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41.
Frantisek Mikes Hongxiang Teng Yasuhiro Koike Yoshiyuki Okamoto 《Journal of polymer science. Part A, Polymer chemistry》2012,50(22):4717-4720
Copolymerizations of hexafluoroisobutylene (HFIB) with vinyl pentafluorobenzoate (VPFB) and vinyl trifluoroacetate (VTFA) were carried out in bulk using perfluorodibenzoyl peroxide as the radical initiator. The copolymers obtained were characterized by proton and fluorine NMR spectroscopy. The monomer reactivity ratios in the polymerization of HFIB with VPFB were r1 (HFIB) = 0, r2 (VPFB) = 0.373, and r1r2 = 0. The results indicated that these copolymers have alternating structures. Similarly, the copolymers of HFIB and VTFA also showed alternating structures. The films of HFIB‐co‐VPFB were prepared by casting THF solution of polymers. Films obtained were flexible and transparent. The refractive indices of copolymers were 1.4549, 1.4490, and 1.4438 at 532, 633, and 839 nm, respectively. The average Tgs of HFIB‐co‐VTFA and HFIB‐co‐VPFB were 52 and 71 °C, respectively. From these results, the Tg of the hypothetical HFIB homopolymer is postulated to be in between 70 and 90 °C, which may be useful in the assessment of Tgs of HFIB copolymers with other vinyl monomers. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
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43.
Taichi Koike Dr. Tomoyuki Kosai Prof. Dr. Takeaki Iwamoto 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(39):9295-9302
Cyclic (alkyl)(amino)silylene (CAASi) 1 has been found to successfully dehydrogenate 1,4-dihydroaromatic compounds containing various substituents to afford the corresponding aromatic compounds. The observed high substrate generality proves 1 to be a potential 1,4-dehydrogenation reagent for organic compounds. For the reaction with 9,10-dimethyl-9,10-dihydroanthracene, silylene 1 activated not only benzylic C−H bonds but also aromatic C−H bonds to yield a silaacenaphthene derivative, which is an unprecedented reaction of silylenes. The results of the experimental and computational study of the reaction of CAASi 1 with 9,10-dihydroanthracene and 1,4-cyclohexadiene are consistent with the notion that 1,4-dehydrogenation with CAASi 1 proceeds mainly through a stepwise hydrogen-abstraction mechanism. 相似文献
44.
Copolymers of pentafluorophenylhexafluoroisopropyl methacrylate (FPPMA) with trifluoroethyl methacrylate (TFEMA) were prepared in THF solution and in bulk using azobisisobutyronitrile as a free radical initiator. The monomer reactivity ratios of TFEMA (M1) and FPPMA (M2) were calculated as r1 = 0.55 and r2 = 0.07. The refractive indices of poly(TFEMA) and poly(FPPMA) are very similar as 1.435 and 1.430, respectively, at 532 nm, and the copolymer films were transparent. The glass transition temperatures (Tg) of the copolymers were in the range of 80–90°C and showed a negative deviation from the Gordon–Taylor equation. The thermal decomposition temperature (Td) was increased with the content of FPPMA in copolymers. Low water absorption for 1:1 FPPMA/TFEMA copolymer was detected. Copolymers of FPPMA with hexafluoroisopropyl methacrylate (HFPMA) were also prepared. The monomer reactivity ratios of HFPMA (M1) and FPPMA (M2) were calculated as r1 = 0.43 and r2 = 0.10. The Tgs of the copolymers were in the range of 88–95°C and showed also a negative deviation from the Gordon–Taylor equation. Tg and Td of the copolymers were increased with the content of FPPMA. The refractive index of poly(HFPMA) (1.384 at 532 nm) is much lower than that of FPPMA homopolymer, but copolymer films obtained were clear and transparent. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
45.
Eiichi Kimura Naomi Katsube Tohru Koike Motoo Shiro Shin Aoki 《Supramolecular chemistry》2013,25(2-3):95-102
We have previously shown that the nucleobase thymine binding to Zn2+ -cyclen (cyclen=1,4,7,10-tetraazacyclododecane) complex became stronger by appending acridine, naphthalene, or quinoline rings to the cyclen. Amongst these, the pendant bis((1-naphthyl)methyl) or bis((4-quinolyl)methyl) groups yielded the most effective thymine-recognizing Zn2+ -cyclen complexes [J. Am. Chem. Soc., 121 (1999) 5426]. The present study was undertaken to find causes of the bis(aromatic) ring effect by X-ray crystal structure analysis and NMR studies. The crystal structure of the Zn2+ -bis((1-naphthyl)methyl)-cyclen complex with a deprotonated 1-methylthymine (1-MeT) failed to show the anticipated evidence for the double ~ - ~ stacking interactions between the two naphthalenes and the Zn 2+ -bound 1-MeT m (1-MeT m =N(3')-deprotonated 1-MeT). Crystal data: formula C36 H47 N7 O7 Zn, M r =755.19, monoclinic, space group P21/ c (No. 14), a =15.438(2) Å, b =14.093(3) Å, c =16.726(2) Å, g =90.53(1) V =3638.7(8) Å 3 Z =4, R =0.035, R w =0.049. However, the 1H NMR studies of Zn2= -bis((4-quinolyl)methyl)-cyclen with 1-MeT in varying H2O/CH3 CN solution showed increasing upfield shifts of Me(5') and H(6') of the Zn2+ -bound 1-MeT in more aqueous media, indicating that the double intercalation with the two quinolines became more significant in more protic environments. We conclude that the double ~ - ~ stacking effect accounts for the enhanced recognition of thymine base by the appended bis((1-naphthyl)methyl) or bis((4-quinolinyl)methyl) groups. 相似文献
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In this paper, we propose a method to accelerate the crystallisation of nematic liquid crystal mixtures based on crystallisation theory. This method is to hold a nematic liquid crystal sample at a temperature suitable for crystal growth after aging it at a temperature suitable for nucleation. After we specified these temperatures of a nematic liquid crystal mixture using differential scanning calorimetry, we demonstrate that the two-temperature aging method is effective for the crystallisation of other nematic liquid crystal mixtures in which the crystal-liquid crystal transition temperature has so far been undetectable. 相似文献
48.
Dr. Yuki Kishimoto Dr. Osamu Nakagawa Akane Fujii Dr. Kotaro Yoshioka Dr. Tetsuya Nagata Prof. Dr. Takanori Yokota Prof. Dr. Yoshiyuki Hari Prof. Dr. Satoshi Obika 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(7):2427-2438
Artificial nucleic acids are widely used in various technologies, such as nucleic acid therapeutics and DNA nanotechnologies requiring excellent duplex-forming abilities and enhanced nuclease resistance. 2′-O,4′-C-Methylene-bridged nucleic acid/locked nucleic acid (2′,4′-BNA/LNA) with 1,3-diaza-2-oxophenoxazine (BNAP ( BH )) was previously reported. Herein, a novel BH analogue, 2′,4′-BNA/LNA with 9-(2-aminoethoxy)-1,3-diaza-2-oxophenoxazine (G-clamp), named BNAP-AEO ( BAEO ), was designed. The BAEO nucleoside was successfully synthesized and incorporated into oligodeoxynucleotides (ODNs). ODNs containing BAEO possessed up to 104-, 152-, and 11-fold higher binding affinities for complementary (c) RNA than those of ODNs containing 2′-deoxycytidine ( C ), 2′,4′-BNA/LNA with 5-methylcytosine ( L ), or 2′-deoxyribonucleoside with G-clamp ( PAEO ), respectively. Moreover, duplexes formed by ODN bearing BAEO with cDNA and cRNA were thermally stable, even under molecular crowding conditions induced by the addition of polyethylene glycol. Furthermore, ODN bearing BAEO was more resistant to 3′-exonuclease than ODNs with phosphorothioate linkages. 相似文献
49.
Graded‐index plastic optical fibers, composed of doped polymers, have advantages over conventional glass optical fibers, but need to be developed further for practical application. Here, a variety of aromatic sulfide dopants were synthesized, and their effects on the refractive indexes and glass transition temperatures (Tg) of poly(methyl methacrylate) and methyl 2‐chloroacrylate/2,2,2‐trichloroethyl methacrylate copolymers were studied. While polymers containing large dopants exhibited relatively high refractive indices, their Tg values were low, making these materials unsuitable for graded‐index plastic optical fiber applications. Six dopants yielded polymers that exhibited higher Tg values than the conventionally used (diphenyl sulfide)‐doped polymer. The dopant dibenzothiophene, in particular, yielded polymers with the highest refractive indexes and Tg values, and polymers containing (phenylthio)benzene dopants also performed well. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
50.
Mesoporous Silica Particles as Topologically Crosslinking Fillers for Poly(N‐isopropylacrylamide) Hydrogels 下载免费PDF全文
Prof. Nobuyoshi Miyamoto Kotaro Shimasaki Kosuke Yamamoto Morio Shintate Yuichiro Kamachi Dr. Bishnu Prasad Bastakoti Dr. Norihiro Suzuki Dr. Ryuhei Motokawa Prof. Yusuke Yamauchi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(46):14955-14958
Here it is demonstrated that mesoporous silicas (MPSs) can be used as effective “topological crosslinkers” for poly(N‐isopropylacrylamide) (PNIPA) hydrogels to improve the mechanical property. Three‐dimensional bicontinuous mesporous silica is found to effectively reinforce the PNIPA hydrogels, as compared to nonporous silica and two‐dimensional hexagonally ordered mesoporous silica. 相似文献