全文获取类型
收费全文 | 760篇 |
免费 | 13篇 |
国内免费 | 5篇 |
专业分类
化学 | 602篇 |
晶体学 | 7篇 |
力学 | 10篇 |
数学 | 46篇 |
物理学 | 113篇 |
出版年
2019年 | 5篇 |
2016年 | 7篇 |
2015年 | 13篇 |
2014年 | 8篇 |
2013年 | 52篇 |
2012年 | 41篇 |
2011年 | 35篇 |
2010年 | 22篇 |
2009年 | 21篇 |
2008年 | 34篇 |
2007年 | 35篇 |
2006年 | 36篇 |
2005年 | 35篇 |
2004年 | 40篇 |
2003年 | 29篇 |
2002年 | 27篇 |
2001年 | 12篇 |
2000年 | 5篇 |
1999年 | 9篇 |
1998年 | 8篇 |
1997年 | 10篇 |
1996年 | 10篇 |
1995年 | 12篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 15篇 |
1991年 | 11篇 |
1990年 | 8篇 |
1989年 | 10篇 |
1988年 | 6篇 |
1987年 | 5篇 |
1986年 | 6篇 |
1985年 | 20篇 |
1984年 | 14篇 |
1983年 | 11篇 |
1982年 | 15篇 |
1981年 | 15篇 |
1980年 | 16篇 |
1979年 | 17篇 |
1978年 | 6篇 |
1977年 | 14篇 |
1976年 | 9篇 |
1975年 | 9篇 |
1974年 | 8篇 |
1973年 | 8篇 |
1972年 | 3篇 |
1970年 | 3篇 |
1967年 | 4篇 |
1960年 | 3篇 |
1930年 | 4篇 |
排序方式: 共有778条查询结果,搜索用时 421 毫秒
761.
Takeo Usui Sachiko Kojima Shun-ichi Kidokoro Kazunori Ueda Hiroyuki Osada Mikiko Sodeoka 《Chemistry & biology》2001,8(12):1209-1220
BACKGROUND: VHR is a dual-specificity phosphatase, which dephosphorylates activated ERK1/2 and weakens the ERK signaling cascade in mammalian cells. A selective inhibitor is expected to be useful for revealing the physiological function of VHR. RESULTS: First, we investigated the molecular mechanism of VHR inhibition by a known natural product, RK-682. Kinetic analysis indicated that inhibition was competitive toward the substrate, and two molecules of RK-682 were required to inhibit one molecule of VHR. Based on the structure-activity relationships for VHR inhibition by RK-682 derivatives, we constructed a binding model using molecular dynamics calculation. Based on this model, we designed and synthesized a novel dimeric derivative. As expected, the dimeric derivative showed increased inhibition of VHR, supporting our proposed mechanism of VHR inhibition by RK-682. CONCLUSION: We have developed a novel inhibitor of VHR based on the results of kinetic analysis and docking simulation. 相似文献
762.
Takeo Yamaguchi Shin-Ichi Nakao Shoji Kimura 《Journal of Polymer Science.Polymer Physics》1997,35(3):469-477
A model that can express the swelling of the filling-type membrane was developed by modifying a model that was developed for a crystalline polymer. The filling-type membrane is composed of two different polymers. One is porous substrate and another is a polymer that filled pores of the substrate. The filling technique can effectively suppress polymer swelling due to the substrate matrix. The model needs two parameters: one is a unit ratio of tie segments in the substrate to the filling polymer, f, which can express a mechanical strength of the substrate, and another is the Flory interaction parameter, χ, between the filling polymer and a solvent that expresses a mixing energy. A porous high-density polyethylene film was used as a porous substrate, and plasma-graft filling polymerization technique could make the filling-type membrane. Methylacrylate was used as a grafting monomer that filled the pores of substrate. A swelling behavior of the filling-type membrane and pure poly(methylacrylate) were measured by the vapor sorption method at different solvent activities. The model was in good agreement with experimental results for the filling-type membrane. Using the model, swelling of the filling-type polymer was compared with a crosslinked polymer, which can be expressed by Flory and Rehner model. The comparison showed that the filling technique is a good way to suppress polymer swelling, and a high crosslinking density is needed to obtain the same level of swelling suppression effect the filling type membrane showed. © 1997 John Wiley & Sons, Inc. 相似文献
763.
Takeo Shimidzu 《Macromolecular Symposia》1996,104(1):127-135
Approaches to polymer superlattice and molecular devices are shown, demonstrating with functional molecule material by incorporation of a functional molecule into the conducting polymer, conjugating copolymer superlattice by a novel potential programmed electro polymerization, ultrahigh anisotropic conductive LB heterolayers, and porphyrin arrays connected with conducting molecular wire and insulating molecular wire. These results show a practical method to fabricate ultimate functional materials such as molecular device which is the smallest functional material, and quantum functional material which creates a novel nature. 相似文献
764.
Bulk radical polymerization of styrene in the presence of nitronyl nitroxides (2-(4-substituted phenyl)-4,4,5,5-tetramethyl-4,5-dihydroimidazolyl-1-oxyl 3-oxide) was studied. All nitronyl nitroxides, like other nitroxyl radicals such as 2,2,6,6-tetramethylpiperidine 1-oxyl radical (TEMPO), act as reversible radical scavengers. The efficiency of controlling the polymerization is affected by the substituent at the 4′-position. The efficiency increases with electron donating strength of 4′-substituents, at least at the beginning of the reaction. However, the thermal stability of nitronyl nitroxides decreases in the same order. Thus, TEMPO is more suitable than nitronyl nitroxides for controlled/“living” radical polymerization of styrene. 相似文献
765.
766.
Masatoshi Miyamoto Keigo Aoi Takeo Saegusa 《Journal of polymer science. Part A, Polymer chemistry》1997,35(5):933-945
The cationic ring-opening polymerization of six-membered cyclic pseudoureas, 2-(1-pyrrolidinyl)- ( 2a ) and 2-morpholino-5,6-dihydro-4H-1,3-oxazine ( 2b ), was examined, which proceeded in two different ways, depending on the nature of initiator. The polymerization of 2 with methyl p-toluenesulfonate or trifluoromethanesulfonate (MeOTf) produced poly[(N-carbamoylimino)trimethylene], while that with benzyl chloride or bromide or methyl iodide gave a polymer consisting of 1,3-diazin-2-one-1,3-diylalkylene unit (the main component) and (N-carbamoylimino)trimethylene unit. The cationic ring-opening polymerization of seven-membered cyclic pseudourea, 2-(1-pyrrolidinyl)-4,5,6,7-tetrahydro-4H-1,3-oxazepine ( 3 ) was also examined. The polymerization of 3 with MeOTf as initiator gave poly{[N-(1-pyrrolidinycarbonyl)imino]tetra-methylene}. With benzyl chloride, on the other hand, no polymerization of 3 proceeded but, instead, the quantitative isomerization of 3 to 1,1′-carbonyldipyrrolidine took place. The polymerization mechanism of 2 and 3 as well as the isomerization mechanism of 3 were discussed with comparing them to the polymerization mechanism of five-membered pseudoureas. © 1977 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 933–945, 1997 相似文献
767.
Yuji Hanzawa Nobuhito Tabuchi Kosuke Saito Satoshi Noguchi Takeo Taguchi 《Angewandte Chemie (International ed. in English)》1999,38(16):2395-2398
The chiral monodentate phosphane ligand ( R )-MOP facilitated the first enantioselective nucleophilic 1,2-addition of an “unmasked” acyl anion to a carbonyl group in the PdII-catalyzed reaction of α,β-unsaturated ketones with acylzirconocene chlorides [Eq. (1), 66 % ee, 88 % yield; (R)-MOP=(R)-2-(diphenylphosphanyl)-2′-methoxy-1,1′-binaphthyl]. 相似文献
768.
769.
770.
This paper describes recent developments in polymerization of cyclic imino ethers, 2-oxazolines and 5,6-dihydro-4H-1,3-oxazines, which have been performed mainly in our laboratory. Cationic ring-opening polymerizations of these two kinds of monomers gave poly(N-acylethylenimine)s and poly(N-acyltrimethylenimine)s, whose hydrolysis produced linear poly-ethylenimine and poly(trimethylenimine), respectively. The mechanism of the polymerization is mainly governed by the nature of monomer and of the counter anion derived from initiator. There are two types of stable propagating species; cyclic onium species and covalent alkyl halide species. In a specific case, e.g., the polymerization of 5-methyl-2-oxazoline with MeI initiator, both ionic and covalent species are involved in equilibrium and propagate concurrently. Then, a new terminology of “Electrophile Polymerization” has been proposed as a broader expression including cationic and covalent propagating species. By utilizing living nature of the cyclic imino ether polymerization, block copolymerizations between these monomers were performed. A poly(cyclic imino ether) chain becomes hydrophilic or lipophilic depending on the monomer. Product AB and ABA type block copolymers were soluble in water and showed excellent surface properties reflected by values of surface tension (γ), when A (or B) and B (or A) are hydrophilic and lipophilic. Thus, various nonionic polymer surfactants of block and graft type have been prepared from cyclic imino ethers. Finally, poly(N-acetylethylenimine) chain showed good compatibility with poly(vinyl chloride). Cellulose diacetate and poly(vinyl chloride) are not miscible, but cellulose diacetate g-poly(N-acetylethylenimine) is miscible with poly(vinyl chloride), the graft chain acting as a “compatibilizer”. 相似文献