Hydrolyzation-Triggered Ultralong Room-Temperature Phosphorescence in Biobased Nonconjugated Polymers.

Amorphous nonconjugated room-temperature phosphorescent (RTP) polymers have aroused ever-increasing attention. However, the variety of such polymers is still rare due to limited preparation strategies. Herein, we report a facile strategy to achieve ultralong RTP emission in biobased nonconjugated polymers through a hydrolyzation process. The investigated polymers are synthesized by free radical solution copolymerization using biomass methyl isoeugenol and maleic anhydride as monomers. Noticeably, the obtained polymers carry no conventional fluorescent units but can exhibit blue fluorescence. More interestingly, after hydrolysis in sodium hydroxide aqueous solution, the resulting hydrolyzed polymers emit both enhanced blue emission and persistent RTP (up to 400 ms) under air conditions, with reversible emission performance switched via the uptake and removal of water. Also worthy to be highlighted is that the emission can be remarkably regulated by the cations in carboxylate or the substituents on the benzene ring. The as-obtained polymers demonstrate potential applications in anticounterfeiting and information encryption.

Polylactide-Based Chiral Porous Monolithic Materials Prepared Using the High Internal Phase Emulsion Template Method for Enantioselective Release.

Polylactide [PLA, two enantiomers: poly(l-lactide) (PLLA) and poly(d-lactide) (PDLA)] has been widely applied as biomaterials because of its biocompatibility, biodegradability, and good mechanical capacity. However, the chirality of PLA materials has not been intensively explored yet. In the present study, chiral porous poly(high internal-phase emulsion)s (polyHIPEs) derived from enantiopure PLAs were successfully prepared via a HIPE template method. The resulting polyHIPEs show optical activity. More interestingly, the polyHIPEs demonstrate enantioselective release capacity, using cinchona alkaloid and naproxen as the model chiral drugs. Notably, PLLA-based polyHIPE shows enantioselectivity in both the drug-loading step and drug-releasing step, while PDLA-based polyHIPE fails. The interesting finding is essentially different from other chiral polymer materials reported earlier. The cytotoxicity test demonstrates that all the three types of polyHIPEs, PLLA-, PDLA-, and PDLLA-based polyHIPE show biocompatibility; however, their different chirality exerts varying effects on cell growth. Accordingly, special attention should be devoted to the chirality of PLA when used as biomaterials.

Poly(N,N-dimethylacrylamide-octadecyl acrylate)-clay hydrogels with high mechanical properties and shape memory ability.

As a type of important intelligent materials, shape memory hydrogels (SMHs) have gathered a lot of interest due to their promising applications. However, preparing SMHs with excellent mechanical properties still remains a big challenge. In this study, a new type of SMHs with excellent mechanical strength is created. The SMHs were prepared by free radical micellar polymerization of hydrophobic monomer (octadecyl acrylate) with gelatin as emulsifier in a aqueous system containing hydrophilic monomer (N,N-dimethylacrylamide, DMA) and clay as reinforcing filler. The polymerization provided physically cross-linked network structures constructed by two non-covalent interactions, i.e. hydrophobic association formed by monomer units and multiple H-bonds among inorganic clay, gelatin and DMA. A judicious combination of the two physically cross-linked networks significantly improved the mechanical strength of hydrogels. More interestingly, the hydrogels demonstrated shape memory behavior due to the hydrophobic poly(octadecyl acrylate) domains. The novel SMHs are expected to find practical applications as biomaterials.

Biomass Vanillin-Derived Polymeric Microspheres Containing Functional Aldehyde Groups: Preparation, Characterization, and Application as Adsorbent.

The contribution reports the first polymeric microspheres derived from a biomass, vanillin. It reacted with methacryloyl chloride, providing monomer vanillin methacrylate (VMA), which underwent suspension polymerization in aqueous media and yielded microspheres in high yield (>90 wt %). By controlling the N2 bubbling mode and by optimizing the cosolvent for dissolving the solid monomer, the microspheres were endowed with surface pores, demonstrated by SEM images and mercury intrusion porosimetry measurement. Taking advantage of the reactive aldehyde groups, the microspheres further reacted with glycine, thereby leading to a novel type of Schiff-base chelating material. The functionalized microspheres demonstrated remarkable adsorption toward Cu(2+) (maximum, 135 mg/g) which was taken as representative for metal ions. The present study provides an unprecedented class of biobased polymeric microspheres showing large potentials as adsorbents in wastewater treatment. Also importantly, the reactive aldehyde groups may enable the microspheres to be used as novel materials for immobilizing biomacromolecules, e.g. enzymes.