Thank you for visiting nature.com. You are using a browser version with limited support for CSS. To obtain
the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in
Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles
and JavaScript.
Three cyclic oxoester-thioester hybrid monomers were studied for anionic and cationic ring-opening polymerizations. Anionic polymerizations using thiol with 2,6-lutidine were successful for the chemoselective cleavage of the thioester with the thiol propagating end, exhibiting the living character to some extent. The polymerization in 2,6-lutidine without an initiator produced macrocyclic polymers. The cationic polymerizations occurred with the aid of CF3SO3H and benzyl alcohol but involved side reactions with low chemoselective ring cleavage. The thioester unit caused the polymers to exhibit a lower Tg with greater thermal and photo degradability.
The thiol-Michael polyaddition of three dialkynyl monomers with several dithiols proceeded using triethylamine as the catalyst to give unsaturated poly(ester-thioether)s with the expected structures (Mn, 2.4 × 103 to 22.6 × 103; molecular dispersity index [Mw/Mn], 1.26–2.00). All of the poly(ester-thioester)s had single glass-transition temperature values between −27 and 49 °C. While the rigid main chains improved the glass transition temperature, all of the poly(ester-thioester)s showed apparent enzymatic hydrolysis by lipase but low biodegradability in biodegradation tests using activated sludge.
Simple control of the thermoresponsive properties of polymers in water over a broad range is achieved by using a designed urethane-containing acrylamide monomer in combination with a hydroxy-containing precursor monomer, which forms a statistical sequence due to its similar backbone. The copolymers exhibited a lower critical solution temperature-type responsive behavior in water, and the effects of structural factors such as composition, molecular weight, end groups and side-chain structure in urethane monomers were systematically evaluated.
Schematic illustrations of the alignment behavior induced by SWaP. Photopolymerization was conducted with a scanned UV slit light. Uniaxial molecular alignment was induced when the polymer concentration in the exposure area was high, while it was random when the polymer concentration was low.
Natural rubber exhibits the strain-induced crystallization (SIC). By using WAXD, the orientation of NR crystal formed by SIC under planar elongation was revisited. We found that the orientational state of the crystal lattice possesses a continuous margin of the orientation angle between 6.4 and 19.6° for the ac plane with respect to the surface of the specimen sheet in the real NR specimen. This orientational state could be accomplished as a result of balancing the preferential parallel orientation of (120) planes (the slip planes) and C = C planes with respect to the surface of the specimen sheet.
Doping lanthanides into lamellar crystals of diacetylene derivatives with terminal carboxylic acids reorganized the lamellar structure and dramatically changed the crystal morphology. Detailed investigation of the crystal growth process revealed that the complexes of lanthanide and diacetylene derivatives, which are slightly formed in the solution phase during lanthanide doping, may act as a pseudonuclear agent and change the morphology of the lamellar crystals. Furthermore, the morphology changes of the lamellar crystal films significantly altered surface properties such as film appearance and water repellency.
The Suzuki–Miyaura coupling reaction of BrC6H4-SiRR’-C6H4Br 1 with phenylboronic acid 3 in the presence of tBu3PPd precatalyst 4 and CsF/18-crown-6 produced a phenyl-disubstituted product, indicating that the Pd catalyst underwent catalyst transfer on the silylene group. The polycondensation of 1 and phenylenediboronic acid 2 yielded cyclic polymers even when excess 1 was used. The obtained cyclic polymers containing the silylene group showed stronger fluorescence in solution than did the methylene counterpart.
The surface properties of the star polymer coating were evaluated with their resistance to protein adsorption and surface zeta (ζ)-potential to clarify the mechanism for inhibition of cell adhesion. The surface of the star polymer coating with a high density of poly(2-hydroxyethyl methacrylate) formed an electrically neutral diffuse brush structure in water and showed high resistance to protein adsorption. Considering the data obtained in the study, the surface ζ-potential and antibiofouling properties were correlated by controlling the molecular architecture of the coating material.
