Bacterial Redox Potential Powers Controlled Radical Polymerization.

Microbes employ a remarkably intricate electron transport system to extract energy from the environment. The respiratory cascade of bacteria culminates in the terminal transfer of electrons onto higher redox potential acceptors in the extracellular space. This general and inducible mechanism of electron efflux during normal bacterial proliferation leads to a characteristic fall in bulk redox potential (Eh), the degree of which is dependent on growth phase, the microbial taxa, and their physiology. Here, we show that the general reducing power of bacteria can be subverted to induce the abiotic production of a carbon-centered radical species for targeted bioorthogonal molecular synthesis. Using two species, Escherichia coli and Salmonella enterica serovar Typhimurium as model microbes, a common redox active aryldiazonium salt is employed to intervene in the terminal respiratory electron flow, affording radical production that is mediated by native redox-active molecular shuttles and active bacterial metabolism. The aryl radicals are harnessed to initiate and sustain a bioorthogonal controlled radical polymerization via reversible addition-fragmentation chain transfer (BacRAFT), yielding a synthetic extracellular matrix of "living" vinyl polymers with predetermined molecular weight and low dispersity. The ability to interface the ubiquitous reducing power of bacteria into synthetic materials design offers a new means for creating engineered living materials with promising adaptive and self-regenerative capabilities.

Ultrasound and Sonochemistry for Radical Polymerization: Sound Synthesis.

The use of ultrasound as an external stimulus for promoting polymerization reactions has received increasing attention in recent years. In this Review article, the fundamental processes that can lead to either the homolytic cleavage of polymer chains, or the sonolysis of solvent (or other) small molecules, under the application of ultrasound are described. These reactions promote the production of reactive radicals, which can be utilized in chain-growth radical polymerizations under the right conditions. A full historical overview of the development of ultrasound-assisted radical polymerization is provided, with special attention given to the recently described systems that are "controlled" by methods of reversible (radical) deactivation. Perspectives are shared on what challenges still remain in polymer sonochemistry, as well as new areas that are yet to be explored.

Fenton-Chemistry-Mediated Radical Polymerization.

In this review, the power of a classical chemical reaction, the Fenton reaction for initiating radical polymerizations, is demonstrated. The reaction between the Fenton reagents (i.e., Fe2+ and H2 O2 ) generates highly reactive hydroxyl radicals, which can act as radical initiators for the polymerization of vinyl monomers. Since the Fenton reaction is fast, easy to set up, cheap, and biocompatible, this unique chemistry is widely employed in various polymer synthesis studies via free radical polymerization or reversible addition-fragmentation chain transfer polymerization, and is utilized in a wide range of applications, such as the fabrication of biomaterials, hydrogels, and core-shell particles. Biologically activated Fenton-mediated radical polymerization, which can be performed in aerobic environments, are particularly useful for applications in biomedical systems.

Star Polymers.

Recent advances in controlled/living polymerization techniques and highly efficient coupling chemistries have enabled the facile synthesis of complex polymer architectures with controlled dimensions and functionality. As an example, star polymers consist of many linear polymers fused at a central point with a large number of chain end functionalities. Owing to this exclusive structure, star polymers exhibit some remarkable characteristics and properties unattainable by simple linear polymers. Hence, they constitute a unique class of technologically important nanomaterials that have been utilized or are currently under audition for many applications in life sciences and nanotechnologies. This article first provides a comprehensive summary of synthetic strategies towards star polymers, then reviews the latest developments in the synthesis and characterization methods of star macromolecules, and lastly outlines emerging applications and current commercial use of star-shaped polymers. The aim of this work is to promote star polymer research, generate new avenues of scientific investigation, and provide contemporary perspectives on chemical innovation that may expedite the commercialization of new star nanomaterials. We envision in the not-too-distant future star polymers will play an increasingly important role in materials science and nanotechnology in both academic and industrial settings.

Tunable, Quantitative Fenton-RAFT Polymerization via Metered Reagent Addition.

A continuous supply of radical species is a key requirement for activating chain growth and accessing quantitative monomer conversions in reversible addition-fragmentation chain transfer (RAFT) polymerization. In Fenton-RAFT, activation is provided by hydroxyl radicals, whose indiscriminate reactivity and short-lived nature poses a challenge to accessing extended polymerization times and quantitative monomer conversions. Here, an alternative Fenton-RAFT procedure is presented, whereby radical generation can be finely controlled via metered dosing of a component of the Fenton redox reaction (H2 O2 ) using an external pumping system. By limiting the instantaneous flux of radicals and ensuring sustained radical generation over tunable time periods, metered reagent addition reduces unwanted radical "wasting" reactions and provides access to consistent quantitative monomer conversions with high chain-end fidelity. Fine tuning of radical concentration during polymerization is achieved simply via adjustment of reagent dose rate, offering significant potential for automation. This modular strategy holds promise for extending traditional RAFT initiation toward more tightly regulated radical concentration profiles and affords excellent prospects for the automation of Fenton-RAFT polymerization.

Blood-Catalyzed RAFT Polymerization.

The use of hemoglobin (Hb) contained within red blood cells to drive a controlled radical polymerization via a reversible addition-fragmentation chain transfer (RAFT) process is reported for the first time. No pre-treatment of the Hb or cells was required prior to their use as polymerization catalysts, indicating the potential for synthetic engineering in complex biological microenvironments without the need for ex vivo techniques. Owing to the naturally occurring prevalence of the reagents employed in the catalytic system (Hb and hydrogen peroxide), this approach may facilitate the development of new strategies for in vivo cell engineering with synthetic macromolecules.

Fenton-RAFT Polymerization: An "On-Demand" Chain-Growth Method.

Fine control over the architecture and/or microstructure of synthetic polymers is fast becoming a reality owing to the development of efficient and versatile polymerization techniques and conjugation reactions. However, the transition of these syntheses to automated, programmable, and high-throughput operating systems is a challenging step needed to translate the vast potential of precision polymers into machine-programmable polymers for biological and functional applications. Chain-growth polymerizations are particularly appealing for their ability to form structurally and chemically well-defined macromolecules through living/controlled polymerization techniques. Even using the latest polymerization technologies, the macromolecular engineering of complex functional materials often requires multi-step syntheses and purification of intermediates, and results in sub-optimal yields. To develop a proof-of-concept of a framework polymerization technique that is readily amenable to automation requires several key characteristics. In this study, a new approach is described that is believed to meet these requirements, thus opening avenues toward automated polymer synthesis.

Single Gold Nanorod Charge Modulation in an Ion Gel Device.

A reliable and reproducible method to rapidly charge single gold nanocrystals in a solid-state device is reported. Gold nanorods (Au NRs) were integrated into an ion gel capacitor, enabling them to be charged in a transparent and highly capacitive device, ideal for optical transmission. Changes in the electron concentration of a single Au NR were observed with dark-field imaging spectroscopy via localized surface plasmon resonance (LSPR) shifts in the scattering spectrum. A time-resolved, laser-illuminated, dark-field system was developed to enable direct measurement of single particle charging rates with time resolution below one millisecond. The added sensitivity of this new approach has enabled the optical detection of fewer than 110 electrons on a single Au NR. Single wavelength resonance shifts provide a much faster, more sensitive method for all surface plasmon-based sensing applications.

Sono-RAFT Polymerization in Aqueous Medium.

The ultrasonic irradiation of aqueous solution is demonstrated to be a suitable source of initiating radicals for a controlled radical polymerization when conducted in the presence of a thiocarbonylthio-containing reversible addition-fragmentation chain transfer (RAFT) agent. This allows for a highly "green" method of externally regulated/controlled polymerization with a potentially broad scope for polymerizable monomers and/or polymer structures.

Highly Living Stars via Core-First Photo-RAFT Polymerization: Exploitation for Ultra-High Molecular Weight Star Synthesis.

Star polymers are highly functional materials that display unique properties in comparison to linear polymers, making them valuable in a wide range of applications. Currently, ultra-high molecular weight (UHMW) star polymers synthesized using controlled radical polymerization are prone to termination reactions that have undesirable effects, such as star-star coupling. Herein, we report the synthesis of the largest star polymers to date using controlled radical techniques via xanthate-mediated photo-reversible addition-fragmentation chain transfer (RAFT) polymerization using a core-first approach. Polymerization from xanthate-functionalized cores was highly living, enabling the synthesis of well-defined star polymers with molecular weights in excess of 20 MDa.

Self-deoxygenating glassware.

The removal of dissolved oxygen (O2) from solution is a prerequisite for many reactions, frequently requiring specialized equipment/reagents or expertise. Herein, we introduce a range of reusable, shelf-stable enzyme-functionalized glassware, which biocatalytically removes O2 from contained aqueous solutions. The effectiveness of the activated glassware is demonstrated by facilitating several O2-intolerant RAFT polymerizations.

Nano-scale clustering of integrin-binding ligands regulates endothelial cell adhesion, migration, and endothelialization rate: novel materials for small diameter vascular graft applications.

Blood contacting devices are commonly used in today's medical landscape. However, such devices (including small diameter vascular grafts) are limited by poor blood compatibility and may fail due to thrombosis. An attractive strategy for improving the blood compatibility of such devices is to generate biomaterials that foster a confluent and functioning endothelial cell layer. Synthesizing materials that display integrin-binding peptide ligands is a common way to promote endothelialization. However, in addition to integrin-ligand binding, integrin clustering is necessary to achieve intracellular signaling events that influence cellular phenotype. In this study, we explored the impact of nano-scale clustering of integrin-binding ligands on endothelial cell functions by designing novel materials that promote the clustering of integrin receptors. RGD-functionalized copolymers were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization and used for the preparation of random and nano-clustered surfaces spanning a range of global and local RGD densities (global densities 0.4-1.9 µg of peptide per mg of polymer and local densities of 1-2.4 ligands per nano-cluster). The adhesion and migration of endothelial cells was improved on nano-clustered surfaces compared to random surfaces. The highest adhesion and migration speed of endothelial cells and the rapid development of the endothelial monolayer were observed on surfaces with the highest local and global peptide density. These results indicate that the nano-clustering of peptide ligands is a promising strategy for next generation cardiovascular biomaterials, especially for small diameter vascular graft applications where the development of a confluent and functioning endothelium holds the potential to prevent device failure due to thrombosis.

A novel solid state photocatalyst for living radical polymerization under UV irradiation.

This study presents the development of a novel solid state photocatalyst for the photoinduced controlled radical polymerization of methacrylates under mild UV irradiation (λmax ≈ 365 nm) in the absence of conventional photoinitiators, metal-catalysts or dye sensitizers. The photocatalyst design was based on our previous finding that organic amines can act in a synergistic photochemical reaction with thiocarbonylthio compounds to afford well controlled polymethacrylates under UV irradiation. Therefore, in the current contribution an amine-rich polymer was covalently grafted onto a solid substrate, thus creating a heterogeneous catalyst that would allow for facile removal, recovery and recyclability when employed for such photopolymerization reactions. Importantly, the polymethacrylates synthesized using the solid state photocatalyst (ssPC) show similarly excellent chemical and structural integrity as those catalysed by free amines. Moreover, the ssPC could be readily recovered and re-used, with multiple cycles of polymerization showing minimal effect on the integrity of the catalyst. Finally, the ssPC was employed in various photo-"click" reactions, permitting high yielding conjugations under photochemical control.

Observed Photoenhancement of RAFT Polymerizations under Fume Hood Lighting.

Given the recent findings of exogenous radical initiator/catalyst-free reversible addition-fragmentation chain transfer (RAFT) radical polymerization under both UV and visible light irradiation, the effect of standard laboratory lighting conditions (fluorescent tube lights) on traditional RAFT reactions, that is, those conducted in the presence of a thermally activated radical initiator, remains unknown. This is investigated in the current study, where a significant "photoenhancement" is observed for most cases under typical RAFT reaction conditions, indicating that fume hood lights can contribute to the generation of radicals in RAFT reactions. Given the observed emission spectrum of a typical fluorescent light source, the photoenhancement is proposed to occur through a visible light activation pathway. These findings are crucial for ensuring maximum reproducibility of controlled polymerizations conducted in the presence of typical sources of irradiation encountered in a standard chemical laboratory.

Beyond Traditional RAFT: Alternative Activation of Thiocarbonylthio Compounds for Controlled Polymerization.

Recent developments in polymerization reactions utilizing thiocarbonylthio compounds have highlighted the surprising versatility of these unique molecules. The increasing popularity of reversible addition-fragmentation chain transfer (RAFT) radical polymerization as a means of producing well-defined, 'controlled' synthetic polymers is largely due to its simplicity of implementation and the availability of a wide range of compatible reagents. However, novel modes of thiocarbonylthio activation can expand the technique beyond the traditional system (i.e., employing a free radical initiator) pushing the applicability and use of thiocarbonylthio compounds even further than previously assumed. The primary advances seen in recent years are a revival in the direct photoactivation of thiocarbonylthio compounds, their activation via photoredox catalysis, and their use in cationic polymerizations. These synthetic approaches and their implications for the synthesis of controlled polymers represent a significant advance in polymer science, with potentially unforeseen benefits and possibilities for further developments still ahead. This Research News aims to highlight key works in this area while also clarifying the differences and similarities of each system.

Controlled Formation of Star Polymer Nanoparticles via Visible Light Photopolymerization.

A recently developed visible light mediated photocontrolled radical polymerization technique using trithiocarbonates (i.e., conventional RAFT agents) as the sole control agent in the absence of additional photoinitiators or catalysts is utilized for the synthesis of core cross-linked star (CCS) polymer nanoparticles. The attractive features of this photopolymerization system, including high end-group fidelity at (near) complete monomer conversion, are exploited to facilitate a high-yielding, one-pot pathway toward well-defined star polymer products. Moreover, reinitiation of the photoactive trithiocarbonate moieties from within the star core is demonstrated to form (pseudo)miktoarm stars via an "in-out" approach, showing extremely high initiation efficiency (95%).