全文获取类型
收费全文 | 1308篇 |
免费 | 41篇 |
国内免费 | 3篇 |
专业分类
化学 | 933篇 |
晶体学 | 5篇 |
力学 | 53篇 |
数学 | 55篇 |
物理学 | 306篇 |
出版年
2024年 | 1篇 |
2023年 | 9篇 |
2022年 | 23篇 |
2021年 | 41篇 |
2020年 | 32篇 |
2019年 | 30篇 |
2018年 | 19篇 |
2017年 | 15篇 |
2016年 | 35篇 |
2015年 | 37篇 |
2014年 | 56篇 |
2013年 | 96篇 |
2012年 | 94篇 |
2011年 | 105篇 |
2010年 | 67篇 |
2009年 | 59篇 |
2008年 | 81篇 |
2007年 | 83篇 |
2006年 | 74篇 |
2005年 | 67篇 |
2004年 | 57篇 |
2003年 | 44篇 |
2002年 | 50篇 |
2001年 | 34篇 |
2000年 | 28篇 |
1999年 | 16篇 |
1998年 | 9篇 |
1997年 | 7篇 |
1996年 | 12篇 |
1995年 | 12篇 |
1994年 | 8篇 |
1993年 | 10篇 |
1992年 | 9篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1988年 | 3篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1976年 | 1篇 |
1975年 | 1篇 |
排序方式: 共有1352条查询结果,搜索用时 296 毫秒
31.
32.
Choi SJ Yoo PJ Baek SJ Kim TW Lee HH 《Journal of the American Chemical Society》2004,126(25):7744-7745
We describe a novel UV-curable mold that is stiff enough for replicating dense sub-100-nm features even with a high aspect ratio. It also allows for flexibility when the mold is prepared on a flexible support such that large area replication can be accomplished. The composite material of the mold is inert to chemicals and solvents. The surface energy is made low with a small amount of releasing agent such that the mold can be removed easily and cleanly after patterning. In addition, the material allows self-replication of the mold. These unique features of the mold material should make the mold quite useful for various patterning purposes. 相似文献
33.
Han JH Yoo SK Seo JS Hong SJ Kim SK Kim C 《Dalton transactions (Cambridge, England : 2003)》2005,(2):402-406
The systematic oxidation reactions of a wide range of alcohols have been carried out by using an iron porphyrin complex in order to understand their relation to cytochrome P-450 enzymes and to have a practical application to organic synthesis. The iron porphyrin complex catalyzed efficiently alcohol oxidation to the respective carbonyl compound via a high-valent iron-oxo porphyrin intermediate ((Porp)Fe=O+). Several mechanistic studies such as isotope 18O labeling, deuterium isotope effect, linear free energy relationship, and ring-opening of radical clock substrate, have suggested that the alcohol is oxidized by a sequence of reactions involving an alpha-hydroxyalkyl radical intermediate and oxygen rebound to form the gem-diol, dehydration of which yields the carbonyl compounds. Moreover, it has been proposed that a two-state reactivity mechanism can also be adopted for alcohol oxidation reactions in iron porphyrin model systems as exhibited by P-450 enzymes. 相似文献
34.
Holzmueller J Genson KL Park Y Yoo YS Park MH Lee M Tsukruk V 《Langmuir : the ACS journal of surfaces and colloids》2005,21(14):6392-6398
Amphiphilic dendron-rod molecules with three hydrophilic poly(ethylene oxide) (PEO) branches attached to a hydrophobic octa-p-phenylene rod stem were investigated for their ability to form two-dimensional micellar structures on a solid surface. A treelike shape of the molecules was reported to be a major factor in the formation of nonplanar micellar structures in solution and in the bulk state (cylindrical and spherical). We observed that in these treelike amphiphilic molecules the hydrophilic terminated dendron branches assemble themselves in surface monolayers with the formation of two-dimensional layered or circular micellar structures. We suggested the formation of the planar ribbon-like structures with interdigitated layering within the loosely packed monolayers and circular, ringlike structures (2D circular aggregates) in the precollapsed state. 相似文献
35.
Rosenberg Edward Freeman William Carlos Zinnia Hardcastle Kenneth Yong Jin Yoo Milone Luciano Gobetto Roberto 《Journal of Cluster Science》1992,3(4):439-457
The general relationships between trinuclear cluster reactivity and the ligand dynamical processes in these systems are explored. Three specific mechanistic studies are presented: (1) the rate and stereochemistry of ligand addition to 3-imidoyl complexes, (2) the factors influencing the rate of carbon-hydrogen bond activation in 3-alkyne complexes, and (3) the origin of anomalously large kinetic deuterium isotope effect in metal to ligand and ligand to metal hydrogen transfer in trinuclear and binuclear complexes. In all three cases, the current state of the mechanistic studies are summarized and the possible rate of specific ligand dynamical processes in controlling the mechanism are put forth. 相似文献
36.
Poly(vinyl chloride) membrane electrodes containing the specified substances are suitable as indicator electrodes in titrations of basic dyes with sodium tetraphenylborate solution and of acidic dyes with crystal violet solution. Useful curves are obtained even at the 10-3 M level. 相似文献
37.
By means of a large-scale molecular dynamics simulation, we show that the Tolman length, although positive, is much smaller in magnitude than previously reported. We found that the range of interparticle interaction can significantly affect the magnitude of the Tolman length. When the range of interaction is longer than five molecular diameters, the Tolman length is on the order of a few hundredths of the molecular diameter, rather than a few tenths known previously. 相似文献
38.
Youngtai Yoo Larry K. Johnson Stephen N. Falling Jeremy R. Lizotte Timothy E. Long 《Journal of polymer science. Part A, Polymer chemistry》2002,40(16):2789-2798
Accelerated crosslinking of novel poly(3,4‐epoxy‐1‐butene) (3,4‐PEPB) oligomers in the presence of a cobalt‐based redox catalyst was investigated. Previous studies using model compounds, 3,4‐dimethoxy‐1‐butene and 1,4‐dimethoxy‐2‐butene, suggested that maleation of hydroxyl‐terminated 3,4‐PEPB oligomers would result in more rapid crosslinking in thin films. Novel maleated oligomers offered a unique combination of both electron‐rich and electron‐poor olefinic sites, and quantitative maleation significantly increased the crosslinking rate of 3,4‐PEPB. Efficient copolymerization between terminal maleate groups and olefinic groups in the repeating unit was proposed to account for accelerated crosslinking rates. Furthermore, the addition of novel reactive diluents, such as maleic acid mono‐ethyl ester, also effectively improved the 3,4‐PEPB crosslinking rate. Sol fraction measurements as a function of coating thickness revealed that the crosslinking rate versus oxygen diffusion was less significant for the maleated oligomers because of the presence of reactive electron‐poor olefins. Sol fractions were constant for catalyst concentrations greater than 0.25–0.50 wt % (as compared with oligomer feed). This observation suggested that a redox process was not a dominant factor in determining crosslinking rates at various experimental conditions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2789–2798, 2002 相似文献
39.
Reaction of 2-adamantyl chloroformate under a variety of solvolytic conditions leads to 2-adamantyl chloride accompanied by solvolysis products, some with and some without retention of the CO(2) unit. For example, in 100% ethanol, only 4.8% 2-adamantyl chloride is formed with the mixed carbonate (88%) being the dominant product, and in 100% 2,2,2-trifluoroethanol, the products are both formed with loss of CO(2), 59% of the chloride and 41% of the ether. With exclusion of the specific rates in 100% and 90% ethanol and methanol, a good Grunwald-Winstein plot against Y(Cl) values (solvent ionizing power) is obtained, with a slope of 0.47 +/- 0.03. The results are compared with those reported earlier for 1-adamantyl chloroformate and isopropyl chloroformate and mechanistic conclusions are drawn. 相似文献
40.
[reaction: see text] A new recyclable supported catalyst system for orthoalkylation was devised using a self-assembly consisting of the barbiturate and 2,4,6-triaminopyrimidine H-bonding motifs. At high temperature, the system is completely homogeneous so as to give an efficient catalytic activity, while it is heterogenized at room temperature to form an insoluble solid phase for the easy recovery of the catalyst after the reaction. 相似文献