全文获取类型
收费全文 | 433篇 |
免费 | 39篇 |
国内免费 | 8篇 |
专业分类
化学 | 305篇 |
晶体学 | 6篇 |
力学 | 13篇 |
数学 | 32篇 |
物理学 | 124篇 |
出版年
2023年 | 2篇 |
2021年 | 5篇 |
2020年 | 6篇 |
2019年 | 9篇 |
2018年 | 6篇 |
2017年 | 10篇 |
2016年 | 13篇 |
2015年 | 19篇 |
2014年 | 20篇 |
2013年 | 30篇 |
2012年 | 30篇 |
2011年 | 42篇 |
2010年 | 20篇 |
2009年 | 19篇 |
2008年 | 26篇 |
2007年 | 25篇 |
2006年 | 17篇 |
2005年 | 14篇 |
2004年 | 17篇 |
2003年 | 18篇 |
2002年 | 21篇 |
2001年 | 11篇 |
2000年 | 18篇 |
1999年 | 10篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 7篇 |
1995年 | 3篇 |
1994年 | 2篇 |
1993年 | 4篇 |
1992年 | 3篇 |
1991年 | 5篇 |
1989年 | 4篇 |
1986年 | 3篇 |
1983年 | 2篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1972年 | 3篇 |
1970年 | 4篇 |
1968年 | 2篇 |
1967年 | 1篇 |
1966年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有480条查询结果,搜索用时 15 毫秒
111.
Joël Brugger Allan Pring Frank Reith Chris Ryan Barbara Etschmann Weihua Liu Brian O’Neill Yung Ngothai 《Radiation Physics and Chemistry》2010,79(2):151-161
The understanding of the physico-chemical processes leading to the formation and weathering of ore deposits plays an increasingly important role in mineral exploration. Synchrotron, neutron, and nuclear radiation are contributing to this endeavour in many ways, including (i) support the modelling of ore transport and deposition, by providing molecular-level understanding of solvent–solute interaction and thermodynamic properties for the important metal complexes in brines, vapours, and supercritical fluids over the range of conditions relevant for the formation of ore deposits (i.e., temperature 25–600 °C; pressure 1–109 Pa; and fluid compositions varying from hypersaline (e.g., >50 wt% NaCl) to volatile-rich (e.g., CO2, CH4, and H2S)); (ii) track the fluids that travelled through rocks and predict their ore-forming potential by analysing hydrothermal minerals and remnants of those fluids trapped in these minerals as ‘fluid inclusions’; (iii) characterize the biochemical controls on metal mobility in soils to predict the geochemical footprint of a buried mineral deposit.X-ray fluorescence (XRF), particle-induced X-ray emission (PIXE), and X-ray absorption spectroscopy (XAS) are the most common techniques used in support of mineral exploration. Analytical challenges are related to (i) the complexity of heterogeneous natural samples, which often contain only low concentrations of the elements of interest; (ii) beam sensitivity, especially for redox-sensitive elements in aqueous fluids or biological samples; (iii) extreme sample environments, e.g., in-situ study of fluids at high pressure and temperature. Thus, critical improvements need to be made on a number of fronts to: (i) develop more efficient detectors, able to map large areas in heterogeneous samples (e.g., 106–108 pixels per map), and also to collect a maximum number of photons to limit sample exposure and beam damage; (ii) integrate techniques (e.g., XRF, XAS, and X-ray diffraction (XRD)) on a single beamline, and promote synergy between neutron-, synchrotron-, and nuclear microprobe-based methods; (iii) advance the theory (e.g., quantitative XANES interpretation; X-ray extended range technique (XERT) measurements) to gain maximum information from the hard-won datasets. 相似文献
112.
Surface grafted sulfobetaine polymers via atom transfer radical polymerization as superlow fouling coatings 总被引:2,自引:0,他引:2
One of the sulfobetaine methacrylate (SBMA) monomers, N-(3-sulfopropyl)-N-(methacryloxyethyl)-N,N-dimethylammonium betaine, was polymerized onto initiator-covered gold surfaces using atom transfer radical polymerization (ATRP) to form uniform polymer brushes. Self-assembled monolayers (SAMs) with ATRP initiators were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The thickness of grafted poly(SBMA) films was measured by ellipsometry. Fibrinogen adsorption on poly(SBMA) grafted surfaces was measured with a surface plasmon resonance (SPR) sensor. Two approaches were compared to graft ATRP initiators onto gold surfaces for surface polymerization and subsequent protein adsorption on these polymer grafted surfaces. The first was to prepare a SAM from omega-mercaptoundecyl bromoisobutyrate onto a gold surface. Superlow fouling surfaces with well-controlled poly(SBMA) brushes were achieved using this approach (e.g., fibrinogen adsorption <0.3 ng/cm2). The second approach was to react bromoisobutyryl bromide with a hydroxyl-terminated SAM on a gold surface. Although protein adsorption decreased as the density of surface initiators increased, the surface prepared using the second approach was not able to achieve as low protein adsorption as the first approach. Key parameters to achieve superlow fouling surfaces were studied and discussed. 相似文献
113.
Treatment of arylglyoxal monohydrates with tetrasulfur tetranitride in p-dioxane at reflux afforded 2-aroyl-5-arylimidizoles and 2-aroyl-5-aryloxazoles in 10 to 31% and 17 to 32% yields, respectively. With non-hydrate of arylglyoxals, yields of the latter increase somewhat, whereas essentially no changes in yields of the former were observed. A mechanism is proposed for the formation of the products. 相似文献
114.
R. S. Chen K. F. Tsang Edward K. N. Yung 《International Journal of Infrared and Millimeter Waves》2000,21(8):1281-1301
In this paper, symmetric successive overrelaxation (SSOR) preconditioned CG technique are introduced into method of lines (MOL) to further enhance the computational efficiency of this semi-analytic method. Millimeter wave scattering by an infinite plane metallic grating is used as the examples to describe its implementation, whose analysis usually needs fast algorithms because of electrically large dimension. For arbitrary incident wave, Helmholz equation and boundary condition are used to calculate the impedance matrix and then to obtain reduced current-voltage linear matrix equation in spatial domain. An effective symmetric successive overrelaxation preconditioned conjugate gradient iterative method, SSOR-PCG, is chosen to solve this matrix equation. With SSOR as the preconditioner as well as its efficient implementing in CG algorithm, PCG method can converge to accurate solution in much fewer iteration steps. 相似文献
115.
The total synthesis of (±)-methyl 3-(3-isocyano-6-oxabilcyclo[3.1.0]hex-2-en-5-yl)-2-propenoate has been achieved using 3-tosyl-2-azabicyclo[2.2.1]hepta-2,5-diene as a key starting material. 相似文献
116.
Erik M. Holmgreen Matthew M. Yung Umit S. Ozkan 《Journal of molecular catalysis. A, Chemical》2007,270(1-2):101-111
Pd-based sulfated zirconia catalysts have been prepared through a single step (one-pot) sol–gel preparation technique, in which both sulfate and Pd precursors were dissolved in an organic solution before the gelation step. Observation of the calcination procedure through TGA/DSC and mass spectrometry revealed that the addition of increasing amounts of Pd resulted in the evolution of organic precursor species at lower temperatures. In situ XRD experiments showed that tetragonal zirconia is formed at lower temperatures and larger zirconia crystallites are formed when Pd is added to the gel. Although tetragonal zirconia was the only phase observed through XRD, Raman spectra of samples calcined at 700 °C showed the presence of both the tetragonal and the monoclinic phase, indicating a surface phase transition. DRIFTS experiments showed NO species adsorbed on Pd2+ cations. Pd/SZ catalysts prepared through this single step method were active for the reduction of NO2 with CH4 under lean conditions. Calcination temperature had a significant effect on this activity, with samples calcined at 700 °C being much more active than those calcined at 600 °C, despite the observed transition to the monoclinic phase. This activity may be linked to observed changes in the surface sulfate species at higher calcination temperatures. 相似文献
117.
Yung P. Koh Gregory B. McKenna Sindee L. Simon 《Journal of polymer science. Part A, Polymer chemistry》2006,44(24):3518-3527
The absolute heat capacity and glass transition temperature (Tg) of unsupported ultrathin films were measured with differential scanning calorimetry with the step-scan method in an effort to further examine the thermodynamic behavior of glass-forming materials on the nanoscale. Films were stacked in layers with multiple preparation methods. The absolute heat capacity in both the glass and liquid states decreased with decreasing film thickness, and Tg also decreased with decreasing film thickness. The magnitude of the Tg depression was closer to that observed for films supported on rigid substrates than that observed for freely standing films. The stacked thin films regained bulk behavior after the application of pressure at a high temperature. The effects of various preparation methods were examined, including the use of polyisobutylene as an interleaving layer between the polystyrene films. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3518–3527, 2006 相似文献
118.
A mechanistic study of the stoichiometric and catalytic H/D exchange reactions involving cationic iridium complexes is presented. Strong evidence suggests that both stoichiometric and catalytic reactions proceed via a monohydrido-iridium species. Stoichiometric deuterium incorporation reactions introduce multiple deuterium atoms into the organic products when aryliridium compounds CpPMe(3)Ir(C(6)H(4)X)(OTf) (X = H, o-CH(3), m-CH(3), p-CH(3)) react with D(2). Multiple deuteration occurs at the unhindered positions (para and meta) of toluene, when X = CH(3). The multiple-deuteration pathway is suppressed in the presence of an excess of the coordinating ligand, CH(3)CN. The compound CpPMe(3)IrH(OTf) (1-OTf) is observed in low-temperature, stoichiometric experiments to support a monohydrido-iridium intermediate that is responsible for catalyzing multiple deuteration in the stoichiometric system. When paired with acetone-d(6)(), [CpPMe(3)IrH(3)][OTf] (4) catalytically deuterates a wide range of substrates with a variety of functional groups. Catalyst 4 decomposes to [CpPMe(3)Ir(eta(3)-CH(2)C(OH)CH(2))][OTf] (19) in acetone and to [CpPMe(3)IrH(CO)][OTf] (1-CO) in CH(3)OH. The catalytic H/D exchange reaction is not catalyzed by simple H(+) transfer, but instead proceeds by a reversible C-H bond activation mechanism. 相似文献
119.
120.
This article provides a survey of results on the exact bandwidth, edgesum, and profile of graphs. A bibliography of work in these areas is provided. The emphasis is on composite graphs. This may be regarded as an update of the original survey of solved bandwidth problems by Chinn, Chvátalová, Dewdney, and Gibbs [10] in 1982. Also several of the application areas involving these graph parameters are described. © John & Sons, Inc. Graph Theory 31: 75–94, 1999 相似文献