全文获取类型
收费全文 | 2140篇 |
免费 | 48篇 |
国内免费 | 27篇 |
专业分类
化学 | 1175篇 |
晶体学 | 7篇 |
力学 | 38篇 |
数学 | 456篇 |
物理学 | 539篇 |
出版年
2023年 | 8篇 |
2022年 | 44篇 |
2021年 | 59篇 |
2020年 | 34篇 |
2019年 | 43篇 |
2018年 | 57篇 |
2017年 | 45篇 |
2016年 | 67篇 |
2015年 | 58篇 |
2014年 | 70篇 |
2013年 | 97篇 |
2012年 | 149篇 |
2011年 | 139篇 |
2010年 | 103篇 |
2009年 | 99篇 |
2008年 | 154篇 |
2007年 | 141篇 |
2006年 | 123篇 |
2005年 | 125篇 |
2004年 | 126篇 |
2003年 | 68篇 |
2002年 | 72篇 |
2001年 | 46篇 |
2000年 | 26篇 |
1999年 | 31篇 |
1998年 | 39篇 |
1997年 | 25篇 |
1996年 | 19篇 |
1995年 | 24篇 |
1994年 | 20篇 |
1993年 | 11篇 |
1992年 | 9篇 |
1991年 | 8篇 |
1990年 | 9篇 |
1989年 | 7篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 5篇 |
1985年 | 7篇 |
1984年 | 3篇 |
1982年 | 3篇 |
1981年 | 6篇 |
1980年 | 6篇 |
1979年 | 3篇 |
1977年 | 4篇 |
1976年 | 2篇 |
1975年 | 4篇 |
1970年 | 2篇 |
1969年 | 3篇 |
1968年 | 2篇 |
排序方式: 共有2215条查询结果,搜索用时 15 毫秒
61.
An electrodynamics-based model was formulated for simulation of ion diffusion in microbial polysaccharides. The fixed charges and electrostatic double layers that may associate with microbial polysaccharides and their effects on ion diffusion were explicitly built into the model. The model extends a common multicomponent ion diffusion formulation that is based on irreversible thermodynamics under a zero ionic charge flux condition, which is only applicable to the regions without fixed charges and electrostatic double layers. An efficient numerical procedure was presented to solve the differential equations in the model. The model well described key features of experimental observations of ion diffusion in negatively charged microbial polysaccharides including accelerated diffusive transport of cations, exclusion of anions, and increased rate of cation transport with increasing negative charge density. The simulated diffusive fluxes of cations and anions were consistent with a cation exchange diffusion concept in negatively charged polysaccharides at the interface of plant roots and soils; and the developed model allows to mathematically study such diffusion phenomena. An illustrative example was also provided to simulate dynamic behavior of ionic current during ion diffusion within a charged bacterial cell wall polysaccharide and the effects of the ionic current on the compression or expansion of the bacterial electrostatic double layer at the interface of the cell wall and bulk solution. 相似文献
62.
Weiping Huang Suwen Liu Xianghai Tang Menachem Motiei Yuri Koltypin A. Gedanken 《Research on Chemical Intermediates》2004,30(7-8):793-805
Ag-TiO2, Cu-TiO2 and Ni-TiO2 were prepared by sonication. The interactions of Ti-gel with silver, copper and nickel ions under ultrasound irradiation are very different, although these ions can be dispersed very well in titania. The results of EDXA and XRD analysis indicate that Ti-gel does not react with AgCl and crystallizes unaffectedly to form rutile. M(OH)2 (M = Cu and Ni), on the other hand, favors polycondensation with Ti-gel and affects the crystallization of Ti-gel. CuO favors stabilization of the anatase phase. Ni2+ ions tend to incorporate more easily into titania than Cu2+ ions do when the samples are calcined. TEM, and BET were also used to characterize the samples. 相似文献
63.
Summary A new transition state algorithm incorporated into the density functional code deMon, has been used to study thetrans cis-hydroxymethylene andtrans-hydroxymethylene formaldehyde isomerization processes and to localize the transition state for the decomposition of 1,3-diazacyclobutane to methyleneimine. Calculations have been performed using both local (LSD) and nonlocal spin density (NLSD) gradient-corrected approximations. Two different basis sets of small and large size have been used for the study in order to analyze the effect of the basis set dimension other than that of the nonlocal corrections on the activation energy barrier value. The results seem to confirm that density functional methods can be considered practical and reliable tools for the localization of transition states. 相似文献
64.
Mizukami S Watanabe S Akimoto Y Kikuchi K 《Journal of the American Chemical Society》2012,134(3):1623-1629
Small molecule labeling techniques for cellular proteins under physiological conditions are very promising for revealing new biological functions. We developed a no-wash fluorogenic labeling system by exploiting fluorescence resonance energy transfer (FRET)-based fluorescein-cephalosporin-azopyridinium probes and a mutant β-lactamase tag. Fast quencher elimination, hydrophilicity, and high resistance against autodegradation were achieved by rational refinement of the structure. By applying the probe to real-time pulse-chase analysis, the trafficking of epidermal growth factor receptors between cell surface and intracellular region was imaged. In addition, membrane-permeable derivatization of the probe enabled no-wash fluorogenic labeling of intracellular proteins. 相似文献
65.
Yuri Park Godwin A. Ayoko Janos Kristof Erzsébet Horváth Ray L. Frost 《Journal of Thermal Analysis and Calorimetry》2012,107(3):1137-1142
High resolution thermogravimetric analysis (TG) has attracted much attention in the synthesis of organoclays and its applications.
In this study, organoclays were synthesised through ion exchange of a single cationic surfactant for sodium ions, and characterised
by methods including X-ray diffraction (XRD) and TG. The changes of surface properties in montmorillonite (MMT) and organoclays
intercalated with surfactant were determined using XRD through the changes in the basal spacing. The TG was applied in this
study to investigate more information of the configuration and structural changes in the organoclays with thermal decomposition.
There are four different decompositions steps in differential thermogravimetric curves. The obtained TG steps are relevant
to the arrangement of the surfactant molecules intercalated in MMT and the thermal analysis indicates the thermal stability
of surfactant modified clays. This investigation provides new insights into the properties of organoclays and is important
in the synthesis and processing of organoclays for environmental applications. 相似文献
66.
Puzenko A Hayashi Y Ryabov YE Balin I Feldman Y Kaatze U Behrends R 《The journal of physical chemistry. B》2005,109(12):6031-6035
We discuss the relaxation dynamics of glycerol-water mixtures, as studied by dielectric spectroscopy in the frequency range from 1 Hz to 250 MHz and at temperatures between 173 and 323 K. The experimental results obtained for the glycerol-rich mixtures suggest that the main dielectric relaxation process, as well as the so-called high-frequency "excess wing" (EW) and dc conductivity, follow the same temperature dependence. This result indicates that all of these processes are induced by the same molecular origin. A new phenomenological function is proposed to describe the whole dielectric spectrum in the covered frequency range, and some possible mechanisms of dielectric behaviors through the dc conductivity, the main relaxation process, and the EW are discussed. 相似文献
67.
A bimetallic titanium(salen) complex has been used to catalyze the asymmetric addition of potassium cyanide to aldehydes attached to Wang resin giving polymer supported cyanohydrin propionates with up to 91% enantiomeric excesses. 相似文献
68.
Irina G. Gazaryan Maya Yu. Rubtsova Yuri L. Kapeliuch José Neptuno Rodriguez-Lopez L. Mark Lagrimini Roger N. F. Thorneley 《Photochemistry and photobiology》1998,67(1):106-110
The properties of a newly isolated anionic tobacco peroxidase from transgenic tobacco plants overexpressing the enzyme have been studied with respect to the chemiluminescent reaction of luminol oxidation. These were compared to the properties of horseradish peroxidase in the cooxidation of luminol and p -iodophenol, the enhanced chemiluminescence reaction. The pH, luminol and hydrogen peroxide concentrations were optimized for maximum sensitivity using the tobacco enzyme. The detection limit for the latter under the optimal conditions (2.5 m M luminol, 2 m M hydrogen peroxide, 100 m M Naborate buffer, pH 9.3) was about 0.1 p M , which is at least five times lower than that for horseradish peroxidase in enhanced chemiluminescence with p -iodophenol. The rate constants for the elementary steps of the enzyme-catalyzed reaction have been determined: k 1 = 4.9 × 106 M −1 s1 , k 2 = 7.3 × 106 M −1 s−1 , k 3 = 2.1 × 106 M −1 s−1 (pH 9.3). The similarity of these rate constants is unusual for plant peroxidases. The high catalytic activity of tobacco peroxidase in the luminescent reaction is explained by the high reactivity of its Compound II toward luminol and the high stability of the holoenzyme with respect to heme dissociation. This seems to be a unique property of this particular enzyme among other plant peroxidases. 相似文献
69.
Yuri M. Boiko Dmitri V. Lebedev Liubov P. Myasnikova 《Colloid and polymer science》2013,291(6):1519-1523
The isothermal luminescence decay kinetics in near-surface nanolayers of plasma-activated bulk samples of amorphous polystyrene (PS) and poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and their miscible blends with weight ratios PS/PPO of 75/25 and 50/50 has been studied at 77 K. The intensities of isothermal luminescence (I) of homopolymer and blend surfaces have been compared. It has been found that the ratio between the luminescence intensities for PS and PPO (I(PS)/I(PPO)) may be as high as 50, while the luminescence intensities for the PS–PPO blends are close to I(PPO). The results obtained indicate that the PPO concentration in the surface layers of the blends is higher than that in the bulk. 相似文献
70.
Oleg G. Sinyashin Irina P. Romanova Gulshat G. Yusupova Valery I. Kovalenko Yuri Y. Efremov Irina I. Vandyukova 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1)
Abstract Data on the structure of cycloadducts of organophosphorus dipolar reagents and fullerenes arc absent, to our knowledge. We died the reactions and the shucturc of cycloadducts of phosphorylated azidcs and nitrile oxide with [60]fullcrcnc. The cycloaddition of diphcnylphosphinic llzide to fullcrme has bcm determined to lead to the 1 -[(N-diphenylphosphoryl)amino]-2-hydroxy[6O]hllcrme (l), the mixhuc of phosphorylated aziridinofullcrcne (2) and derivative of fullerne (3) with one aziridine fragment and one aminohydmxy-fragment, or to product (4), depending on the conditions of don . 相似文献