8.0 and 6.5 kJ mol–1, respectively. These reorientational motions of ClO4– are slightly distorted at the TC. Fourier transform far‐infrared and middle‐infrared spectra with decreasing of temperature indicated characteristic changes at the vicinity of PT at TC, which suggested lowering of the crystal structure symmetry. All these experimental facts suggest that the discovered phase transition is associated with small change of H2O ligands and somewhat major change of ClO4– anions reorientational dynamics, and with insignificant change of the crystal structure, too. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
676.
Pure and impurity (strontium) added calcium tartrate tetrahydrate single crystals were grown by the gel method. The FT‐IR spectra of these crystals were recorded in the wavenumber range 400–4000 cm–1. The thermograms of the grown crystals were recorded in the temperature range 50–900 °C. FT‐IR spectra reveals the presence of water molecules, O‐H bond, C‐O and carbonyl C=O bonds. The thermograms show that these crystals are thermally unstable and decompose into its oxide through many stages. DTA curve of the pure crystal shows three endothermic and one exothermic peaks. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
677.
THE TWO-PHOTON DEGENERATE JAYNES-CUMMINGS MODEL WITH AND WITHOUT ROTATING-WAVE APPROXIMATION 下载免费PDF全文
We take into account the two-photon process and generalize the Jaynes-Cummings (JC) model to the case of atomic level degenerate in the projections of the angular momenta, and we establish two-photon degenerate JC models with and without the rotating-wave approximation (RWA) quantum theory. Comparing the atom population inversion of the generalized JC model with that of the original JC model, we found that the revival period of the degenerate JC model becomes longer and the maximum amplitude of atomic inversion decreases with RWA. Without RWA, the quantum chaos of the generalized JC model is much weaker than that of the original JC model. 相似文献
678.
The direct method developed by Clarkson and Kruskal (1989 J. Math. Phys. 30 2201) for finding the symmetry reductions of a nonlinear system is extended to find the conditional similarity solutions. Using the method of the Jimbo-Miwa (JM) equation, we find that three well-known (2+1)-dimensional models-the asymmetric Nizhnik--Novikov-Veselov equation, the breaking soliton equation and the Kadomtsev-Petviashvili equation-can all be obtained as the conditional similarity reductions of the JM equation. 相似文献
679.
680.
Bound states of Klein-Gordon equation for ring-shaped harmonic oscillator scalar and vector potentials 下载免费PDF全文
Solving Klein-Gordon equation with equal ring-shaped harmonic oscillator scalar and vector potentials, we obtain the exact normalized bound-state wavefunction and energy equation. 相似文献