Ultra-High-Molecular-Weight Poly(Dioxolane): Enhancing the Mechanical Performance of a Chemically Recyclable Polymer.

We report a method to synthesize ultra-high-molecular-weight poly(1,3-dioxolane) (UHMW pDXL), a chemically recyclable thermoplastic material with excellent physical properties. We aimed to enhance the mechanical properties of sustainable polymers by increasing the molecular weight and found that UHMW pDXL exhibits similar tensile properties to ultra-high-molecular-weight polyethylene (UHMWPE). The new polymerization method uses metal-free and economically friendly initiators to achieve UHMW pDXL with molecular weights greater than 1000 kDa. The development of UHMW pDXL provides a potential solution for capturing value from plastic waste and addressing the detrimental effects of plastic waste.

Bifunctional Catalysis Prevents Inhibition in Reversible-Deactivation Ring-Opening Copolymerizations of Epoxides and Cyclic Anhydrides.

Reversible-deactivation chain transfer is a viable strategy to increase the catalytic efficiency of ring-opening polymerizations, such as the alternating copolymerization of epoxides and cyclic anhydrides. In conjunction with the catalyst, protic chain transfer agents (CTAs) initiate polymerization and facilitate rapid proton transfer between active and dormant chains. Functional-group-tolerant Lewis acid catalysts are therefore required to successfully apply protic CTAs in reversible-deactivation ring-opening copolymerizations (RD-ROCOP), yet the predominant binary Lewis acid catalyst/nucleophilic cocatalyst systems suffer lower polymerization rates when used with protic CTAs. New mechanistic insight into the inhibition pathways reveals that the alcohol chain ends compete with epoxide binding to the Lewis acid and hydrogen-bond with anionic chain ends to impede epoxide ring opening. We report that a bifunctional aminocyclopropenium aluminum salen complex maintains excellent activity in the presence of protic functionality, exhibiting resilience against these inhibition pathways, even at high CTA concentrations. We apply reversible-deactivation chain transfer in the bifunctional ROCOP system to demonstrate precise molecular-weight control, CTA functional group scope, and accessible polymer architectures.

Mechanism-Inspired Design of Bifunctional Catalysts for the Alternating Ring-Opening Copolymerization of Epoxides and Cyclic Anhydrides.

Advances in catalysis have enabled the ring-opening copolymerization of epoxides and cyclic anhydrides to afford structurally and functionally diverse polyesters with controlled molecular weights and dispersities. However, the most common systems employ binary catalyst/cocatalyst pairs which suffer from slow polymerization rates at low loadings. Inspired by new mechanistic insight into the function of binary metal salen/nucleophilic cocatalyst systems at low concentrations, we report a bifunctional complex in which the salen catalyst and an aminocyclopropenium cocatalyst are covalently tethered. A modular ligand design circumvents the extended linear syntheses typical of bifunctional catalysts, enabling systematic variation to understand and enhance catalytic activity. The optimized bifunctional aluminum salen catalyst maintains excellent activity for the ring-opening copolymerization of epoxides and cyclic anhydrides at low concentrations (≥0.025 mol %), and the aminocyclopropenium cocatalyst suppresses undesirable transesterification and epimerization side reactions, preserving the integrity of the polymer backbone.

Enabling Room-Temperature Mechanochromic Activation in a Glassy Polymer: Synthesis and Characterization of Spiropyran Polycarbonate.

Mechanochromic functionality realized through force-responsive molecules (i.e., mechanophores) has great potential for spatially localized damage warning in polymers. However, in structural plastics, for which damage warning is most critical, this approach has had minimal success because brittle failure typically precedes detectable color change. Herein, we report on the room-temperature mechanochromic activation of spiropyran in high Tg bisphenol A polycarbonate. The mechanochromic functionality was introduced by polymerization of dihydroxyspiropyran as a comonomer while retaining the excellent thermomechanical properties of the polycarbonate. The mechanochromic behavior is thoroughly evaluated in response to changes in stress, deformation, and time, providing new insights regarding how loading history controls stress accumulation in polymer chains. In addition, a new method to incorporate mechanochromic functionality in structures without dispersing costly mechanophores in the bulk is demonstrated by using a mechanochromic laminate. The room-temperature mechanochromic activation in a structural polymer combined with the new and efficient preparation and processing methods bring us closer to the application of mechanochromic smart materials.

Aqueous RAFT Synthesis of Glycopolymers for Determination of Saccharide Structure and Concentration Effects on Amyloid ß Aggregation.

GM1 ganglioside is known to promote amyloid-ß (Aß) peptide aggregation in Alzheimer's disease. The roles of the individual saccharides and their distribution in this process are not understood. Acrylamide-based glycomonomers with either ß-d-glucose or ß-d-galactose pendant groups were synthesized to mimic the stereochemistry of saccharides present in GM1 and characterized via 1H NMR and electrospray ionization mass spectrometry. Glycopolymers of different molecular weights were synthesized by aqueous reversible addition-fragmentation chain transfer (aRAFT) polymerization and characterized by NMR and GPC. The polymers were used as models to investigate the effects of molecular weight and saccharide unit type on Aß aggregation via thioflavin-T fluorescence and PAGE. High molecular weight (∼350 DP) glucose-containing glycopolymers had a profound effect on Aß aggregation, promoting formation of soluble oligomers of Aß and limiting fibril production, while the other glycopolymers and negative control had little effect on the Aß propagation process.

Antimicrobial Peptide Mimicking Primary Amine and Guanidine Containing Methacrylamide Copolymers Prepared by Raft Polymerization.

Naturally occurring antimicrobial peptides (AMPs) display the ability to eliminate a wide variety of bacteria, without toxicity to the host eukaryotic cells. Synthetic polymers containing moieties mimicking lysine and arginine components found in AMPs have been reported to show effectiveness against specific bacteria, with the mechanism of activity purported to depend on the nature of the amino acid mimic. In an attempt to incorporate the antimicrobial activity of both amino acids into a single water-soluble copolymer, a series of copolymers containing lysine mimicking aminopropyl methacrylamide (APMA) and arginine mimicking guanadinopropyl methacrylamide (GPMA) were prepared via aqueous RAFT polymerization. Copolymers were prepared with varying ratios of the comonomers, with degree of polymerization of 35-40 and narrow molecular weight distribution to simulate naturally occurring AMPs. Antimicrobial activity was determined against Gram-negative and Gram-positive bacteria under conditions with varying salt concentration. Toxicity to mammalian cells was assessed by hemolysis of red blood cells and MTT assays of MCF-7 cells. Antimicrobial activity was observed for APMA homopolymer and copolymers with low concentrations of GPMA against all bacteria tested, with low toxicity toward mammalian cells.

Antimicrobial poly(methacrylamide) derivatives prepared via aqueous RAFT polymerization exhibit biocidal efficiency dependent upon cation structure.

Antimicrobial peptides (AMPs) show great potential as alternative therapeutic agents to conventional antibiotics as they can selectively bind and eliminate pathogenic bacteria without harming eukaryotic cells. It is of interest to develop synthetic macromolecules that mimic AMPs behavior, but that can be produced more economically at commercial scale. Herein, we describe the use of aqueous reversible addition-fragmentation chain transfer (RAFT) polymerization to prepare primary and tertiary amine-containing polymers with precise molecular weight control and narrow molecular weight distributions. Specifically, N-(3-aminopropyl)methacrylamide (APMA) was statistically copolymerized with N-[3-(dimethylamino)propyl]methacrylamide (DMAPMA) or N-[3-(diethylamino)propyl]methacrylamide (DEAPMA) to afford a range of (co)polymer compositions. Analysis of antimicrobial activity against E. coli (Gram-negative) and B. subtilis (Gram-positive) as a function of buffer type, salt concentration, pH, and time indicated that polymers containing large fractions of primary amine were most effective against both strains of bacteria. Under physiological pH and salt conditions, the polymer with the highest primary amine content caused complete inhibition of bacterial growth at low concentrations, while negligible hemolysis was observed over the full range of concentrations tested, indicating exceptional selectivity. The cytotoxicity of select polymers was evaluated against MCF-7 cells.

Chemically recyclable thermoplastics from reversible-deactivation polymerization of cyclic acetals.

Identifying plastics capable of chemical recycling to monomer (CRM) is the foremost challenge in creating a sustainable circular plastic economy. Polyacetals are promising candidates for CRM but lack useful tensile strengths owing to the low molecular weights produced using current uncontrolled cationic ring-opening polymerization (CROP) methods. Here, we present reversible-deactivation CROP of cyclic acetals using a commercial halomethyl ether initiator and an indium(III) bromide catalyst. Using this method, we synthesize poly(1,3-dioxolane) (PDXL), which demonstrates tensile strength comparable to some commodity polyolefins. Depolymerization of PDXL using strong acid catalysts returns monomer in near-quantitative yield and even proceeds from a commodity plastic waste mixture. Our efficient polymerization method affords a tough thermoplastic that can undergo selective depolymerization to monomer.

Miscible Polyether/Poly(ether-acetal) Electrolyte Blends.

This study shows that it is possible to obtain homogeneous mixtures of two chemically distinct polymers with a lithium salt for electrolytic applications. This approach is motivated by the success of using mixtures of organic solvents in modern lithium-ion batteries. The properties of mixtures of a polyether, poly(ethylene oxide) (PEO), a poly(ether-acetal), poly(1,3,6-trioxocane) (P(2EO-MO)), and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt were studied by small-angle neutron scattering (SANS) and electrochemical characterization in symmetric cells. The SANS data are used to determine the miscibility window and quantify the effect of added salt on the thermodynamic interactions between the polymers. In the absence of salt, PEO/P(2EO-MO) blends are homogeneous and characterized by attractive interactions, i.e., a negative Flory-Huggins interaction parameter, χ. The addition of small amounts of salt results in a positive effective Flory-Huggins interaction parameter, χ eff, and macrophase separation. Surprisingly, miscible blends and negative χ eff parameters are obtained when the salt concentration is increased beyond a critical value. The electrochemical properties of PEO/P(2EO-MO)/LiTFSI blends at a given salt concentration were close to those obtained in PEO/LiTFSI electrolytes at the same salt concentration. This suggests that in the presence of PEO the electrochemical properties exhibited by P(2EO-MO) chains are similar to those of PEO chains. This work opens the door to a new direction for creating new and improved polymer electrolytes either by combining existing polymers and salt or by synthesizing new polymers with the specific aim of including them in miscible polymer blend electrolytes.

Guanidine-Containing Methacrylamide (Co)polymers via aRAFT: Toward a Cell Penetrating Peptide Mimic().

We report the synthesis and controlled radical homo- and block copolymerization of 3-guanidinopropyl methacrylamide (GPMA) utilizing aqueous reversible addition-fragmentation chain transfer (aRAFT) polymerization. The resulting homopolymer and block copolymer with N-(2-hydroxypropyl) methacrylamide (HPMA) were prepared to mimic the behavior of cell penetrating peptides (CPPs) and poly(arginine) (> 6 units) which have been shown to cross cell membranes. The homopolymerization mediated by 4-cyano-4-(ethylsulfanylthiocarbonylsulfanyl)pentanoic acid (CEP) in aqueous buffer exhibited pseudo-first-order kinetics and linear growth of molecular weight with conversion. Retention of the "living" thiocarbonylthio ω-end-group was demonstrated through successful chain extension of the GPMA macroCTA yielding GPMA(37)-b-GPMA(61) (M(w)/M(n) =1.05). Block copolymers of GPMA with the non-immunogenic, biocompatible HPMA were synthesized yielding HPMA(271)-b-GPMA(13) (M(w)/M(n) = 1.15). Notably, intracellular uptake was confirmed by fluorescence microscopy, confocal laser scanning microscopy, and flow cytometry experiments after 2.5 h incubation with KB cells at 4 °C and at 37 °C utilizing FITC-labeled, GPMA-containing copolymers. The observed facility of cellular uptake and the structural control afforded by aRAFT polymerization suggest significant potential for these synthetic (co)polymers as drug delivery vehicles in targeted therapies.