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1.
Takayuki Yaegashi Shinya Yodoya Masahiko Nakamura Hiroki Takeshita Katsuhiko Takenaka Tomoo Shiomi 《Journal of polymer science. Part A, Polymer chemistry》2004,42(4):999-1007
Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (Rp) equation was Rp ∝ [DEA]1.1[AIBN]0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r1 = 5.83 and r2 = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004 相似文献
2.
Atsuhiro Fujimori Mikako Ishitsuka Hiroo Nakahara Eisuke Ito Masahiko Hara Kaname Kanai Hisao Ishii Yukio Ouchi Kazuhiko Seki 《Journal of Polymer Science.Polymer Physics》2004,42(12):2329-2336
Photopolymerization of cadmium 10,12-pentacosadiynoate (CdDA) in Langmuir–Blodgett (LB) films, with the molecular packing well arranged by moderate preannealing, was investigated with near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. Greenish films of polydiacetylene with an absorption wavelength of 705 nm were obtained through the photopolymerization of preannealed monomer LB films, and this resulted in an extended π-conjugate system based on the well-ordered monomer in a two-dimensional arrangement. The electronic structures of the polydiacetylenes were found to be correlated to the variation of the molecular arrangements in the films from the changes in the NEXAFS spectra through photopolymerization in the LB films. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2329–2336, 2004 相似文献
3.
Yoshinori Nishiwaki Masahiko Shimoyama Toshio Nakanishi Toshio Ninomiya Izumi Nakai 《Analytical sciences》2006,22(10):1297-1300
Total reflection X-ray fluorescence spectrometry (TXRF) has been applied for trace elemental analysis of small glass fragments. A small glass sample (a fragment with weight less than 0.5 mg) was decomposed by 100 microg of HF/HNO3 acid; the material was condensed to 10 microl and was dried on a Si wafer. Since the size of the dried residue on the Si wafer was less than 1 cm in diameter, an incident X-ray beam with about 1 cm in width could effectively excite elemental components in such a small glass fragment. The precision of the present technique was checked by analyzing the glass fragments (<0.5 mg) from NIST SRM612; the relative standard deviations (RSD) of less than 8.1% were achieved for elemental ratios that were normalized by Sr. Fragments (<0.5 mg) obtained from 23 figured sheet glasses were used as samples for estimating the utility of this technique to forensic discrimination. Comparison of five elemental ratios of Ti/Sr, Mn/Sr, Zn/Sr, Rb/Sr, and Pb/Sr calculated from X-ray fluorescence spectra was effective in distinguishing glass fragments that could not be differentiated by their refractive indexes (RI). 相似文献
4.
5.
The anti-tumor agent, tamoxifen, is easily synthesized by the successive allylation of benzaldehyde and the Friedel-Crafts alkylation reaction of anisole with the intermediary homoallyl silyl ethers, followed by the migration of the double bond to form the desired tetra-substituted ethylenes. Several derivatives of tamoxifen are also produced according to a similar synthetic strategy. 相似文献
6.
Ahmed Jalal Uddin Yutaka Ohkoshi Yasuo Gotoh Masanobu Nagura Tetsuya Hara 《Journal of Polymer Science.Polymer Physics》2003,41(22):2878-2891
The effect of moisture on the mechanical relaxation processes of semiaromatic semicrystalline polyamides synthesized by a long‐chain aliphatic diamine and terephthalic acid was investigated by dynamic viscoelastic analysis (DVA) and differential scanning calorimetry (DSC). Moreover, the implication of moisture with the amorphous and crystalline domains was also examined by temperature‐dependent wide‐angle X‐ray diffraction and Fourier transform infrared spectra. The characteristics of the relaxations such as α, β, γ, and the pronounced peak shoulder appeared at 25–100 °C in DVA tan δ curves were found to be strongly susceptible to the presence of moisture. With moisture evaporation, the peak shoulder of 25–100 °C and the β‐relaxation disappeared. The former is anticipated to originate from to the side group motion of hydrogen‐bonded water, whereas the later one is from the motions of the amide–water complex units. With the disappearance of the β‐relaxation, the γ‐relaxation appeared simultaneously in much lower temperatures and ultimately coupled with the δ‐relaxation. The γ‐relaxation is attributed to be associated with the molecular motion of the amide group and δ‐relaxation with for the motion of the methylene units. The existence of two types of water was identified in the polymer, namely, tightly bound and loosely bound. The tightly bound water is believed to be directly connected by hydrogen bonding with the strong polar groups and the loosely bound water weakly links with those connected water making hydrogen bridges. The moisture acts as a plasticizer in the polymer matrix, which causes quite a large depression in its glass transition temperature (Tg). WAXD and FTIR studies corroborated the existence of water solely in amorphous regions, i.e., no rapport of water with the crystalline parts. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2878–2891, 2003 相似文献
7.
Using Gawedzki and Kupiainen's rigorous block spin transformation method, we study critical phenomena in 4 spin systems in four dimensions. In Part I of this work we investigate in detail the renormalization group trajectory of the system not exactly at the critical point. 相似文献
8.
Masahiko Kurihara Fumitoshi Hirayama Kaneto Uekama Masaki Yamasaki 《Journal of inclusion phenomena and macrocyclic chemistry》1990,8(4):363-373
Inclusion complexation of nocloprost, a potent antiulcer prostaglandin derivative, with -, -, and -cyclodextrins (CyDs) in aqueous solutions has been studied by the solubility method and13C-NMR spectroscopy. The steric requirement of host-guest interaction was reflected in the magnitude of the stability constants and the thermodynamic parameters of the inclusion complexes. Solid complexes of nocloprost with - and -CyDs in a molar ratio of 1 : 2 were obtained on the basis of aBs-type phase solubility diagram. The X-ray diffraction data suggested that nocloprost is included in the cylindrical channel formed by coaxial alignment of -CyD molecules to give a channel type structure. Release and thermal behavior of the solid complexes was examined and compared with nocloprost itself. The results indicated that the -CyD complex may have great utility among the three CyDs, being a rapid dissolving form of nocloprost with improved thermal stability. 相似文献
9.
(+)-Biotin (1) was synthesized in 25% overall yield over 11 steps from L-cysteine. The contiguous asymmetric centers at C-3a and C-6a were formed through a novel and highly stereoselective Lewis base-catalyzed cyanosilylation of alpha-amino aldehyde 3 to provide anti-O-TMS-cyanohydrin 4 with high stereoselectivity and in high yield (anti/syn = 92:8, 96%). Treatment of 4 with a di-Grignard reagent, 1,4-bis(bromomagnesio)butane, followed by carbon dioxide, efficiently installed the 4-carboxybutyl chain at C-4 to give keto acid 5. The final cyclization to bicyclic compound 7b, a precursor to 1, was realized by a palladium-catalyzed intramolecular allylic amination of cis-allylic carbonate 6b that was elaborated from 5. 相似文献
10.
A simple and rapid method for apolipoprotein analysis in serum high-density lipoproteins (HDL) has been developed using high-performance liquid chromatography (HPLC) with sodium phosphate buffer (pH 7.0) containing 0.1% sodium dodecyl sulphate (SDS) as eluent. In contrast to the use of urea solution as an eluent, apolipoproteins can be analysed by applying an incubation mixture of HDL and the eluent buffer. A TSK-GEL column of G3000SW was found to be more profitable than G2000SW or G4000SW for analysis of HDL apolipoproteins. Elution patterns monitored by absorbance at 280 nm using a G3000SW column can give precise quantitative as well as qualitative information about apolipoproteins of molecular weight between 10(4) and 10(5). HPLC patterns of HDL apolipoproteins were compared between individual human subjects with various diseases. Elution profiles for lipid components in an incubation mixture were also examined. 相似文献