全文获取类型
收费全文 | 2511篇 |
免费 | 94篇 |
国内免费 | 5篇 |
专业分类
化学 | 2068篇 |
晶体学 | 14篇 |
力学 | 22篇 |
数学 | 264篇 |
物理学 | 242篇 |
出版年
2024年 | 2篇 |
2023年 | 21篇 |
2022年 | 73篇 |
2021年 | 80篇 |
2020年 | 60篇 |
2019年 | 54篇 |
2018年 | 28篇 |
2017年 | 30篇 |
2016年 | 81篇 |
2015年 | 87篇 |
2014年 | 91篇 |
2013年 | 150篇 |
2012年 | 174篇 |
2011年 | 200篇 |
2010年 | 117篇 |
2009年 | 111篇 |
2008年 | 194篇 |
2007年 | 200篇 |
2006年 | 158篇 |
2005年 | 150篇 |
2004年 | 105篇 |
2003年 | 103篇 |
2002年 | 68篇 |
2001年 | 18篇 |
2000年 | 34篇 |
1999年 | 19篇 |
1998年 | 11篇 |
1997年 | 17篇 |
1996年 | 16篇 |
1995年 | 12篇 |
1994年 | 9篇 |
1993年 | 13篇 |
1992年 | 8篇 |
1991年 | 7篇 |
1990年 | 9篇 |
1988年 | 7篇 |
1987年 | 10篇 |
1986年 | 10篇 |
1985年 | 16篇 |
1984年 | 10篇 |
1983年 | 6篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1980年 | 5篇 |
1979年 | 7篇 |
1978年 | 6篇 |
1975年 | 2篇 |
1938年 | 1篇 |
1933年 | 1篇 |
1931年 | 1篇 |
排序方式: 共有2610条查询结果,搜索用时 31 毫秒
931.
Francesco Baldi Fabio Bignotti Isabella Peroni Silvia Agnelli Theonis Riccò 《Polymer Testing》2012,31(3):455-465
The applicability of wire cutting in determining the fracture resistance, Gc, of polyacrylamide (PAAm) hydrogels, with different polymer contents and mechanical stiffness, was investigated. The various gels were synthesized both in the form of cylindrical and bar-shaped samples. Following the experimental scheme proposed in literature for wire cutting, each hydrogel, in the form of cylindrical specimen, was subjected to wire cutting with wires of different diameters. For each hydrogel, Gc was also separately measured by more conventional fracture tests on notched specimens prepared from the bar-shaped samples.The results demonstrated that, although Gc of the PAAm hydrogels here examined could not be evaluated by the direct application of the simple scheme proposed in literature, wire cutting is a promising approach for the measurement of the fracture resistance of chemical gels with relatively high stiffness, also in consideration of its proven experimental simplicity. 相似文献
932.
Silvia Dulanská Boris Remenec L’ubomír Mátel Igor Antalík 《Journal of Radioanalytical and Nuclear Chemistry》2012,292(1):97-101
Two separation techniques for plutonium determination using AnaLig® Pu02 molecular recognition technology product (MRT) and extraction chromatography TRU® resin were tested. The methods performance was investigated by analysis of National Physical Laboratory (NPL-Alpha-Beta High, ABH 2003, 2005) intercomparison test samples. The results obtained for both procedures were compared in terms of activities and recoveries. Data analysis showed good agreement with the reference values. The AnaLig® Pu02 separation method for 239,240Pu, 238Pu determination was successfully validated with the same performance as the TRU® resin method. 相似文献
933.
Detoni CB Souto GD da Silva AL Pohlmann AR Guterres SS 《Photochemistry and photobiology》2012,88(4):913-921
It is desirable and challenging to prevent E-resveratrol (E-RSV) from photoisomerizing to its Z-configuration to preserve its biological and pharmacological activities. The aim of this research was to evaluate the photostability of E-RSV-loaded supramolecular structures and the skin penetration profile of chemically and physically stable nanoestructured formulations. Different supramolecular structures were developed to act as carriers for E-RSV, that is, liposomes, polymeric lipid-core nanocapsules and nanospheres and solid lipid nanoparticles. The degrees of photostability of these formulations were compared with that of an ethanolic solution of E-RSV. The skin penetration profiles of the stable formulations were obtained using vertical diffusion cells (protected from light and under UVA radiation) with porcine skin as the membrane, followed by tape stripping and separation of the viable epidermis and dermis in a heated water bath. Photoisomerization was significantly delayed by the association of resveratrol with the nanocarriers independently of the supramolecular structure. Liposomes were the particles capable of maintaining E-RSV concentration for the longest time. On the other hand, E-RSV-loaded liposomes reduced in size showing low physical stability under UVA radiation. In the dark, the skin penetration profiles were very similar, but under UVA radiation the E-RSV-loaded nanocarriers showed increasing amounts in the total epidermis. 相似文献
934.
P Alvarez-Fitz L Alvarez S Marquina J Luna-Herrera VM Navarro-García 《Molecules (Basel, Switzerland)》2012,17(7):8464-8470
Biotransformation processes have been successfully utilized to obtain products of pharmaceutical, chemical, food, and agricultural interest, which are difficult to obtain by classic chemical methods. The compound with antituberculous activity, 9-methoxy-tariacuripyrone (1), isolated from Aristolochia brevipes, was submitted to biotransformation with the yeast Saccharomyces cerevisiae under culture, yielding 5-amino-9-methoxy-3,4-dihydro-2H-benzo[h]chromen-2-one (2). The structure of (2) was elucidated on the basis of spectroscopic analyses. The results mainly show the reduction of the double bond and the nitro group of compound (1). Metabolite (2) demonstrated an increase in anti-tuberculous activity (MIC = 3.12 μg/mL) against the drug-sensitive Mycobacterium tuberculosis (H37Rv) strain, with respect to that shown by (1). 相似文献
935.
Conversion of methanol to hydrocarbons: how zeolite cavity and pore size controls product selectivity 总被引:1,自引:0,他引:1
Olsbye U Svelle S Bjørgen M Beato P Janssens TV Joensen F Bordiga S Lillerud KP 《Angewandte Chemie (International ed. in English)》2012,51(24):5810-5831
Liquid hydrocarbon fuels play an essential part in the global energy chain, owing to their high energy density and easy transportability. Olefins play a similar role in the production of consumer goods. In a post-oil society, fuel and olefin production will rely on alternative carbon sources, such as biomass, coal, natural gas, and CO(2). The methanol-to-hydrocarbons (MTH) process is a key step in such routes, and can be tuned into production of gasoline-rich (methanol to gasoline; MTG) or olefin-rich (methanol to olefins; MTO) product mixtures by proper choice of catalyst and reaction conditions. This Review presents several commercial MTH projects that have recently been realized, and also fundamental research into the synthesis of microporous materials for the targeted variation of selectivity and lifetime of the catalysts. 相似文献
936.
Lamarra M Muccioli L Orlandi S Zannoni C 《Physical chemistry chemical physics : PCCP》2012,14(16):5368-5375
We address the calculation of charge carrier mobility of liquid-crystalline columnar semiconductors, a very promising class of materials in the field of organic electronics. We employ a simple coarse-grained theoretical approach and study in particular the temperature dependence of the mobility of the well-known triphenylene family of compounds, combining a molecular-level simulation for reproducing the structural changes and the Miller-Abrahams model for the evaluation of the transfer rates within the hopping regime. The effects of electric field, positional and energetic disorder are also considered. Simulations predict a low energetic disorder (~0.05 eV), slightly decreasing with temperature within the crystal, columnar and isotropic phases, and fluctuations of the square transfer integral of the order of 0.003 eV(2). The shape of the temperature-dependent mobility curve is however dominated by the variation of the transfer integral and barely affected by the disorder. Overall, this model reproduces semi-quantitatively all the features of experimentally measured mobilities, on one hand reinforcing the correctness of the hopping transport picture and of its interplay with system morphology, and on the other suggesting future applications for off-lattice modeling of organic electronics devices. 相似文献
937.
Ferrer S Martí S Moliner V Tuñón I Bertrán J 《Physical chemistry chemical physics : PCCP》2012,14(10):3482-3489
Salicylate synthase from Mycobacterium tuberculosis, MbtI, is a highly promiscuous Mg(2+) dependent enzyme with up to four distinct activities detected in vitro: isochorismate synthase (IS), isochorismate pyruvate lyase (IPL), salicylate synthase (SS) and chorismate mutase (CM). In this paper, Molecular Dynamic (MD) simulations employing hybrid quantum mechanics/molecular mechanics (QM/MM) potentials have been carried out to get a detailed knowledge of the IS and the IPL activities at the molecular level. According to our simulations, the architecture of the MbtI active site allows catalyzing the two reactions: the isochorismate formation, by means of a stepwise mechanism, and the salicylate production from isochorismate, that appears to be pericyclic in nature. Findings also explain the role of the magnesium cation and the pH dependence activity experimentally observed in MbtI. Mg(2+) would be polarizing and pre-organizing the substrate and active site, as well as shifting the pK(a) values of key active site residues. 相似文献
938.
Sylvia Schattauer Beate Reinhold Steve Albrecht Christoph Fahrenson Marcel Schubert Silvia Janietz Dieter Neher 《Colloid and polymer science》2012,290(18):1843-1854
In this work, a nonaqueous method is used to fabricate thin TiO2 layers. In contrast to the common aqueous sol–gel approach, our method yields layers of anatase nanocrystallites already at low temperature. Raman spectroscopy, electron microscopy and charge extraction by linearly increasing voltage are employed to study the effect of sintering temperature on the structural and electronic properties of the nanocrystalline TiO2 layer. Raising the sintering temperature from 120 to 600?°C is found to alter the chemical composition, the layer’s porosity and its surface but not the crystal phase. The room temperature mobility increases from 2?×?10?6 to 3?×?10?5?cm2/Vs when the sinter temperature is increased from 400 to 600?°C, which is explained by a better interparticle connectivity. Solar cells comprising such nanoporous TiO2 layers and a soluble derivative of cyclohexylamino-poly(p-phenylene vinylene) were fabricated and studied with regard to their structural and photovoltaic properties. We found only weak polymer infiltration into the oxide layer for sintering temperatures up to 550?°C, while the polymer penetrated deeply into titania layers that were sintered at 600?°C. Best photovoltaic performance was reached with a nanoporous TiO2 film sintered at 550?°C, which yielded a power conversion efficiency of 0.5?%. Noticeably, samples with the TiO2 layer dried at 120?°C displayed short-circuit currents and open circuit voltages only about 15–20?% lower than for the most efficient devices, meaning that our nonaqueous route yields titania layers with reasonable transport properties even at low sintering temperatures. 相似文献
939.
Silvia Berto Francesco Crea Pier Giuseppe Daniele Antonio Gianguzza Alberto Pettignano Silvio Sammartano 《Coordination chemistry reviews》2012,256(1-2):63-81
The interactions of dioxouranium(VI) cation with different organic and inorganic ligands of environmental and biological interest were carefully examined with the aim to draw a chemical speciation picture of this ion in natural aquatic ecosystems and in biological fluids. Since UO22+ ion shows a significant tendency to hydrolyze, particular attention was paid in considering the hydrolysis species formation both in the presence and in absence of ligands. The results reported in the literature show that formation of the hydrolytic species assumes a great importance in the complexation models for all the UO22+-ligand systems considered. In particular, the following ligands have been taken into account: (i) hydroxyl, chloride, fluoride, sulfate, carbonate and phosphate, as inorganic ligands, and (ii) carboxylates (with particular reference to oxalate and citrate), amines, amino acids, poly(amino carboxylates) (complexones), nucleotides, phosphonates, mercapto compounds and sulfonates, as organic ligands. In order to elucidate the speciation of uranyl in the presence of dissolved natural organic matter, the interactions with humic and fulvic acids were also considered. The strength of interaction in all the systems considered was expressed in terms of stability constants of complex species and, if available, of the relative thermodynamic stability parameters. When possible, if data reported in the literature were sufficiently homogeneous, trends of stability were found for the different ligands of the same class and for ligands of different classes. Moreover, relationships were derived for poly-functional ligands, such as poly-carboxylate, poly-amine and poly(amino carboxylate) ones, useful to predict the stability constants as a function of the number of binding sites per molecule, considering also, as in the case of amino acids, the contribution of the single functional groups to the whole stability of uranyl species formed. In addition, using the stability data collected for the uranyl-ligand systems considered, the sequestering capacity of some classes of ligands towards uranyl was calculated in terms of pL0.5, i.e., the ligand concentration useful to bind at least 50% of the cation. A comparison of pL0.5 of the most important classes of ligands considered was made to point out the different effectiveness in the UO22+ sequestration by the different ligands which can be present in multi-component solutions as natural waters and biological fluids. Finally, some considerations are reported about the different experimental techniques employed to study the complex formation in solution. 相似文献
940.
Paula Ortega Silvia Moreno Mª Pilar Tarazona Fco. Javier de la Mata Rafael Gómez Ramirez 《European Polymer Journal》2012,48(8):1413-1421
New hyperbranched polymers based on a carbosiloxane–carbosilane skeleton with aromatic units in the backbone have been prepared via one-pot hydrosilylation reaction using HSi(Me)2–O–CH2–C6H4–OSiMe–(CH2)4(C3H5)2 as a novel AB2 monomer. These polymers are easy to prepare, have narrow polydispersity values and present allyl groups on the surface which can be used as synthetic platforms for the introduction of different terminal groups like amine groups through hydrosilylation reactions, opening the door to functionalized polymers. The polymerization process was monitored using real-time 1H NMR spectroscopy and the resulting hyperbranched polymers were characterized using 1H NMR, 13C NMR, 29Si NMR and SEC/MALLS. The degree of branching in these polymers was determined by quantitative 29Si NMR spectroscopy and found to be very close to the theoretical value of 0.50 for AB2 systems. The hydrolytic degradation of these polymers in protic solvents has been studied by 29Si NMR. 相似文献