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41.
Stijn F. L. Mertens Matthew Gara Alla S. Sologubenko Joachim Mayer Sönke Szidat Karl W. Krämer Timo Jacob David J. Schiffrin Thomas Wandlowski 《Advanced functional materials》2011,21(17):3259-3267
Dynamic core–shell nanoparticles have received increasing attention in recent years. This paper presents a detailed study of Au–Hg nanoalloys, whose composing elements show a large difference in cohesive energy. A simple method to prepare Au@Hg particles with precise control over the composition up to 15 atom% mercury is introduced, based on reacting a citrate stabilized gold sol with elemental mercury. Transmission electron microscopy shows an increase of particle size with increasing mercury content and, together with X‐ray powder diffraction, points towards the presence of a core–shell structure with a gold core surrounded by an Au–Hg solid solution layer. The amalgamation process is described by pseudo‐zero‐order reaction kinetics, which indicates slow dissolution of mercury in water as the rate determining step, followed by fast scavenging by nanoparticles in solution. Once adsorbed at the surface, slow diffusion of Hg into the particle lattice occurs, to a depth of ca. 3 nm, independent of Hg concentration. Discrete dipole approximation calculations relate the UV–vis spectra to the microscopic details of the nanoalloy structure. Segregation energies and metal distribution in the nanoalloys were modeled by density functional theory calculations. The results indicate slow metal interdiffusion at the nanoscale, which has important implications for synthetic methods aimed at core–shell particles. 相似文献
42.
Dr. Véronique Jubera Dr. Marie Chavoutier Dr. Alla Artemenko Dr. Philippe Veber Dr. Matias Velazquez Dr. Alain Garcia 《Chemphyschem》2011,12(7):1288-1293
Synthesized powders and grown single crystals of nominal compositions Li6Ln(BO3)3:Yb3+ (Ln=Y, Gd) were investigated by means of powder and single‐crystal X‐ray diffraction (XRD), as well as optical near‐IR spectroscopy in conjunction with electron paramagnetic resonance (EPR) spectroscopy. The appearance of two distinct zero‐phonon lines suggests the existence of two kinds of Yb3+ ions in the single crystals. The XRD results exclude the possibility of a phase transition occurring between room and low temperatures. EPR spectra of single crystals show the presence of both isolated ions and pairs of ytterbium ions substituted for Y3+. A strong temperature dependence of the intensity of Yb–Yb pairs resonance lines coincides with temperature dependence of emission peak at 978 nm, confirming a common origin of the defect giving rise to these spectra. Calculated from EPR spectra, the distance between pairs of Yb3+ is in good agreement with crystallographic ones: R=3.856 Å, Rcryst=3.849 Å. 相似文献
43.
44.
Francisca Zamora Khalid Hakkou Abdelilah Alla Manuel Rivas Isaac Roff Manuel Mancera Sebastin Muoz‐Guerra Juan A. Galbis 《Journal of polymer science. Part A, Polymer chemistry》2005,43(19):4570-4577
The synthesis and characterization of a new series of aromatic polyesters based on D‐mannitol and galactitol are described. These polyesters were obtained by polycondensation reaction of the terephthaloyl chloride or isophthaloyl chloride and 2,3,4,5‐tetra‐O‐methyl‐D‐mannitol or 2,3,4,5‐tetra‐O‐methyl‐galactitol in o‐dichlorobenzene. All the new polyesters were characterized by elemental analyses, GPC, IR, and NMR. They were soluble in chloroform, but insoluble in water and other polar oxygenated solvents. They showed a notable hygroscopicity, lower for those containing isophthalic units. DSC and X‐ray diffraction studies showed that D‐mannitol‐based polyesters were stiffer and less crystalline than those derived from galactitol, which presented a noticeably lower thermal stability. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4570–4577, 2005 相似文献
45.
Darwin P. R. Kint Antxon Martínez de Ilarduya Abdelilah Alla Sebastin Muoz‐Guerra 《Journal of polymer science. Part A, Polymer chemistry》2003,41(1):124-134
Poly(ethylene terephthalate‐co‐isophthalate‐co‐5‐tert‐butylisophthalate) (PETItBI) terpolymers were investigated with reference to poly(ethylene terephthalate) (PET) homopolymer and poly(ethylene terephthalate‐co‐isophthalate) (PETI) copolymers. Three series of PETItBI terpolyesters, characterized by terephthalate contents of 90, 80, and 60 mol %, respectively, with different isophthalate/5‐tert‐butylisophthalate molar ratios, were prepared from ethylene glycol and mixtures of dimethyl terephthalate, dimethyl isophthalate, and 5‐tert‐butylisophthalic acid. The composition of the terpolymers and the composition of the feed agreed. All terpolymers had a random microstructure and number‐average molecular weights ranging from 10,000 to 20,000. The PETItBI terpolyesters displayed a higher glass‐transition temperature and a lower melting temperature than the PETI copolymers having the same content of terephthalic units. Thermal stability appeared essentially unchanged upon the incorporation of the 5‐tert‐butylisophthalic units. The PETItBIs were crystalline for terephthalate contents higher than 80 mol %, and they crystallized at lower rates than PETI. The crystal structure of the crystalline terpolymers was the same as that of PET with the 1,3‐phenylene units being excluded from the crystalline phase. Incorporation of isophthalate comonomers barely affected the tensile modulus and strength of PET, but the brittleness of the terpolymers decreased for higher contents in 5‐tert‐butylisophthalic units. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 124–134, 2003 相似文献
46.
Francisca Zamora Khalid Hakkou Abdelilah Alla Jos L. Espartero Sebastin Muoz‐Guerra Juan A. Galbis 《Journal of polymer science. Part A, Polymer chemistry》2005,43(24):6394-6410
The synthesis and characterization of new aromatic homo‐ and copolyesters based on l‐arabinitol and xylitol are described. These polymers were obtained by polycondensation reaction of the 2,3,4‐tri‐O‐methyl‐l‐arabinitol or 2,3,4‐tri‐O‐methyl‐xylitol, or their mixtures with ethylene glycol, with terephthaloyl chloride or isophthaloyl chloride in o‐dichlorobenzene or in the melt phase from the corresponding methyl phthalates. All the polymers were characterized by GPC, IR, and NMR. Their Mw values ranged between 11,500 and 46,500, with polydispersities from 1.5 to 2.3. They were found to be soluble in chloroform, but insoluble in water. In contrast with the homopolymers completely made with EG, they showed a significant hygroscopicity. DSC and TGA studies showed that the melting temperature of polyethylene terephthalate is depressed by the presence of pentitol units, whereas the thermal stability is kept above 350 °C. Only copolyesters containing 10% or less of pentitol units showed melting and produced X‐ray diffraction patterns characteristic of crystalline material. d‐Arabinitol‐based homopolyesters appeared to be more crystalline than those derived from xylitol and also presented a higher thermal stability. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6394–6410, 2005 相似文献
47.
Alla Zablotskaya Izolda Segal Yuris Popelis Edmunds Lukevics Shipra Baluja Irina Shestakova Ilona Domracheva 《应用有机金属化学》2006,20(11):721-728
A series of triorganylsilyl(β‐dialkylaminoethoxy)silanes was prepared and characterized by elemental analysis, 1H, 13C, 29Si NMR and mass spectroscopy. Comparative study of 29Si resonance of newly synthesized compounds showed correlation between its value and substituent nature at the silicon atom, and is shifted upfield for β‐triorganyl(N,N‐dialkylaminoethoxy)silanes in comparison with corresponding methiodides, revealing weak N…Si interaction for proper silanes. In vitro antitumour and antimicrobial properties were investigated. The biological activity data exhibited a marked enhancement of inhibitory activity on trialkylsilylation against tumour cell lines and all the test bacterial/fungal strains. Copyright © 2006 John Wiley & Sons, Ltd. 相似文献
48.
Finite-size scaling of the order parameter O in the disordered phase is presented for percolation in 2d and 3d and compared to the behavior of the magnetization of the Ising model. We find that the order parameter O grows logarithmically with the system size L for p < pc and thus the analogy with the Ising model is not complete. Furthermore we find evidence for scaling behavior of the type O ~ L?y/v (pc ? p)β?y where the exponent y is not dv/2 as in the Is ing case. 相似文献
49.
I.V. Chikina N. Limodin A. Langlois M. Brazovskaia C. Even P. Pieranski 《The European Physical Journal B - Condensed Matter and Complex Systems》1998,3(2):189-196
We investigate monolayers of 2-alcohols (2-C9 to 2-C16) obtained by placing a drop of pure alcohol at the water surface. These
alcohols are chiral molecules and we study the racemic mixtures. By ellipsometry and surface tension measurements we are able
to characterize the 2D crystallization-melting transition with temperature. We find a first order transition. Using X-ray
under grazing incidence we show that the racemic mixture crystallizes at 2D on a hexagonal cell. We find a parity effect on
the lateral pressure at the transition and on the stability of the Bragg peak. We compare all results with those observed
for 1-alcohols.
Received: 11 April 1997 / Revised: 18 August 1997 / Accepted: 9 October 1997 相似文献
50.