Biomolecule-polymer conjugates are constructs that take advantage of the functional or otherwise beneficial traits inherent to biomolecules and combine them with synthetic polymers possessing specially tailored properties. The rapid development of novel biomolecule-polymer conjugates based on proteins, peptides, or nucleic acids has ushered in a variety of unique materials, which exhibit functional attributes including thermo-responsiveness, exceptional stability, and specialized specificity. Key to the synthesis of new biomolecule-polymer hybrids is the use of controlled polymerization techniques coupled with either grafting-from, grafting-to, or grafting-through methodology, each of which exhibit distinct advantages and/or disadvantages. In this review, we present recent progress in the development of biomolecule-polymer conjugates with a focus on works that have detailed the use of grafting-from methods employing ATRP, RAFT, or ROMP.

SYNOPSISAn attempt is made to develop a novel series of cable sheathing compounds with variation in chlorine content and sufficient fire retardance and unique low-smoke characteristics. These are prepared by blending PVC and functionalized polyolefins in different compositions. PE and EPDM have been functionalized by grafting dibutyl maleate (DBM) using DCP as initiator. FRLS compounds made from PVC-functionalized polyolefin blends possess the special characteristics of low-smoke, low-acid-gas generation, increased fire retardance, and improved volume resistivity, which are much better in comparison with a typical PVC sheathing compound. Thermoplastic elastomer (TPE) based nonhalogen FRLS compounds are also reported. The mechanisms for grafting, polymer-polymer and polymer-filler interactions have been presented. 1673

Polymers that stabilize biomolecules are important as excipients in protein formulation. Herein, we describe a class of degradable polymers that have tunable degradation rates depending on the polymer backbone and can stabilize proteins to aggregation. Specifically, zwitterion-and trehalose-substituted polycaprolactone, polyvalerolactone, polycarbonate, and polylactide were prepared and characterized with regards to their hydrolytic degradation and ability to stabilize insulin to mechanical agitation during heat. Ring-opening polymerization (ROP) of allylsubstituted monomers was performed by using organocatalysis, resulting in well-defined alkene-substituted polymers with good control over molecular weight and dispersity. The polymers were then modified by using photocatalyzed thiol−ene reactions to install protein-stabilizing carboxybetaine and trehalose side chains. The resulting polymers were water-soluble and exhibited a wide range of half-lives, from 12 h to more than 3 months. The polymers maintained the ability to stabilize the therapeutic protein insulin from activity loss due to aggregation, demonstrating their potential as degradable excipients for protein formulation.

This manuscript is dedicated to Professor Mitsuo Sawamoto's outstanding achievements in polymer chemistry and recognizes his recent retirement from 40 years of exceptional service to Kyoto University.ABSTRACT: Amphiphilic self-folding random copolymers exhibit different solution behaviors depending on the identity of the hydrophobic/hydrophilic units. Herein, it is demonstrated that changing the hydrophilic unit from poly(ethylene glycol) to the sugar trehalose causes increased discrepancy in the polarity difference with a fluorinated hydrophobic segment and changes the aggregation state of the polymer in water. The PEG-fluorinated and trehalose/PEG-fluorinated amphiphilic random copolymers were the most efficient at encapsulating a fluorinated agrochemical. The small-molecule agrochemical exerts a strong influence on the selfassembly of the polymers, demonstrating that fluorous interactions result in not only intramolecular self-folding behavior but also intermolecular polymer association to form well-defined nanoparticles.