全文获取类型
收费全文 | 1279篇 |
免费 | 28篇 |
国内免费 | 2篇 |
专业分类
化学 | 1055篇 |
晶体学 | 22篇 |
力学 | 4篇 |
数学 | 108篇 |
物理学 | 120篇 |
出版年
2023年 | 14篇 |
2022年 | 77篇 |
2021年 | 55篇 |
2020年 | 31篇 |
2019年 | 33篇 |
2018年 | 22篇 |
2017年 | 23篇 |
2016年 | 48篇 |
2015年 | 41篇 |
2014年 | 45篇 |
2013年 | 116篇 |
2012年 | 86篇 |
2011年 | 77篇 |
2010年 | 51篇 |
2009年 | 59篇 |
2008年 | 53篇 |
2007年 | 65篇 |
2006年 | 62篇 |
2005年 | 47篇 |
2004年 | 51篇 |
2003年 | 36篇 |
2002年 | 26篇 |
2001年 | 18篇 |
2000年 | 14篇 |
1999年 | 9篇 |
1998年 | 12篇 |
1997年 | 8篇 |
1996年 | 6篇 |
1995年 | 15篇 |
1994年 | 7篇 |
1993年 | 10篇 |
1992年 | 9篇 |
1991年 | 5篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 6篇 |
1986年 | 8篇 |
1985年 | 9篇 |
1984年 | 3篇 |
1983年 | 8篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 8篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1974年 | 3篇 |
1962年 | 2篇 |
1937年 | 1篇 |
排序方式: 共有1309条查询结果,搜索用时 15 毫秒
91.
Adsorption of lignite-derived humic acids on coal-based mesoporous activated carbons 总被引:1,自引:0,他引:1
The adsorption by a coal-based mesoporous activated carbon of humic acids (HAs) isolated from two Polish lignites was studied. For comparison, a commercial Aldrich humic acid was also included into this study. The differences in chemical structure and functional groups of HAs were determined by elemental analysis and infrared spectroscopy DRIFT. Two activated carbons used differed in terms of mesopore volume, mesopore size distribution, and chemical properties of the surface. The kinetics of adsorption of HAs have been discussed using three kinetic models, i.e., the first-order Lagergren model, the pseudo-second-order model, and the intraparticle diffusion model. It was found that the adsorption of HAs from alkaline solution on mesoporous activated carbon proceeds according to the pseudo-second-order model. The correlation coefficients were close to 1. The intraparticle diffusion of HA molecules within the carbon particle was identified to be the rate-limiting step. Comparing the two activated carbons, the carbon with a higher volume of pores with widths of 10-50 nm showed a greater removal efficiency of HA. An increase in the Freundlich adsorption capacity with decreasing carbon content of HA was observed. Among the HAs studied, S-HA shows characteristics indicating the highest contribution of small-size fraction. The S-HA was removed by both activated carbons to the highest extent. The effect of pH solution on the adsorption of HA was examined over the range pH 5.4-12.2. It was found that the extent of adsorption decreased with decreasing pH of the solution. 相似文献
92.
The lipidic cubic phase can be characterized as a curved bilayer forming a three-dimensional, crystallographical, well-ordered structure that is interwoven by aqueous channels. It provides a stable, well-organized environment in which diffusion of both water-soluble and lipid-soluble compounds can take place. Cubic phases based on monoacylglycerols form readily and attract our interest due to their ability to incorporate and stabilize proteins. Their lyotropic and thermotropic phase behaviour has been thoroughly investigated. At hydration over 20%, lipidic cubic phases Ia3d and Pn3m are formed. The latter is stable in the presence of excess water, which is important when the cubic phase is considered as an electrode-modifying material. Due to high viscosity, the cubic phases can be simply smeared over solid substrates such as electrodes and used to host enzymes and synthetic catalysts, leading to new types of catalytically active modified electrodes as shown for the determination of cholesterol, CO(2), or oxygen. The efficiency of transport of small hydrophilic molecules within the film can be determined by voltametry using two types of electrodes: a normal-size electrode working in the linear diffusion regime, and an ultramicroelectrode working under spherical diffusion conditions. This allows determining both the concentration and diffusion coefficient of the electrochemically active probe in the cubic phase. The monoolein-based cubic phase matrices are useful for immobilizing enzymes on the electrode surface (e.g., laccases from Trametes sp. and Rhus vernicifera were employed for monitoring dioxygen). The electronic contact between the electrode and the enzyme was maintained using suitable electroactive probes. 相似文献
93.
Staśkowiak E Dudkowiak A 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(9):2033-2039
The paper deals with some fast and slow processes of excitation energy deactivation in bacteriochlorophyll c and bacteriopheophytin c. The experiments were carried out in the air, and in oxygen or nitrogen atmosphere at different temperatures. The parameters such as fluorescence yield, the yield of triplet state generation and photostability were estimated. On the basis of these parameters an attempt was made to preliminary select the pigments best suited for medical applications. It seems that the photosensitive and highly fluorescent bacteriochlorophyll c could be used as a fluorescence probe for diagnosis, whereas its derivative without the magnesium ion is better suited for the photochemical reactions occurring during therapeutic treatment. 相似文献
94.
JPC – Journal of Planar Chromatography – Modern TLC - Emodin and twelve phenolic acids (ellagic, gallic, protocatechuic, homoprotocatechuic, caffeic, p-hydroxybenzoic, p-coumaric,... 相似文献
95.
Anna M. Trzeciak Petr Štěpni?ka Ewa Mieczyńska 《Journal of organometallic chemistry》2005,690(13):3260-3267
The rhodium complex trans-[Rh(CO)(Hdpf-κP)(dpf-κ2O,P)] (1), (Hdpf = 1′-(diphenylphosphino)ferrocenecarboxylic acid) was used as an efficient and recyclable catalyst for 1-hexene hydroformylation producing ca. 80% of aldehydes at 10 atm CO/H2 and 80 °C. After the reaction, unchanged complex 1 was separated from the reaction mixture and used again three times with the same catalytic activity. The effect of modifying ligands, phosphines and phosphites, on the reactivity of 1 was investigated. The active catalytic systems containing 1 or trans-[Rh(CO)(L)(dpf-κ2O,P)] (2) were formed in situ from acetylacetonato rhodium(I) precursors [Rh(CO)2(acac)] (3) or [RhL(CO)(acac)] (4) and Hdpf or Medpf (L = phosphine, Medpf = methyl ester of Hdpf). 相似文献
96.
Ewa Szajdzinska-Pietek Ren Maldonado Larry Kevan Richard R. M. Jones 《Journal of colloid and interface science》1986,110(2)
Electron spin echo modulation studies with a series of x-doxylstearic acids (x = 5, 7, 10, 12, and 16) have been carried out for sodium- and tetramethylammonium dodecylsulfate and dodecyltrimethylammonium chloride frozen micellar solutions containing protiated and perdeuterated 1-butanol. Modulation effects due to nitroxide interactions with deuterium in water and butanol have been measured versus doxyl group position. The effect of 1-butanol on the micellar surface and internal micellar structure has been evaluated and the average location of 1-butanol in these micelles has been deduced to be in the outer annulus of the micelle core. 相似文献
97.
The mechanism of the indium electrodeposition on gold from acidic KBr solutions has been investigated by means of the rotating ring-disc electrode technique. The measurements showed that the overall electrode reaction In(III) + 3 e In consists of two successive charge transfer steps, i.e. In(III) + 2 e In(I) and In(I) + e In, with soluble monovalent indium as an intermediate. The current efficiency for In(I) generation under steady-state conditions is 100% in the case of low disc current densities. The disproportionation of In(I) in the bulk of solution occurs in slightly acidified solutions,pH=2, in addition to the In(I) electrochemical reduction. Based on the ring current transients, it was established that the two-electron transfer step is preceded by the formation of a thin passive film of indium metal.
Untersuchung der elektrochemischen Reduktion von In(III)-Ionen an Gold in sauren Bromidlösungen mit der rotierenden Ring-Scheiben-Elektrode
Zusammenfassung Mit Hilfe der rotierenden Ring-Scheiben-Elektrode wurde der Mechanismus der kathodischen Abscheidung von Indium auf Gold in sauren KBr-Lösungen untersucht. Aus den Messungen folgt, daß die Bruttoreaktion In(III) + 3e In über zwei aufeinanderfolgende Durchtrittsreaktionen, In(III) + 2 e In(I) und In(I) + e In, mit löslichem einwertigem Indium als Zwischenprodukt abläuft. Bei kleinen Stromdichten werden die In(I)-Ionen mit 100%iger Stromausbeute erzeugt. In schwächer sauren Lösungen (pH=2) konnte außer der elektrochemischen Reduktion von In(I) zusätzlich dessen Disproportionierung innerhalb der Lösung ermittelt werden. Auf Grund der Ringstrom-Zeit-Kurven wurde auch festgestellt, daß die Bildung von einer dünnen In-Metallschicht, die ein passives Verhalten aufweist, dem Zweielektronenübergang vorangegangen ist.相似文献
98.
Prof. Dr. Antoni W. Morawski Dr. Ewelina Kusiak-Nejman Dr. Iwona Pełech Katarzyna Ćmielewska Dr. Daniel Sibera Piotr Staciwa Dr. Agnieszka Wanag Marcin Gano Dr. Ewa Ekiert Dr. Joanna Kapica-Kozar Kordian Witkowski Prof. Dr. Urszula Narkiewicz 《ChemistryOpen》2022,11(4):e202100262
A new approach to hydrogen production from water is described. This simple method is based on carbon dioxide-mediated water decomposition under UV radiation. The water contained dissolved sodium hydroxide, and the solution was saturated with gaseous carbon dioxide. During saturation, the pH decreased from about 11.5 to 7–8. The formed bicarbonate and carbonate ions acted as scavengers for hydroxyl radicals, preventing the recombination of hydroxyl and hydrogen radicals and prioritizing hydrogen gas formation. In the presented method, not yet reported in the literature, hydrogen production is combined with carbon dioxide. For the best system with alkaline water (0.2 m NaOH) saturated with CO2 under UV-C, the hydrogen production amounted to 0.6 μmol h−1 during 24 h of radiation. 相似文献
99.
100.
Michnik Anna Kiełboń Agnieszka Duch Klaudia Sadowska-Krępa Ewa Pokora Ilona 《Journal of Thermal Analysis and Calorimetry》2022,147(12):6739-6743
Journal of Thermal Analysis and Calorimetry - The results of studies of physiological fluids by differential scanning calorimetry (DSC) for the purpose of diagnosis and monitoring of diseases are... 相似文献