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        Synthesis of Dual Stimuli-Responsive Polymers Through Atom Transfer Radical Mechanism in Aqueous Media

        Abu B. Siddique,안진욱,김현준,박형종,이영진,이건창,강호중,이재열,김세훈,김정안 한국고분자학회 2017 Macromolecular Research Vol.25 No.1

        New dual stimuli-responsive (thermo- & pH-) polymers were successfully synthesized through an atom transfer radical mechanism in aqueous media. N-Isopropylacrylamide (NiPAM) ([N]) as a precursor of temperatureresponsive moiety and sulfonamide-modified styrenic monomer and methacrylamide ([S]) were employed for the synthesis of the smart copolymers. The molar ratio of NiPAM to sulfonamide composed of the polymer backbone played an important role in the control of the phase transitional behavior of the formed block polymers. When the composition ratio of [S]/[N] decreases from 1/1 to 1/2, the dual stimuli-responsive phase behavior was clearly observed. Another important factor for the control of the phase morphology was to obtain the reactivity ratios, r1 and r2, of the two monomers. In this study, Cu(I)-catalyzed copolymerization of sulfadimethoxinyl methacrylamide (MASX; M1) and NiPAM (M2) as the precursors of smart materials yielded r1 = 8.046 and r2=1.572, leading to the production of a gradient type of copolymer in aqueous media.

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        Michael Addition of Thiol Compounds on ω-Maleate Poly(ethylene oxide)s: Model Study for the “Site-Specific” Modification of Proteins

        윤홍빈,이유라,서동화,김새온,Abu B. Siddique,이재열,임지우,김정안 한국고분자학회 2018 Macromolecular Research Vol.26 No.2

        In this study, we successfully synthesized ω-maleate poly(ethylene oxide)s (PEOs) as the modifier for proteins through the thiol-ene Michael addition reaction. Both α-azido-ω-maleate PEO and α-t-butoxy-ω-maleate PEO were obtained from the reaction of ‘living’ polymeric alkoxides with maleic anhydride (over 98 mol%). To examine their availability as one of basic matrices for the thiol-ene Michael addition, model compounds as the precursors of protein carrying the thiol group such as thioacetic acid, cysteamine, and cysteine were employed. Their addition on the maleate group was over 98 mol% under sonication or ultraviolet (UV) irradiation. The acidic condition appeared to affect to yield a diastereomeric mixture. All the PEOs carrying the ω-maleate group appeared to be applied for the efficient modifiers in the “sitespecific” PEGylation of peptides or proteins. All the functionalized PEOs including ω-succinate PEO were characterized by a combination of size exclusion chromatographic (SEC), 1H nuclear magnetic resonance (NMR), and Fourier transform-infrared (FT-IR) spectroscopic analyses.

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