全文获取类型
收费全文 | 334篇 |
免费 | 7篇 |
国内免费 | 1篇 |
专业分类
化学 | 304篇 |
晶体学 | 4篇 |
力学 | 3篇 |
数学 | 12篇 |
物理学 | 19篇 |
出版年
2021年 | 2篇 |
2020年 | 3篇 |
2019年 | 4篇 |
2018年 | 5篇 |
2016年 | 2篇 |
2015年 | 8篇 |
2014年 | 6篇 |
2013年 | 21篇 |
2012年 | 15篇 |
2011年 | 22篇 |
2010年 | 21篇 |
2009年 | 16篇 |
2008年 | 26篇 |
2007年 | 13篇 |
2006年 | 15篇 |
2005年 | 20篇 |
2004年 | 9篇 |
2003年 | 12篇 |
2002年 | 6篇 |
2001年 | 2篇 |
2000年 | 10篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1997年 | 4篇 |
1996年 | 1篇 |
1995年 | 9篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 5篇 |
1991年 | 7篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1987年 | 9篇 |
1986年 | 7篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 5篇 |
1981年 | 1篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1975年 | 5篇 |
1974年 | 2篇 |
1972年 | 1篇 |
1938年 | 1篇 |
1914年 | 1篇 |
排序方式: 共有342条查询结果,搜索用时 31 毫秒
21.
Dukeson DR Ungar G Balagurusamy VS Percec V Johansson GA Glodde M 《Journal of the American Chemical Society》2003,125(51):15974-15980
A second generation monodendron with dodecyl end-groups based on the AB(3) monomer 3,4,5-trihydroxy benzoate has previously been shown to form a thermotropic cubic phase with Pmthremacr;n symmetry (Balagurusamy et al., J. Am. Chem. Soc. 1997, 119, 1539). A structure consisting of spherical "micelles" was proposed originally, but an alternative choice of structure factor phases, giving a structure of interlocked squashed columns, could not be ruled out by diffraction data on the original material alone. We have therefore synthesized two selectively fluorinated equivalent compounds, the carboxylic acid and its Rb salt, to be able to apply a variant of the isomorphous replacement crystallographic technique. On the basis of the electron density maps of the new labeled compounds, reconstructed using small-angle X-ray diffraction intensities, the interlocking columns model is unequivocally rejected and the spheres model is upheld. Furthermore, the location of the metal cation in the center of the "micelles" is directly confirmed. Micellar diameter was shown to decrease on fluorination of the dodecyl chain ends, and increase significantly on introduction of Rb. This is interpreted in terms of changes in the number of wedge-shaped dendrons fitting into a spherical micelle due to their changing taper angle. It was found that the Rb-rich regions at the centers of six out of eight "micelles" in the unit cell are elongated in the direction of their closest packing. This adds support to the suggestion of a partial "column-like" character of stacked rows of such micelles, consistent with the position of the Pmthremacr;n phase next to the columnar phase in the phase sequence of most taper-shape compounds. The results illustrate the potential of isomorphous replacement, used a great deal in protein crystallography, in structure investigation of liquid crystals and supramolecular soft matter. 相似文献
22.
23.
Sven Fleischmann Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2010,48(21):4884-4888
Single‐electron transfer living radical polymerization (SET‐LRP) has developed as a reliable, robust and straight forward method for the construction well‐defined polymers. To span an even larger variety of functional monomers, we investigated the copolymerization of methyl methacrylate with methacrylic acid by SET‐LRP. Copolymerizations were catalyzed by Cu(0)/Me6‐TREN and performed in MeOH/H2O mixtures at 50 °C. The SET‐LRP copolymerizations of varying methacrylic acid content were evaluated by kinetic experiments. At low (2.5%) and moderate (10%) MAA loadings, the copolymerizations obeyed perfect first order kinetics (kpapp = 0.008 min?1 and kpapp = 0.006 min?1) and exhibited a linear increase in molecular weights with conversion providing narrow molecular weight distributions. The SET‐LRP of MMA/25%‐MAA was found to be significantly slower (kpapp = 0.0035 min?1). However, a reasonable first‐order kinetics in monomer consumption was maintained, and the control of the polymerization process was preserved since the molecular weight increased linearly with conversion and could therefore be adjusted. This work demonstrates that the copolymerization of methacrylic acid by SET‐LRP is feasible and the design of well‐defined macromolecules comprising acidic functionality can be achieved. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
24.
25.
Gerard Lligadas Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2008,46(10):3174-3181
The Cu(0)/Me6‐TREN‐catalyzed single‐electron transfer mediated living radical polymerization (SET‐LRP) of methyl acrylate in the presence of the classic 4‐methoxyphenol free radical inhibitor was investigated. Kinetic experiments, combined with 1H NMR, and MALDI‐TOF MS analysis of the resulting polyacrylates demonstrated that SET‐LRP is a robust synthetic method that does not require the purification of the monomers to remove the radical inhibitor. It is anticipated that these results will contribute to the expansion of technological and fundamental applications of SET‐LRP since it allows the synthesis of polymers with a structural perfection that previously was not accessible by any other method, starting from unpurified monomers, solvents, initiators, and ligands. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3174–3181, 2008 相似文献
26.
Virgil Percec Hildeberto Nava Hkan Jonsson 《Journal of polymer science. Part A, Polymer chemistry》1987,25(7):1943-1965
The influence of molecular weight on thermal transitions and on their thermodynamic parameters is discussed for a random thermotropic liquid crystalline copolyether based on the reaction of a 1:1 molar mixture of 1,5-dibromopentane and 1,7-dibromoheptane with 4,4′-dihydroxy-α-methylstilbene. Optimum phase transfer catalyzed polyetherification reaction conditions were established for the synthesis of polymers containing bromoalkane chain ends only over a wide variety of molecular weights. All these copolyethers present a crystalline and an enantiotropic nematic mesophase over the entire range of molecular weights studied. Both the thermal transitions and their thermodynamic parameters are strongly molecular weight-dependent up to M n = 10,000–12,000, after which they remain constant. The enthalpies and entropies of isotropization of the copolyethers are higher than those of melting. This is in contrast to the same thermodynamic parameters of the corresponding homopolyethers. The enthalpies and entropies of isotropization of both homopolymers and copolymers present similar values, suggesting that copolymerization does decrease the degree of order in the crystalline phase but does not significantly change the alignment degree of the mesogenic units in the nematic mesophase. 相似文献
27.
Brad M. Rosen Gerard Lligadas Christian Hahn Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2009,47(15):3940-3948
The development of a novel nucleophilic thio‐bromo “Click” reaction, specifically base‐mediated thioetherification of thioglycerol with α‐bromoesters was reported in an earlier article. The combination of this thio‐bromo click reaction with subsequent acylation with 2‐bromopropionyl bromide provides an iterative two‐step divergent growth approach to the synthesis of a new class of poly(thioglycerol‐2‐ propionate) (PTP) dendrimers. In this article, the addition of a third step, the single‐electron transfer living radical polymerization (SET‐LRP) of methyl acrylate (MA), was shown to provides access to a three‐step “branch” and “grow” divergent approach to dendritic macromolecules wherein poly(methyl acrylate) (PMA) connects the branching subunits. This facile methodology can provide a diversity of dendritic macromolecular topologies and will ultimately provide the means to the development of self‐organizable dendritic macromolecules. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3940–3948, 2009 相似文献
28.
Gerard Lligadas Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2008,46(14):4917-4926
Single‐electron transfer living radical polymerization (SET‐LRP) proceeds by an outer‐sphere single‐electron transfer mechanism that induces a heterolytic bond cleavage of the initiating and propagating R‐X (where X = Cl, Br, and I) species. Therefore, unlike the homolytic bond cleavage mechanism claimed for ATRP, SET‐LRP is expected to show a small dependence of the nature of the halide group on the apparent rate constant of activation. This means the R‐X with X = Cl, Br, and I must all be efficient initiators for SET‐LRP and no chain transfer must be observed in the case of initiators with X = Br and I. Here, we report the SET‐LRP of methyl acrylate initiated with the alkyl chlorides methyl‐2‐chloropropionate (MCP) and chloroform (CHCl3) and catalyzed by Cu(0)/Me6‐TREN/CuCl2 in DMSO at 25 °C. A combination of kinetic and structural analysis was used to elucidate the MCP and CHCl3 initiating behavior under SET‐LRP conditions, and to demonstrate the very small dependence of the SET‐LRP apparent rate constant of propagation on X while providing polymers with well defined architecture. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4917–4926, 2008 相似文献
29.
30.
Nga H. Nguyen Xuan Jiang Sven Fleischmann Brad M. Rosen Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2009,47(21):5629-5638
The effect of initial ligand concentration on the apparent rate constant of propagation of single‐electron transfer living radical polymerization (SET‐LRP) of MA in DMSO at 25 °C was examined using various lengths of Cu(0) wire as catalyst. It was determined that unlike other parameters such as initiator concentration, solvent concentration, and deactivator concentration, no simple external rate‐order for the ligand concentration could be determined. Rather, the response of the rate of SET‐LRP to initial ligand concentration is complex and is likely determined by a competition of ligand‐dependent extent of disproportionation as well as the role of ligand concentration in the surface mediated activation process. Results suggest that a minimum concentration of ligand is needed to achieve both acceptable reaction rate and reaction control, and therefore, ligand concentration must be considered in designing experimental conditions for SET‐LRP. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5629–5638, 2009 相似文献