全文获取类型
收费全文 | 268篇 |
免费 | 9篇 |
国内免费 | 1篇 |
专业分类
化学 | 202篇 |
力学 | 1篇 |
数学 | 19篇 |
物理学 | 56篇 |
出版年
2021年 | 3篇 |
2020年 | 5篇 |
2019年 | 4篇 |
2018年 | 4篇 |
2017年 | 2篇 |
2016年 | 5篇 |
2015年 | 5篇 |
2014年 | 5篇 |
2013年 | 8篇 |
2012年 | 16篇 |
2011年 | 16篇 |
2010年 | 13篇 |
2009年 | 7篇 |
2008年 | 16篇 |
2007年 | 20篇 |
2006年 | 15篇 |
2005年 | 16篇 |
2004年 | 7篇 |
2003年 | 11篇 |
2002年 | 14篇 |
2001年 | 10篇 |
2000年 | 13篇 |
1999年 | 3篇 |
1998年 | 5篇 |
1997年 | 3篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1993年 | 8篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 1篇 |
1989年 | 4篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1977年 | 3篇 |
1975年 | 1篇 |
1971年 | 1篇 |
1968年 | 2篇 |
1966年 | 1篇 |
1963年 | 1篇 |
1962年 | 1篇 |
1935年 | 1篇 |
排序方式: 共有278条查询结果,搜索用时 15 毫秒
1.
2.
Katsuhiro Inomata Chieko Fukuda Kuniyoshi Hori Hideki Sugimoto Eiji Nakanishi 《Journal of Polymer Science.Polymer Physics》2007,45(2):129-137
The phase behavior and crystallization of graft copolymers consisting of poly(n‐hexyl methacrylate) (PHMA) as an amorphous main chain and poly(ethylene glycol) (PEG) as crystallizable side chains (HMAx with 15 ≤ x ≤ 73, where x represents the weight percentage of PEG) were investigated. Small‐angle X‐ray scattering profiles measured above the melting temperature of PEG suggested that a microdomain structure with segregated PHMA and PEG domains was formed in HMA40 and HMA46. This phase behavior was qualitatively described by a calculated phase diagram based on the mean‐field theory. Because of the segregation of PEG into microdomains, the crystallization temperature of the PEG side chains in HMAx was higher than that in poly(methyl acrylate)‐graft‐poly(ethylene glycol) having a similar value of x, which was considered to be in a disordered state above the melting temperature. In HMAx with x ≤ 40, PEG crystallization was strongly restricted, probably because the PEG microdomains were isolated in the PHMA matrix. As a result, the growth of PEG spherulite was not observed because the PEG crystallization occurred after vitrification of the PHMA segregated domains. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 129–137, 2007 相似文献
3.
A novel type of heterogenized CuCl2 catalysts was designed for the oxidative carbonylation of methanol to dimethyl carbonate (DMC) taking account of the plausible reaction mechanism and intermediates. To prevent severe corrosion of the reaction equipment materials due to Cl– while keeping the catalytic activity of the homogeneous CuCl2 catalyst, we adopted, as supports (or ligands) of CuCl2, four polymers, bearing a 2,2-bipyridine (bpy) or pyridine (py) unit, namely, poly(2,2-bipyridine-5,5-diyl) (Pbpy), poly(pyridine-2,5-diyl) (Ppy), poly(N,N-bisphenylene-2,2-bipyridine-4,4-dicarboxylic amide) (Bpya), and poly(4-methyl-4-vinyl-2,2-bipyridine) (Pvbpy), together with one chelate compound, 8-quinolinol. The catalytic activity, stability of heterogenized CuCl2 and their corrosivities to stainless steels were examined in the liquid-phase reaction of the oxidative carbonylation of methanol. These polymer-supported catalysts showed considerable catalytic activity and stability for the DMC synthesis. In particular, the Pbpy-CuCl2 and Ppy-CuCl2 catalysts exhibited high DMC yields and selectivity comparable to those of the homogeneous CuCl2 catalyst. This high activity appears to be associated with the presence of the -conjugated system in the polymers, which affect the redox reactions of Cu involved in the catalytic reaction. All of the polymer-supported CuCl2 catalysts could be easily recycled after filtration, and the initial catalytic activity was maintained after three times of use. The corrosive characters of the catalysts were closely related to CuCl2 leaching from the supports, which reflects the ability of supports to coordinate Cu. These experimental results suggest that both the electronic structure and the coordination ability of the polymer supports are key factors for the development of an effective catalytic system. 相似文献
4.
Preparation and physical properties of flame retardant acrylic resin containing nano-sized aluminum hydroxide 总被引:1,自引:0,他引:1
Kazuki Daimatsu Yasunori Kato Katsuhiro Inomata Kazuki Takemura 《Polymer Degradation and Stability》2007,92(8):1433-1438
Poly(methylmethacrylate) (PMMA) shows high strength and transparency but is a flammable material. In this study, the surface of aluminum hydroxide was modified with methacrylate containing phosphoric acid moieties before dispersion in MMA, and organic-inorganic nano-hybrid materials were obtained by bulk polymerization in the presence of the surface-modified aluminum hydroxide. The resulting hybrid materials retained the high transparency of PMMA, with transparency values similar to that of pure PMMA. Moreover, the flame resistance of the hybrid materials was improved in comparison with that of pure PMMA, with depression of the horizontal burning rate becoming a maximum at an inorganic content of 3 wt%. These results suggest that the use of aluminum hydroxide surface-modified with phosphoric acid groups is an efficient method for obtaining good performance fire-resistant polymer materials. 相似文献
5.
Watanabe M Sue K Adschiri T Inomata H Smith RL Arai K 《Chemical communications (Cambridge, England)》2001,(21):2270-2271
In supercritical water the rate of methanol oxidation was controlled by ionic behavior as follows: the oxidation rate of methanol decreased with increasing proton and hydroxide ion concentration, possibly due to stabilization of the reactant, while that of CO was suppressed by added protons and enhanced by added hydroxide ions. 相似文献
6.
(Z)- and (E)-2-Ethoxyperfluoro-2-(phenylselenenyl)alk-2-enenitriles 2-4 prepared by our original method underwent transmetalation on treatment with n-BuLi or EtMgBr, and the successive reaction with aldehyde and ketones afforded the corresponding allylic alcohols 10a-f, 9a, and 11a,b in good to high yields. Hydrolysis of the alcohols gave alpha-cyano-alpha,beta-unsaturated perfluoroalkyl ketones 13a-c, 13e, 12a, and 15a. alpha-Cyanoperfluoroalkyl ketones were easily converted to alpha,beta-unsaturated 3-aryl-2-cyanoallylic alcohols 18-22 having interesting biological activities and chemical reactivities. 相似文献
7.
K. Kitamura Hideyuki Mano Yoshie Shimamoto Yoshihiro Tadokoro Koji Tsuruta Shinji Kitagawa 《Analytical and bioanalytical chemistry》1997,358(4):509-513
The second-derivative spectra of chlorpromazine (CPZ) or triflupromazine (TFZ) in buffer solutions (pH 7.4) containing various amounts of BSA (the reference solutions contained the same amount of BSA) showed derivative isosbestic points. The residual background signals derived from incomplete suppression of BSA signals can be entirely eliminated in the second-derivative spectra and BSA has spectrophotometrically one kind of binding site for CPZ or TFZ. The fractions of the drugs bound to BSA were calculated from the derivative intensity differences (ΔD values) of CPZ or TFZ before and after the addition of BSA. Scatchard plot experiments suggested that the binding of the drugs to BSA could be explained as a partition like non-specific binding model. The association constants (K) of CPZ or TFZ with BSA were calculated from the ΔD values according to the non-specific binding model by a nonlinear least-squares method. The K values were almost constant for all of the drug concentrations studied, and good reproducibility was obtained. The fractions predicted by the K values were in good coincidence to the observed values. These results confirm the usefulness of the proposed derivative method which does not need any separation procedures. 相似文献
8.
Improved synthesis of four stereoisomeric chiral 1,3-dimethyl-1,2,3,4-tetrahydroisoquinolines (1a, b, ent-1a, b) was achieved via the super acid-induced cyclization of chiral N-[1-methyl-2-(phenylsulfinyl)ethyl]-N-(1-phenylethyl)formamides (4a, b, ent-4a, b) using the Pummerer-type cyclization reaction as a key step. The cyclization leading to the isoquinoline ring proceeded in a quantitative manner when trifluoromethane sulfonic acid (TFSA) was used as the super acid, although Friedel-Crafts-type alkylation of 4-phenylsulfanyl TIQ derivatives (5) with benzene used as the solvent accompanied cyclization to yield the 4-phenyl-TIQs (7). The byproduct (7) was exclusively formed when a large excess amount of TFSA was used. 相似文献
9.
Ishikawa Y Matsumoto Y Nishida Y Taniguchi S Watanabe J 《Journal of the American Chemical Society》2003,125(21):6558-6562
Silicon carbide (SiC) and diamond were decomposed to CO(2)(g) by the photocatalysis with TiO(2) at room temperature, although the decomposition rate of diamond was very slow. According to the XPS spectra of Si2p on the SiC surface, SiO(2) was simultaneously formed on the surface by the TiO(2) photocatalysis. The thickness of the SiO(2) formed on the SiC surface during the photocatalytic oxidation for 1 h was estimated to be about 40 A from the depth profile of the XPS spectra using Ar etching. The SiC surface was oxidized by the TiO(2) photocatalysis even under the condition without a direct contact with the TiO(2). This indicates that the photocatalytic oxidation of the SiC occurs due to active oxygen species photogenerated on the TiO(2) surface, but not by hole produced in the valence band of the TiO(2). Moreover, a remote surface treatment system using the quartz beads coated with TiO(2) was developed for the SiC surface oxidation. Consequently, the TiO(2) photocatalysis will be very useful for the surface treatment of SiC such as photopatterning without defects and damage to the substrate because the photocatalytic reaction is carried out under mild conditions. 相似文献
10.
Copper(II) complex with
-piperidine-3-carboxylic acid (
-Hpipe-3):[Cu(
-pipe-3)2(H2O)] and cobalt(II) and nickel(II) complexes with piperidine-4-carboxylic acid (Hpipe-4):[M(Hpipe-4)2(H2O)4]Cl2 (M: Co, Ni) have been prepared and characterized by means of IR and powder diffuse reflection spectra, thermal analysis, and magnetic susceptibility. The crystal structures of these complexes have been determined by X-ray diffraction. The crystal of [Cu(
-pipe-3)2(H2O)] is orthorhombic with the space group Pbcn. The copper atom is in a square pyramidal geometry, ligated by two carboxylato oxygen atoms, two nitrogen atoms, and a water molecule. One molecule of this complex consists of either
-piperidine-3-carboxylic acid or
-piperidine-3-carboxylic acid. The crystals of [M(Hpipe-4)2(H2O)4]Cl2 are monoclinic with space group P21/n. In these complexes the metal atom is in an octahedral geometry ligated by two carboxylato oxygen atoms and four water molecules. 相似文献