全文获取类型
收费全文 | 271篇 |
免费 | 5篇 |
专业分类
化学 | 263篇 |
数学 | 2篇 |
物理学 | 11篇 |
出版年
2019年 | 1篇 |
2016年 | 1篇 |
2015年 | 2篇 |
2014年 | 5篇 |
2013年 | 8篇 |
2012年 | 7篇 |
2011年 | 10篇 |
2010年 | 6篇 |
2009年 | 6篇 |
2008年 | 12篇 |
2007年 | 11篇 |
2006年 | 13篇 |
2005年 | 28篇 |
2004年 | 22篇 |
2003年 | 25篇 |
2002年 | 15篇 |
2001年 | 16篇 |
2000年 | 16篇 |
1998年 | 2篇 |
1996年 | 7篇 |
1995年 | 2篇 |
1994年 | 5篇 |
1993年 | 2篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1989年 | 2篇 |
1986年 | 1篇 |
1985年 | 6篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 5篇 |
1981年 | 3篇 |
1980年 | 9篇 |
1979年 | 5篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1940年 | 3篇 |
1938年 | 1篇 |
排序方式: 共有276条查询结果,搜索用时 15 毫秒
1.
2.
3.
Tamaru SI Yamamoto M Shinkai S Khasanov AB Bell TW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(24):5270-5276
A dicarboxylate host (1) binds cationic monosaccharides such as D-glucosamine HCl (2), D-galactosamine-HCl (3), and D-mannosamine-HCl (4) with high affinity (K1 = 8.0 x 10(4)-2.0 x 10(5) M(-1)) in methanol. In circular dichroism (CD) spectroscopy a positive exciton-coupling band was observed near 290 nm; this indicates that the saccharides are recognized by multiple point interactions. Since the corresponding neutral monosaccharides are not significantly bound, one may conclude that complex formation is primarily due to the electrostatic interaction between NH3+ in the guest and one carboxylate in the host and secondarily due to hydrogen-bonding interactions of OH groups with the other carboxylate and/or nitrogen bases. Molar ratio plots and Job plots indicate that host 1 and cationic monosaccharide guests form CD-active, pseudo-cyclic 1:1 complexes at low guest concentration followed by the formation of CD-silent, acyclic 1:2 1-saccharide complexes at high guest concentration. The possible binding modes are discussed in detail on the basis of molecular mechanics calculations and chemical shift changes in 1H NMR spectra. The results of competition experiments with several cationic reference compounds bearing fewer OH groups than 2-4 are consistent with the proposed binding model. Thus, the present study is a rare example of saccharide recognition in a protic solvent, where in general, hydrogen-bonding interactions are rarely useful because of strong solvation energy. These are apparently the strongest saccharide complexes involving noncovalent interactions between host and guest. We believe that the findings are significant as a milestone toward development of new saccharide recognition systems ultimately useful in aqueous solution. 相似文献
4.
Atsushi Ikeda Tsukasa HatanoToshifumi Konishi Jun-ichi KikuchiSeiji Shinkai 《Tetrahedron》2003,59(19):3537-3540
In a light-to-photocurrent conversion system based on a C60-porphyrin bilayer prepared by electrostatic alternate adsorption, porphyrin units in a porphyrin polymer have been isolated by cyclodextrin utilizing the host-guest interaction. In this system, a high quantum yield was achieved by suppression of self-quenching of porphyrin units. 相似文献
5.
Atsushi Ikeda Masaru Kawaguchi Yoshio Suzuki Tsukasa Hatano Munenori Numata Seiji Shinkai Akio Ohta Makoto Ohta 《Journal of inclusion phenomena and macrocyclic chemistry》2000,38(1-4):163-170
The calixarene-fullerene interaction,which causes only a slight change in the absorptionspectra, has been substantiated by calorimetricmeasurements: the H° values arecomparable with those obtained from the associationconstants estimated by a spectroscopic method. Furthermore, we determined the association constantbetween homooxacalix[3]arene and [60]fullerenederivatives with a porphyrin moiety by fluorescencespectra. 相似文献
6.
Kiyonaka S Sugiyasu K Shinkai S Hamachi I 《Journal of the American Chemical Society》2002,124(37):10954-10955
In materials science, a dynamic property sensitive to an environmental change (heat, light, electric current, pH, and other chemical or physical changes) is indispensable for intelligent materials. Such organic materials, however, are very limited even in conventional polymers. This paper clearly demonstrates that, regardless of the low molecular weight, a glycosylated amino acid derivative newly screened by a combinatorial method forms a macroscopic supramolecular hydrogel that reversibly swells or shrinks in response to the external temperature. Using the unique thermal response of the present hydrogel, we carried out the controlled release of DNA and the perfect removal of bisphenol A from the polluted water. Recently, advanced supramolecular polymers, in which monomers are noncovalently connected, are expected to be highly advantageous over traditional polymers because of their tunable and recyclable characteristics. The present result newly confers a dynamic feature on the supramolecular polymers, which is desirable for the sophisticated application in many fields. 相似文献
7.
A convenient direct transformation of -nitrobenzyl 6-(1′-hydroxyethyl)-1-azabicyclo-(3.2.0)heptane-3,7-dione-2-carboxylate to -formimidoyl thienamycin utilizing the silylated derivative of -formimidoyl cysteamine is described. 相似文献
8.
Seiji Shinkai Youichiro Hara Osamu Manabe 《Journal of polymer science. Part A, Polymer chemistry》1982,20(4):1097-1105
Three thiazolium-containing polymers, Th-7, Th-33, and Th-18-Py [where Th-x and Py mean x mol % thiazolium unit and pyridinium unit (54 mol %), respectively], were synthesized from partially p-chloromethylated polystyrene. The catalytic activities of these polymer catalysts in acyloin condensation of aldehydes and decarboxylation of α-keto acids were estimated kinetically by oxidative trapping of the key intermediate by flavin (flavin-trapping technique). In aqueous solution at 30°C, the catalytic activity of Th-18-Py and Th-33 in condensation of p-chlorobenzaldehyde was comparable with that of the cationic-micelle-bound thiazolium ion, whereas Th-7 and a monomeric thiazolium compound (N-benzylthiazolium bromide) scarcely exhibited any catalytic activity. The catalysis of the polymer-bound thiazolium ions was sensitively suppressed by increased ionic strength. These results suggest that the pendent thiazolium ion is activated by the relatively high charge density along the polymer chain: the cationic environment is able to facilitate dissociation of the thiazolium ion to the ylid form and deprotonation of the thiazolium-aldehyde adduct to the key intermediate. 相似文献
9.
Organic templates for the generation of inorganic materials 总被引:6,自引:0,他引:6
van Bommel KJ Friggeri A Shinkai S 《Angewandte Chemie (International ed. in English)》2003,42(9):980-999
Mankind's fascination with shapes and patterns, many examples of which come from nature, has greatly influenced areas such as art and architecture. Science too has long since been interested in the origin of shapes and structures found in nature. Whereas organic chemistry in general, and supramolecular chemistry especially, has been very successful in creating large superstructures of often stunning morphology, inorganic chemistry has lagged behind. Over the last decade, however, researchers in various fields of chemistry have been studying novel methods through which the shape of inorganic materials can be controlled at the micro- or even nanoscopic level. A method that has proven very successful is the formation of inorganic structures under the influence of (bio)organic templates, which has resulted in the generation of a large variety of structured inorganic structures that are currently unattainable through any other method. 相似文献
10.
Numata M Asai M Kaneko K Bae AH Hasegawa T Sakurai K Shinkai S 《Journal of the American Chemical Society》2005,127(16):5875-5884
We have found that single-chain schizophyllan and curdlan (s-SPG and s-curdlan, respectively) can dissolve as-grown and cut single-walled carbon nanotubes (ag-SWNTs and c-SWNTs, respectively) in aqueous solution. The vis-NIR spectra of the composites suggest that c-SWNTs are dissolved as a bundle, whereas ag-SWNTs exist as one or only a few pieces in the tubular hollow constructed by the helical structure inherent to these beta-1,3-glucans. EDX and CLSM measurements and TEM observation established that the distribution map of these polysaccharides overlaps well with the image of SWNTs, indicating that these two components form a composite. Very interestingly, when c-SWNTs were dissolved with the aid of s-SPG or s-curdlan in water, a clear periodical structure with inclined stripes, as detected by AFM, appeared on the fibrous composite surface. Because this periodical structure has never been recognized for the composites with other water-soluble polymers, one can regard that s-SPG or s-curdlan wraps c-SWNTs constructing a helically twined structure. High-resolution TEM observation of an ag-SWNTs/s-SPG composite gave a clearer image in that two s-SPG chains twine one ag-SWNT and the helical motif is right-handed. When this sample was subjected to the AFM measurement, the composite showed the 2-3 nm height. This height implies that one piece of ag-SWNT is included in the s-SPGs helical structure. As a summary, it has been established that beta-1,3-glucans such as s-SPG and s-curdlan not only dissolve SWNTs but also create a novel superstructure on the surface. 相似文献