Takaya Terashima

Enzymes are a source of inspiration for chemists attempting to create versatile synthetic catalysts. In order to arrive at a polymeric chain carrying catalytic units separated spatially, it is a prerequisite to fold these polymers in water into well-defined compartmentalized architectures thus creating a catalytic core. Herein, we report the synthesis, physical properties, and catalytic activity of a water-soluble segmented terpolymer in which a helical structure in the apolar core is created ar

Amphiphilic random methacrylate copolymers, consisting of poly(ethylene glycol) (PEG) and alkyl pendent groups, undergo reversible single-chain self-folding in water via intramolecular hydrophobic interaction, to generate a dynamic unimolecular hydrophobic nanospace, similar in shape but structurally different relative to micelles and microgel star polymers. These copolymers were prepared by the ruthenium-catalyzed living radical copolymerization of a PEG methacrylate (PEGMA) and an alkyl methac

Star polymers containing ruthenium complex in the core were prepared by ruthenium-catalyzed living radical polymerization, where the metal catalysts were directly encapsulated on linking reactions of living poly(MMA) in the presence of ethylene glycol dimethacrylate as a linker and diphenyl-4-styrylphosphine as a ligand incorporated in the core. The products were characterized by SEC/MALLS, UV-vis, NMR, AFM, TEM, and ICP-AES and were employed as polymer catalysts for the oxidation reaction of al

Amphiphilic and thermosensitive star polymers with Ru(II) complex−encapsulating microgel cores were directly synthesized in high yield via RuCl2(PPh3)3-catalyzed living radical polymerization. For the solvo- and thermal responsiveness, the arms stem from a block copolymer of poly(ethylene glycol) methyl ether methacrylate (PEGMA) with a small amount of methyl methacrylate. For the metal encapsulation into the core, a phosphine-ligand monomer [CH2CH(C6H4)PPh2] was “copolymerized” with a divinyl c

Self-assembly of hydrophilic poly(ethylene glycol) and hydrophobic dodecyl-graft amphiphilic copolymers in water was investigated in detail, by focusing on the effects of the monomer sequence and chain flexibility on micelles.

Versatile self-assembly systems to nanostructured materials in both solid and solution were developed with common amphiphilic random copolymers bearing hydrophilic poly(ethylene glycol) (PEG) and hydrophobic crystalline octadecyl pendants. The copolymers efficiently induced precision self-assembly of the pendants to provide not only core-crystalline, thermoresponsive micelles and vesicles in water and reverse micelles in hexane but also sub-10 nm lamellar or spherical microphase separation struc

Amphiphilic/fluorous random copolymers bearing poly(ethylene glycol) chains and perfluorinated alkane pendants were developed as novel non-cytotoxic polymeric materials for protein conjugation.

Abstract Thermoregulated phase‐transfer catalysis for the transfer hydrogenation of 2‐octanone in 2‐propanol/H 2 O biphasic media was achieved with ruthenium‐bearing microgel‐core star polymers with amphiphilic, thermosensitive poly(ethylene glycol) (PEG) arms [Ru(II)‐PEG star], which were directly prepared by the ruthenium‐catalyzed living radical polymerization in conjunction with a phosphine ligand‐carrying styrene derivative. The star polymers were first placed in the aqueous (lower) layer a

A star is born: Star polymer catalysts that carry a versatile microgel-core reaction vessel were obtained from catalyst interchange, coupled with ruthenium-catalyzed living radical polymerization, in situ hydrogenation, and removal and introduction of metals (see picture). Thanks to the catalyst encapsulation in the unique environment, the star catalysts show high activity, versatility, functionality tolerance, and recyclability in living radical polymerization.

Amphiphilic random copolymers comprising different hydrophilic poly(ethylene glycol) (PEG, average number of oxyethylene units = 4.5 or 8.5) and hydrophobic butyl or dodecyl pendants were designed to investigate self-folding and self-assembly behavior in water. The copolymers with controlled composition and chain length were synthesized by ruthenium-catalyzed living radical copolymerization. We revealed that the pendant design was one of the most critical factors to selectively induce intramolec

Amphiphilic random copolyacrylamides bearing hydrophilic poly(ethylene glycol) (PEG) and hydrophobic dodecyl pendants induce precision self‐assembly to produce quite small uniform and/or necklace micelles (≈10 nm) in water. The size, structure, and thermoresponsive properties of the micelles are controlled by the primary structure (composition and chain length) of the copolymers. For this, random copolymers with different composition, chain length, and molecular weight distribution are synthesiz

Abstract One‐pot, spontaneous, and in‐situ incorporation of Ru(II) complexes into a microgel (solubilized nanometer‐scale network) has been achieved in near quantitative efficiency by a polymer‐linking reaction of linear living poly(methyl methacrylate) (PMMA) with a bifunctional methacrylate (ethylene glycol dimethacrylate or bisphenol A dimethacrylate; linking agent) and a phosphine‐ligand monomer [diphenyl‐4‐styryl‐phosphine ( 3 ); i.e., CH 2 CHC 6 H 4  p ‐PPh 2 ] in the RuCl 2 (PPh 3 ) 3

Amphiphilic random copolymers bearing hydrophilic poly(ethylene glycol) (PEG) and hydrophobic alkyl pendants showed dynamic self-sorting behavior, that is, self-recognition, under competitive conditions in aqueous media. The self-sorting universally takes place not only in water but also in hydrogels and on the material surfaces, according to encoded information originating from the primary structure of composition and pendants. Binary blends of the copolymers with different composition or alkyl