全文获取类型
收费全文 | 1046篇 |
免费 | 40篇 |
国内免费 | 5篇 |
专业分类
化学 | 878篇 |
晶体学 | 7篇 |
力学 | 12篇 |
数学 | 106篇 |
物理学 | 88篇 |
出版年
2024年 | 3篇 |
2023年 | 9篇 |
2022年 | 30篇 |
2021年 | 41篇 |
2020年 | 26篇 |
2019年 | 27篇 |
2018年 | 23篇 |
2017年 | 29篇 |
2016年 | 48篇 |
2015年 | 28篇 |
2014年 | 31篇 |
2013年 | 60篇 |
2012年 | 67篇 |
2011年 | 98篇 |
2010年 | 52篇 |
2009年 | 54篇 |
2008年 | 83篇 |
2007年 | 73篇 |
2006年 | 54篇 |
2005年 | 53篇 |
2004年 | 44篇 |
2003年 | 41篇 |
2002年 | 21篇 |
2001年 | 10篇 |
2000年 | 12篇 |
1999年 | 5篇 |
1998年 | 4篇 |
1996年 | 6篇 |
1995年 | 7篇 |
1991年 | 4篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1974年 | 1篇 |
1971年 | 1篇 |
1970年 | 4篇 |
1968年 | 3篇 |
1967年 | 1篇 |
1963年 | 1篇 |
1931年 | 1篇 |
1910年 | 2篇 |
1909年 | 8篇 |
1908年 | 2篇 |
1906年 | 1篇 |
排序方式: 共有1091条查询结果,搜索用时 0 毫秒
1.
2.
The Rio de la Plata is a large and shallow water body that discharges onto the Atlantic Ocean. The main driving forces for the river flow are the bathymetry, tides, the outflow from the Paraná and Uruguay rivers and the winds. A numerical model covering the entire river was set up with the objective of increasing our understanding of the hydrographical features and morphological dynamics in the Estuary. The simulations revealed a counter-clockwise residual circulation in the Samborombón Bay and an eastward net flow near the Uruguayan coast. The residual flow is forced by both the tides and the bathymetry. The residence time for the entire river ranges from 40 to 80 days. However, residence times above 120 days was found in the Samborombón Bay. Three corridors of flow have been identified. 相似文献
3.
4.
A new method to improve the analysis of phytochelatins and their precursors (cysteine, gamma-Glu-Cys, and glutathione) derivatized with monobromobimane (mBrB) in complex biological samples by capillary zone electrophoresis is described. The effects of the background electrolyte pH, concentration, and different organic additives (acetonitrile, methanol, and trifluoroethanol) on the separation were studied to achieve optimum resolution and number of theoretical plates of the analyzed compounds in the electropherograms. Optimum separation of the thiol peptides was obtained with 150 mM phosphate buffer at pH 1.60. Separation efficiency was improved when 2.5% v/v methanol was added to the background electrolyte. The electrophoretic conditions were 13 kV and capillary dimensions with 30 cm length from the inlet to the detector (38 cm total length) and 50 microm inner diameter. The injection was by pressure at 50 mbar for 17 s. Under these conditions, the separation between desglycyl-peptides and phytochelatins was also achieved. We also describe the optimum conditions for the derivatization of biological samples with mBrB to increase electrophoretic sensitivity and number of theoretical plates. The improved method was shown to be simple, reproducible, selective, and accurate in measuring thiol peptides in complex biological samples, the detection limit being 2.5 microM glutathione at a wavelength of 390 nm. 相似文献
5.
Mnica S. Brito Anna Lúcia C. H. Villavicencio Jorge Mancini-filho 《Radiation Physics and Chemistry》2002,63(3-6):337-340
In order to give the consumer the assurance that meat processed by irradiation is a safe product, a great deal of research has been developed in the world. The effect of irradiation on the hygienic quality of meat and meat products is considered as related to the control of meat-borne parasites of humans; elimination of pathogens from fresh meat and poultry; and elimination of pathogens from processed meat. Lipid oxidation and associated changes are the major causes of the quality deterioration of meat during storage. Irradiation of lipids induces the production of free radicals, which react with oxygen, leading to the formation of carbonyls, responsible for alterations in food nutritional and sensorial characteristics. Trans fatty acids are present in ground beef and can also be formed during its processing. Interestingly, the trans fatty acids, due to their chemical and physical characteristics, show more resistance to the oxidizing process. This property motivated us to investigate the level of the trans fatty acids, as well as the level of oxidation in irradiated ground beef. Irradiation of ground beef was performed by gamma rays from a 60Co source. The applied radiation doses were 0; 1.0; 2.0; 3.0; 4.0; 5.0; 6.0; 7.0 and 8.0 kGy. Lipid peroxidation in terms of TBA number and carbonyl content was monitored during storage. The sample characteristics and trans fatty acids composition were measured, following irradiation and after 60 and 90 days of storage at –10°C. 相似文献
6.
Ana M. Reverdito Liliana Orelli Mnica Dalmaso Isabel Perillo Beatriz M. Fernndez 《Journal of heterocyclic chemistry》1991,28(2):273-281
Reaction of 1,2-diaryl-3-methyl-1,4,5,6-tetrahydropyrimidinium iodides 1a-i with alkaline solutions afforded N-aroyl-N-aryl-N'-methyltrimethylenediamines 2a-i . Compounds 2 are stable under acid conditions but in neutral or alkaline media spontaneously rearrange giving N-aroyl-N'-aryl-N-methyltrimethylenediamines 3a-i . Treating compounds 3 with concentrated acids reverse reaction takes place. Kinetic studies were performed on this intramolecular N → N' aroyl transfer over the Ho-pH range -0.9 to 2.30. Compounds 3 undergo acyl transfer to give 2 by a mechanism which involves a change in the rate determining step from formation to acid-catalysed decomposition of a six-membered heterocyclic intermediate on going from Ho to pH values. The existence of maxima in the pH rate profile allow to determine apparent pKa values of the hexahydropyrimidine intermediates which gave good correlation with the Swain F substituent constants. Stability of these heterocycles was also predicted by determination of thermodinamic parameters. Comparisons are made with the behaviour of five-membered heterocyclic intermediates (imidazolidine derivatives) which were studied in an earlier paper. 相似文献
7.
We calculate energy barriers of atom- and proton-transfer reactions in hydrogen-bonded complexes in the gas phase. Our calculations do not involve adjustable parameters and are based on bond-dissociation energies, ionization potentials, electron affinities, bond lengths, and vibration frequencies of the reactive bonds. The calculated barriers are in agreement with experimental data and high-level ab initio calculations. We relate the height of the barrier with the molecular properties of the reactants and complexes. The structure of complexes with strong hydrogen bonds approaches that of the transition state, and substantially reduces the barrier height. We calculate the hydrogen-abstraction rates in H-bonded systems using the transition-state theory with the semiclassical correction for tunneling, and show that they are in excellent agreement with the experimental data. H-bonding leads to an increase in tunneling corrections at room temperature. 相似文献
8.
Sánchez ME Turina AV García DA Nolan MV Perillo MA 《Colloids and surfaces. B, Biointerfaces》2004,34(2):77-86
In the present work, we studied the ability of thymol to affect the organization of model membranes and the activity of an intrinsic membrane protein, the GABA(A) receptor (GABA(A)-R). In this last aspect, we tried to elucidate if the action mechanism of this terpene at the molecular level, involves its binding to the receptor protein, changes in the organization of the receptor molecular environment, or both. The self-aggregation of thymol in water with a critical micellar concentration approximately = 4 microM and its ability to penetrate in monomolecular layers of soybean phosphatidylcholine (sPC) at the air-water interface, even at surface pressures above the equilibrium, lateral pressure of natural bilayers were demonstrated. Thymol affected the self-aggregation of Triton X-100 and the topology of sPC vesicles. It also increased the polarity of the membrane environment sensed by the electrochromic dye merocyanine. A dipolar moment of 1.341 Debye was calculated from its energy-minimized structure. Its effect on the binding of [3H]-flunitrazepam ([3H]-FNZ) to chick brain synaptosomal membranes changed qualitatively from a tendency to the inhibition to a clear activatory regime, up on changing the phase state of the terpene (from a monomeric to a self-aggregated state). Above its CMC, thymol increased the affinity of the binding of [3H]-FNZ (K(d-control)= 2.9, K(d-thymol)= 1.7 nM) without changing the receptor density (B(max-control)= 910, B(max-thymol)= 895 fmol/mg protein). The activatory effect of thymol on the binding of [ [3H]-FNZ was observed even in the presence of the allosteric activator gamma-aminobutyric acid (GABA) at a concentration of maximal activity, and was blocked by the GABA antagonist bicuculline. Changes in the dipolar arrangement and in the molecular packing of GABA(A)-R environment are discussed as possible mediators of the action mechanism of thymol. 相似文献
9.
Jian Yang Vernica Postils Michael I. Lipschutz Meg Fasulo Christophe Raynaud Eric Clot Odile Eisenstein T. Don Tilley 《Chemical science》2020,11(19):5043
A cationic nickel complex of the bis(8-quinolyl)(3,5-di-tert-butylphenoxy)phosphine (NPN) ligand, [(NPN)NiCl]+, is a precursor to efficient catalysts for the hydrosilation of alkenes with a variety of hydrosilanes under mild conditions and low catalyst loadings. DFT studies reveal the presence of two coupled catalytic cycles based on [(NPN)NiH]+ and [(NPN)NiSiR3]+ active species, with the latter being more efficient for producing the product. The preferred silyl-based catalysis is not due to a more facile insertion of alkene into the Ni–Si (vs. Ni–H) bond, but by consistent and efficient conversions of the hydride to the silyl complex.A cationic nickel complex of the bis(8-quinolyl)(3,5-di-tert-butylphenoxy)phosphine (NPN) ligand, [(NPN)NiCl]+, is a precursor to efficient catalysts for the hydrosilation of alkenes with hydrosilanes under mild conditions and low catalyst loadings. 相似文献
10.
Iodine-poly(2-vinylpyridine-co-styrene-co-divinylbenzene) charge transfer complexes with antibacterial activity 总被引:1,自引:0,他引:1
Angela Cristina Jandrey Mônica Regina Marques Palermo de Aguiar José Luiz Mazzei 《European Polymer Journal》2007,43(11):4712-4718
In this work, we have developed three different copolymers based on 2-vinylpyridine, styrene and crosslinked with divinylbenzene (10-30 mol%). The copolymers were morphologically and chemically characterized by apparent density, swelling degree, elemental analysis, Fourier transform infrared spectrophotometry and optical microscopy. The formation of iodine complexes with these copolymers was carried out by two different procedures: with solvent, or not. The influence of the copolymers structure on the capacity of anchoring iodine has been investigated. The antibacterial properties of polymeric charge transfer complexes were determined towards 103-107 cells/mL dilutions from the auxotrophic AB1157 Escherichia coli strain. 相似文献