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31.
Guido F. Smits Maarten C. Krol Pieter N. Van Kampen Cornelis Altona 《Journal of Molecular Structure》1986,139(3-4):247-253
Contrary to expectation, the gauche conformer of 1,2-difluoroethane is more stable than the trans conformer in the gas phase. In order to understand the underlying causes of the “gauche effect”, a complete geometry relaxation was performed for the gauche and trans conformers of 1,2-difluoroethane with the 4-21G, 4-31G and 4-31G** basis sets. The 4-31G** optimized geometry of the gauche conformer compares well with the experimental values obtained from a number of electron-diffraction studies. A correction for the correlation energy, calculated by means of second-order Møller—Plesset perturbation theory with the 6-31G** basis set, proves to be essential to obtain a correct estimate of the energy difference between the gauche and trans conformers 1,2-difluoroethane. 相似文献
32.
Maarten H. van der Vlerk 《Mathematical Methods of Operations Research》2005,62(2):225-242
We consider multiple simple recourse (MSR) models, both continuous and integer versions, which generalize the corresponding
simple recourse (SR) models by allowing for a refined penalty cost structure for individual shortages and surpluses. It will
be shown that (convex approximations of) such MSR models can be represented as explicitly specified continuous SR models,
and thus can be solved efficiently by existing algorithms.
This research has been made possible by a fellowship of the Royal Netherlands Academy of Arts and Sciences. 相似文献
33.
34.
Patrick J. M. Stals Jeffrey C. Everts Robin de Bruijn Ivo A. W. Filot Maarten M. J. Smulders Rafael Martín‐Rapún Dr. Evgeny A. Pidko Dr. Tom F. A. de Greef Dr. Anja R. A. Palmans Dr. E. W. Meijer Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(3):810-821
N‐Centred benzene‐1,3,5‐tricarboxamides (N‐BTAs) composed of chiral and achiral alkyl substituents were synthesised and their solid‐state behaviour and self‐assembly in dilute alkane solutions were investigated. A combination of differential scanning calorimetry (DSC), polarisation optical microscopy (POM) and X‐ray diffraction revealed that the chiral N‐BTA derivatives with branched 3,7‐dimethyloctanoyl chains were liquid crystalline and the mesophase was assigned as Colho. In contrast, N‐BTA derivatives with linear tetradecanoyl or octanoyl chains lacked a mesophase and were obtained as crystalline compounds. Variable‐temperature infrared spectroscopy showed the presence of threefold, intermolecular hydrogen bonding between neighbouring molecules in the mesophase of the chiral N‐BTAs. In the crystalline state at room temperature a more complicated packing between the molecules was observed. Ultraviolet and circular dichroism spectroscopy on dilute solutions of N‐BTAs revealed a cooperative self‐assembly behaviour of the N‐BTA molecules into supramolecular polymers with preferred helicity when chiral alkyl chains were present. Both the sergeants‐and‐soldiers as well as the majority‐rules principles were operative in stacks of N‐BTAs. In fact, the self‐assembly of N‐BTAs resembles closely that of their carbonyl (C?O)‐centred counterparts, with the exception that aggregation is weaker and amplification of chirality is less pronounced. The differences in the self‐assembly of N‐ and C?O‐BTAs were analysed by density functional theory (DFT) calculations. These reveal a substantially lower interaction energy between the monomeric units in the supramolecular polymers of N‐BTAs. The lower interaction energy is due to the higher energy penalty for rotation around the Ph? NH bond compared to the Ph? CO bond and the diminished magnitude of dipole–dipole interactions. Finally, we observed that mixed stacks are formed in dilute solution when mixing N‐BTAs and C?O BTAs. 相似文献
35.
Marco L. Hennrich Shabaz Mohammed A. F. Maarten Altelaar Albert J. R. Heck 《Journal of the American Society for Mass Spectrometry》2010,21(12):1957-1965
Here, we explore a de novo sequencing strategy in which we combine Lys-N protein digestion with differential isotopic dimethyl
labeling to facilitate the (de novo) identification of multiply charged peptides in ESI-MS, both under CID and ETD conditions.
For a large fraction of the Lys-N generated peptides, all primary amines are present at the N-terminal lysine, enabling specific
labeling of the N-terminus. Differential derivatization of only the peptide N-terminus in combination with the simultaneous
fragmentation of the corresponding isotopologues allows the straightforward distinction of N-terminal fragments from C-terminal
and internal fragments. Furthermore, also singly and multiply charged N-terminal fragments can easily be distinguished due
to the mass differences of the isotope labeled fragment pairs. As a proof of concept, we applied this approach to proteins
isolated from an avocado fruit, and were able to partially de novo sequence and correctly align, with green plant homologues,
a previously uncharacterized avocado ascorbate peroxidase. 相似文献
36.
Gerard A. van Albada Maarten G. van der Horst Simon J. Teat Patrick Gamez Olivier Roubeau Ilpo Mutikainen Urho Turpeinen Jan Reedijk 《Polyhedron》2009
In this study the synthesis, crystal structure and characterization of three new transition metal polynuclear compounds with formula [Cu(dipm)(μ-dca)2]n(H2O) (1), [Ni(dipm)(μ-dca)2]n(C2H6O)1/2 (2) and [Cd(dipm)(μ-dca)2]n (3) (in which dipm = bis(pyrimidin-2-yl)amine and dca = dicyanamide) are reported. The isostructural compounds 1 and 2 contain a double-bridging end-to-end dca unit connecting two metal ions and a single bridging end-to-end dca unit between subsequent metals. Compound 3 exhibits only single bridging end-to-end dca units, oriented in three directions, giving rise to a 3D framework. 相似文献
37.
Alem N Yazyev OV Kisielowski C Denes P Dahmen U Hartel P Haider M Bischoff M Jiang B Louie SG Zettl A 《Physical review letters》2011,106(12):126102
Crystalline systems often lower their energy by atom displacements from regular high-symmetry lattice sites. We demonstrate that such symmetry lowering distortions can be visualized by ultrahigh resolution transmission electron microscopy even at single point defects. Experimental investigation of structural distortions at the monovacancy defects in suspended bilayers of hexagonal boron nitride (h-BN) accompanied by first-principles calculations reveals a characteristic charge-induced pm symmetry configuration of boron vacancies. This symmetry breaking is caused by interlayer bond reconstruction across the bilayer h-BN at the negatively charged boron vacancy defects and results in local membrane bending at the defect site. This study confirms that boron vacancies are dominantly present in the h-BN membrane. 相似文献
38.
Akin to the mathematical recreations, John Wilkins' Mathematicall Magick ( 1648) elaborates the pleasant, useful and wondrous part of practical mathematics, dealing in particular with its material culture of machines and instruments. We contextualize the Mathematicall Magick by studying its institutional setting and its place within changing conceptions of art, nature, religion and mathematics. We devote special attention to the way Wilkins inscribes mechanical innovations within a discourse of wonder. Instead of treating ‘wonder’ as a monolithic category, we present a typology, showing that wonders were not only recreative, but were meant to inspire Wilkins' readers to new mathematical inventions. 相似文献
39.
Imprecision of input data is one of the main obstacles that prevent geometric algorithms from being used in practice. We model an imprecise point by a region in which the point must lie. Given a set of imprecise points, we study computing the largest and smallest possible values of various basic geometric measures on point sets, such as the diameter, width, closest pair, smallest enclosing circle, and smallest enclosing bounding box. We give efficient algorithms for most of these problems, and identify the hardness of others. 相似文献
40.