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41.
42.
Abderrahim A?t Adoubel Christophe J. Morin Nadine Mofaddel Georges Dupas Paul-Louis Desbène 《Analytical and bioanalytical chemistry》2009,394(2):597-608
Enantiomer separations of underivatised amino acids were carried out by using ligand exchange capillary electrophoresis (LECE).
Chiral discrimination is based on the formation of ternary complexes between copper(II), a chiral selector (L-proline or trans-4-hydroxy-L-proline) and an amino acid. All amino acids containing aromatic moieties or not were detected at 214 nm because
of their interactions with copper(II). In order to reduce copper(II) adsorption onto capillary walls, we used hexadimethrine
bromide to reverse the electroosmotic flow. Using this original strategy, the studied enantiomers migrated in the opposite
direction of the anodic electroosmosis. After optimising the analytical conditions taking into account the chiral resolution
and the detection sensitivity, we performed very satisfactory enantioseparations not only of aromatic amino acids (tryptophan,
tyrosine, phenylalanine and histidine) but also of aliphatic amino acids (threonine, serine, isoleucine and valine). These
enantioseparations were performed in a short analysis time at 35 °C. In order to rationalise the obtained results, we evaluated
the complexation constants corresponding to the formed ternary complexes by capillary electrophoresis and we used molecular
mechanics modelling. 相似文献
43.
Muhammad Nawaz Tahir Markus Messerschmidt Michael Klein Victor Martinez Patrick Theato Nadine Metz Sonngard Hartmann Ute Kolb Vadim Ksenofontov Franz Renz Wolfgang Tremel 《Polyhedron》2009,28(9-10):1728-1733
The precursor [FeIII(L)Cl (L = N,N′-bis(2′-hydroxy-3′-methyl-benzyliden)-1,7-diamino-4-azaheptane) is combined with [Mo(CN)8]4? yields a star shaped nona-nuclear cluster, [MoIV{(CN)FeIII(L)}8]Cl4. This Fe8Mo molecule is a high-spin system at room temperature. On cooling to 20 K some of the iron(III) centres in the molybdenum(IV)-star switch to the low-spin state as proven by Mössbauer spectroscopy. This molecule was deposited on TiO2 nanowires by electrostatic interactions between the cluster cations and the surface functionalized titanium oxide nanowire. The synthesis and surface binding of the multistable molecular switch was demonstrated using IR and UV–Vis spectroscopy (high-resolution) transmission electron microscopy ((HR)TEM) and Mössbauer spectroscopy. High- and low-temperature Mössbauer spectra indicate that the spin state transition of the free cluster molecules is preserved after surface binding. The above results emphasize the possibility of fabricating molecule-based low-dimensional structures by using traditional bottom-up approaches based on the electrostatic interaction between the cluster cations and polymer functionalized nanowires. These results can be generalized for the application to both charged and non-charged molecules. 相似文献
44.
Nadine Werth Mathias S. Müller Johann Meier Alexander W. Koch 《Optics Communications》2011,284(9):2317-2322
Using Laser-based Speckle-Interferometers, the shape of optically rough surfaces can be measured precisely and contactlessly from variable measuring distances even in regions of difficult access. This work is concerned with the integration of a micromirror array (MMA) into an electronic Speckle-Pattern-Interferometer. With the adaptive optics, it is intended to adapt the phasefront of a reference wave to critical surface areas of the measurement object. Yet, due to the topography of the MMA, diffraction effects occur which affect the phase and intensity of the generated wavefront. We demonstrate how these diffraction effects can be efficiently modelled by a Fraunhofer diffraction method. We compare the results of this model to theoretical data obtained by a numerical Fresnel diffraction model and to measurement data obtained from a measurement setup incorporating a multi mirror array. 相似文献
45.
Sheetal Saxena Alexander Summa Dominik Elsässer Michael Rüger Karl Mannheim 《The European Physical Journal C - Particles and Fields》2011,71(11):1815
As the largest mass concentrations in the local Universe, nearby clusters of galaxies and their central galaxies are prime
targets in searching for indirect signatures of dark matter annihilation (DMA). We seek to constrain the dark matter annihilation
emission component from multi-frequency observations of the central galaxy of the Virgo cluster. The annihilation emission
component is modeled by the prompt and inverse-Compton gamma rays from the hadronization of annihilation products from generic
weakly interacting dark matter particles. This component is fitted to the excess of the observed data above the spectral energy
distribution (SED) of the jet in M87, described with a best-fit synchrotron-self-Compton (SSC) spectrum. While this result
is not sufficiently significant to claim a detection, we emphasize that a dark matter “double hump signature” can be used
to unambiguously discriminate the dark matter emission component from the variable jet-related emission of M87 in future,
more extended observation campaigns. 相似文献
46.
In biomedical engineering, it is a common practice to replace injured cartilage by implants, which are seeded with human cartilage cells. Before implanting, the implants are cultivated and usually stimulated electrically or mechanically in a bioreactor to initiate cell multiplication and oriented cell growth. A new experimental set-up is developed leading to the possibility of stimulating such implants in a multi-dimensional, physiologically consistent way. In cooperation with the University Medical Centre Aachen, a human knee simulator is developed. Cell-seeded implants are placed in a recreated human environment and stimulated with several load cycles of reproduced walking. After the cultivation period, the implanted material is removed and biologically and mechanically evaluated. The quality of the implanted material as well as the influence of the body-conformable load on the material is studied. To understand the correlation between tissue remodelling and mechanical load history, the load and movement scenario is also numerically investigated. For this reason, the experiment is transferred to a geometrically realistic FE model of a human knee. As a first approach, an elastic material model is used. The aim is to have a predictive FE model with an optimal trade-off between accuracy and efficiency using an appropriate material formulation. The results will be compared to experimental data. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
47.
The purpose of this work is to describe an abstract theory of Hardy-Sobolev spaces on doubling Riemannian manifolds via an atomic decomposition. We study the real interpolation of these spaces with Sobolev spaces and finally give applications to Riesz inequalities. 相似文献
48.
Cristina Tortora Mireille Gettler Summa Marina Marino Francesco Palumbo 《Advances in Data Analysis and Classification》2016,10(4):441-464
Factor clustering methods have been developed in recent years thanks to improvements in computational power. These methods perform a linear transformation of data and a clustering of the transformed data, optimizing a common criterion. Probabilistic distance (PD)-clustering is an iterative, distribution free, probabilistic clustering method. Factor PD-clustering (FPDC) is based on PD-clustering and involves a linear transformation of the original variables into a reduced number of orthogonal ones using a common criterion with PD-clustering. This paper demonstrates that Tucker3 decomposition can be used to accomplish this transformation. Factor PD-clustering alternatingly exploits Tucker3 decomposition and PD-clustering on transformed data until convergence is achieved. This method can significantly improve the PD-clustering algorithm performance; large data sets can thus be partitioned into clusters with increasing stability and robustness of the results. Real and simulated data sets are used to compare FPDC with its main competitors, where it performs equally well when clusters are elliptically shaped but outperforms its competitors with non-Gaussian shaped clusters or noisy data. 相似文献
49.
Lourdes Infantes MaryF. Mahon Louise Male PaulR. Raithby SimonJ. Teat Jürgen Sauer Nadine Jagerovic Jos Elguero Sam Motherwell 《Helvetica chimica acta》2003,86(4):1205-1221
The structures of six new tetrazines have been determined and their molecular packing has been compared to the supermolecular architecture observed in related carboxylic acid dimers. In the tetrazines, covalent N? N bonds are considered to replace the intermolecular O? H???O hydrogen bonds of the carboxylic acids. In the systems investigated, it is apparent that, in the majority of cases, the covalent six‐membered ring of the tetrazine is an appropriate replacement for the carboxylic acid synthon. This apparent interplay between molecular and supramolecular units may have applications in the crystal engineering of new materials. 相似文献
50.
Coropceanu V Kwon O Wex B Kaafarani BR Gruhn NE Durivage JC Neckers DC Brédas JL 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(7):2073-2080
The nature of vibronic coupling in fused polycyclic benzene-thiophene structures has been studied using an approach that combines high-resolution gas-phase photoelectron spectroscopy measurements with first-principles quantum-mechanical calculations. The results indicate that in general the electron-vibrational coupling is stronger than the hole-vibrational coupling. In acenedithiophenes, the main contributions to the hole-vibrational coupling arise from medium- and high-frequency vibrations. In thienobisbenzothiophenes, however, the interaction of holes with low-frequency vibrations becomes significant and is larger than the corresponding electron-vibrational interaction. This finding is in striking contrast with the characteristic pattern in oligoacenes and acenedithiophenes in which the low-frequency vibrations contribute substantially only to the electron-vibrational coupling. The impact of isomerism has been studied as well. 相似文献