The Structural Dispersity of Oligoethylene Glycol-Containing Polymer Brushes Determines Their Interfacial Properties.

Ought to their bioinert properties and facile synthesis, poly[(oligoethylene glycol)methacrylate]s (POEGMAs) have been raised as attractive alternatives to poly(ethylene glycols) (PEGs) in an array of (bio)material applications, especially when they are applied as polymer brush coatings. However, commercially available OEG-methacrylate (macro)monomers feature a broad distribution of OEG lengths, thus generating structurally polydisperse POEGMAs when polymerized through reversible deactivation radical polymerization. Here, we demonstrate that the interfacial physicochemical properties of POEGMA brushes are significantly affected by their structural dispersity, i.e., the degree of heterogeneity in the length of side OEG segments. POEGMA brushes synthesized from discrete (macro)monomers obtained through chromatographic purification of commercial mixtures show increased hydration and reduced adhesion when compared to their structurally polydisperse analogues. The observed alteration of interfacial properties is directly linked to the presence of monodisperse OEG side chains, which hamper intramolecular and intermolecular hydrophobic interactions while simultaneously promoting the association of water molecules. These phenomena provide structurally homogeneous POEGMA brushes with a more lubricious and protein repellent character with respect to their heterogeneous counterparts. More generally, in contrast to what has been assumed until now, the properties of POEGMA brushes cannot be anticipated while ruling out the effect of dispersity by (macro)monomer feeds. Simultaneously, side chain dispersity of POEGMAs emerges as a critical parameter for determining the interfacial characteristics of brushes.

Polymer Brushes on Nanoparticles for Controlling the Interaction with Protein-Rich Physiological Media.

The interaction of nanoparticles (NPs) with biological environments triggers the formation of a protein corona (PC), which significantly influences their behavior in vivo. This review explores the evolving understanding of PC formation, focusing on the opportunity for decreasing or suppressing protein-NP interactions by macromolecular engineering of NP shells. The functionalization of NPs with a dense, hydrated polymer brush shell is a powerful strategy for imparting stealth properties in order to elude recognition by the immune system. While poly(ethylene glycol) (PEG) has been extensively used for this purpose, concerns regarding its stability and immunogenicity have prompted the exploration of alternative polymers. The stealth properties of brush shells can be enhanced by tailoring functionalities and structural parameters, including the molar mass, grafting density, and polymer topology. Determining correlations between these parameters and biopassivity has enabled us to obtain polymer-grafted NPs with high colloidal stability and prolonged circulation time in biological media.

Reactivity Prediction of Cu-Catalyzed Halogen Atom Transfer Reactions Using Data-Driven Techniques.

In catalysis, linear free energy relationships (LFERs) are commonly used to identify reaction descriptors that enable the prediction of outcomes and the design of more effective catalysts. Herein, LFERs are established for the reductive cleavage of the C(sp3)-X bond in alkyl halides (RX) by Cu complexes. This reaction represents the activation step in atom transfer radical polymerization and atom transfer radical addition/cyclization. The values of the activation rate constant, kact, for 107 Cu complex/RX couples in 5 different solvents spanning over 13 orders of magnitude were effectively interpolated by the equation: log kact = sC(I + C + S), where I, C, and S are, respectively, the initiator, catalyst, and solvent parameters, and sC is the catalyst-specific sensitivity parameter. Furthermore, each of these parameters was correlated to relevant descriptors, which included the bond dissociation free energy of RX and its Tolman cone angle θ, the electron affinity of X, the radical stabilization energy, the standard reduction potential of the Cu complex, the polarizability parameter π* of the solvent, and the distortion energy of the complex in its transition state. This set of descriptors establishes the fundamental properties of Cu complexes and RX that determine their reactivity and that need to be considered when designing novel systems for atom transfer radical reactions. Finally, a multivariate linear regression (MLR) approach was adopted to develop an objective model that surpassed the predictive capability of the LFER equation. Thus, the MLR model was employed to predict kact values for >2000 Cu complex/RX pairs.

Oxygen Tolerance during Surface-Initiated Photo-ATRP: Tips and Tricks for Making Brushes under Environmental Conditions.

Achieving tolerance toward oxygen during surface-initiated reversible deactivation radical polymerization (SI-RDRP) holds the potential to translate the fabrication of polymer brush-coatings into upscalable and technologically relevant processes for functionalizing materials. While focusing on surface-initiated photoinduced atom transfer radical polymerization (SI-photoATRP), we demonstrate that a judicious tuning of the composition of reaction mixtures and the adjustment of the polymerization setup enable to maximize the compatibility of this grafting technique toward environmental conditions. Typically, the presence of O2 in the polymerization medium limits the attainable thickness of polymer brushes and causes the occurrence of "edge effects", i.e., areas at the substrates' edges where continuous oxygen diffusion from the surrounding environment inhibits brush growth. However, the concentrations of the Cu-based catalyst and "free" alkyl halide initiator in solution emerge as key parameters to achieve a more efficient consumption of oxygen and yield uniform and thick brushes, even for polymerization mixtures that are more exposed to air. Precise variation of reaction conditions thus allows us to identify those variables that become determinants for making the synthesis of brushes more tolerant toward oxygen, and consequently more practical and upscalable.

Atom Transfer Radical Polymerization: A Mechanistic Perspective.

Since its inception, atom transfer radical polymerization (ATRP) has seen continuous evolution in terms of the design of the catalyst and reaction conditions; today, it is one of the most useful techniques to prepare well-defined polymers as well as one of the most notable examples of catalysis in polymer chemistry. This Perspective highlights fundamental advances in the design of ATRP reactions and catalysts, focusing on the crucial role that mechanistic studies play in understanding, rationalizing, and predicting polymerization outcomes. A critical summary of traditional ATRP systems is provided first; we then focus on the most recent developments to improve catalyst selectivity, control polymerizations via external stimuli, and employ new photochemical or dual catalytic systems with an outlook to future research directions and open challenges.

Dual electrochemical and chemical control in atom transfer radical polymerization with copper electrodes.

In Atom Transfer Radical Polymerization (ATRP), Cu0 acts as a supplemental activator and reducing agent (SARA ATRP) by activating alkyl halides and (re)generating the CuI activator through a comproportionation reaction, respectively. Cu0 is also an unexplored, exciting metal that can act as a cathode in electrochemically mediated ATRP (eATRP). Contrary to conventional inert electrodes, a Cu cathode can trigger a dual catalyst regeneration, simultaneously driven by electrochemistry and comproportionation, if a free ligand is present in solution. The dual regeneration explored herein allowed for introducing the concept of pulsed galvanostatic electrolysis (PGE) in eATRP. During a PGE, the process alternates between a period of constant current electrolysis and a period with no applied current in which polymerization continues via SARA ATRP. The introduction of no electrolysis periods without compromising the overall polymerization rate and control is very attractive, if large current densities are needed. Moreover, it permits a drastic charge saving, which is of unique value for a future scale-up, as electrochemistry coupled to SARA ATRP saves energy, and shortens the equipment usage.

Red-Light-Induced, Copper-Catalyzed Atom Transfer Radical Polymerization.

Despite advances in photochemical atom transfer radical polymerization (photoATRP), these systems often rely on the use of UV light for the activation/generation of the copper-based catalytic species. To circumvent the problems associated with the UV light, we developed a dual photoredox catalytic system to mediate photoinduced ATRP under red-light irradiation. The catalytic system is comprised of a Cu catalyst to control the polymerization via ATRP equilibrium and a photocatalyst, such as zinc(II) tetraphenylporphine or zinc(II) phthalocyanine, to generate the activator CuI species under red-light irradiation. In addition, this system showed oxygen tolerance due to the consumption of oxygen in the photoredox reactions, yielding well-controlled polymerizations without the need for deoxygenation processes.

Toward Green Atom Transfer Radical Polymerization: Current Status and Future Challenges.

Reversible-deactivation radical polymerizations (RDRPs) have revolutionized synthetic polymer chemistry. Nowadays, RDRPs facilitate design and preparation of materials with controlled architecture, composition, and functionality. Atom transfer radical polymerization (ATRP) has evolved beyond traditional polymer field, enabling synthesis of organic-inorganic hybrids, bioconjugates, advanced polymers for electronics, energy, and environmentally relevant polymeric materials for broad applications in various fields. This review focuses on the relation between ATRP technology and the 12 principles of green chemistry, which are paramount guidelines in sustainable research and implementation. The green features of ATRP are presented, discussing the environmental and/or health issues and the challenges that remain to be overcome. Key discoveries and recent developments in green ATRP are highlighted, while providing a perspective for future opportunities in this area.

Biocompatible photoinduced CuAAC using sodium pyruvate.

Sodium pyruvate, a natural intermediate produced during cellular metabolism, is commonly used in buffer solutions and media for biochemical applications. Here we show the use of sodium pyruvate (SP) as a reducing agent in a biocompatible aqueous photoinduced azide-alkyne cycloaddition (CuAAC) reaction. This copper(I)-catalyzed 1,3-dipolar cycloaddition is triggered by SP under UV light irradiation, exhibits oxygen tolerance and temporal control, and provides a convenient alternative to current CuAAC systems, particularly for biomolecular conjugations.

Assemblies of Polyacrylonitrile-Derived Photoactive Polymers as Blue and Green Light Photo-Cocatalysts for Cu-Catalyzed ATRP in Water and Organic Solvents.

Photoluminescent nanosized quasi-spherical polymeric assemblies prepared by the hydrothermal reaction of polyacrylonitrile (PAN), ht-PLPPAN, were demonstrated to have the ability to photo-induce atom transfer radical polymerization (ATRP) catalyzed by low, parts per million concentrations of CuII complex with tris(2-pyridylmethyl)amine (TPMA). Such photo induced ATRP reactions of acrylate and methacrylate monomers were performed in water or organic solvents, using ht-PLPPAN as the photo-cocatalyst under blue or green light irradiation. Mechanistic studies indicate that ht-PLPPAN helps to sustain the polymerization by facilitating the activation of alkyl bromide species by two modes: 1) green or blue light-driven photoreduction of the CuII catalyst to the activating CuI form, and 2) direct activation of dormant alkyl bromide species which occurs only under blue light. The photoreduction of the CuII complex by ht-PLPPAN was confirmed by linear sweep voltammetry performed under illumination. Analysis of the polymerization kinetics in aqueous media indicated even though CuI complexes comprised only 1-1.4% of all Cu species at equilibrium, they exhibited high activation rate constant and activated the alkyl bromide initiators five to six orders of magnitude faster than ht-PLPPAN.

Conjugated Cross-linked Phenothiazines as Green or Red Light Heterogeneous Photocatalysts for Copper-Catalyzed Atom Transfer Radical Polymerization.

Using the power of light to drive controlled radical polymerizations has provided significant advances in synthesis of well-defined polymers. Photoinduced atom transfer radical polymerization (ATRP) systems often employ UV light to regenerate copper activator species to mediate the polymerization. Taking full advantage of long-wavelength visible light for ATRP would require developing appropriate photocatalytic systems that engage in photoinduced electron transfer processes with the ATRP components to generate activating species. Herein, we developed conjugated microporous polymers (CMP) as heterogeneous photocatalysts to exploit the power of visible light in promoting copper-catalyzed ATRP. The photocatalyst was designed by cross-linking phenothiazine (PTZ) as a photoactive core in the presence of dimethoxybenzene as a cross-linker via the Friedel-Crafts reaction. The resulting PTZ-CMP network showed photoactivity in the visible region due to the extended conjugation throughout the network because of the aromatic groups connecting the PTZ units. Therefore, photoinduced copper-catalyzed ATRP was performed with CMPs that regenerated activator species under green or red light irradiation to start the ATRP process. This resulted in efficient polymerization of acrylate and methacrylate monomers with high conversion and well-controlled molecular weight. The heterogeneous nature of the photocatalyst enabled easy separation and efficient reusability in subsequent polymerizations.

Comparative performance of ex situ artificial solid electrolyte interphases for Li metal batteries with liquid electrolytes.

The design of artificial solid electrolyte interphases (ASEIs) that overcome the traditional instability of Li metal anodes can accelerate the deployment of high-energy Li metal batteries (LMBs). By building the ASEI ex situ, its structure and composition is finely tuned to obtain a coating layer that regulates Li electrodeposition, while containing morphology and volumetric changes at the electrode. This review analyzes the structure-performance relationship of several organic, inorganic, and hybrid materials used as ASEIs in academic and industrial research. The electrochemical performance of ASEI-coated electrodes in symmetric and full cells was compared to identify the ASEI and cell designs that enabled to approach practical targets for high-energy LMBs. The comparative performance and the examined relation between ASEI thickness and cell-level specific energy emphasize the necessity of employing testing conditions aligned with practical battery systems.

Reflection on the Matyjaszewski Lab Webinar Series and the Rise of Webinars in Polymer Chemistry.

Webinar series are helping our community of polymer scientists to stay engaged and connected, despite the cancellation of in-person meetings and the periodic closure of laboratories to contain the spread of the coronavirus pandemic. The sustainable and inclusive character of these virtual events make them valuable learning and networking opportunities. As organizers of the Matyjaszewski Lab Webinar Series, we share herein our experience, highlighting the benefits of virtual meetings and providing a short guide for webinar organizers. Researchers, particularly young scientists, are encouraged to organize such virtual events to broaden their skills and strengthen their professional network.

p-Substituted Tris(2-pyridylmethyl)amines as Ligands for Highly Active ATRP Catalysts: Facile Synthesis and Characterization.

A facile and efficient two-step synthesis of p-substituted tris(2-pyridylmethyl)amine (TPMA) ligands to form Cu complexes with the highest activity to date in atom transfer radical polymerization (ATRP) is presented. In the divergent synthesis, p-Cl substituents in tris(4-chloro-2-pyridylmethyl)amine (TPMA3Cl ) were replaced in one step and high yield by electron-donating cyclic amines (pyrrolidine (TPMAPYR ), piperidine (TPMAPIP ), and morpholine (TPMAMOR )) by nucleophilic aromatic substitution. The [CuII (TPMANR2 )Br]+ complexes exhibited larger energy gaps between frontier molecular orbitals and >0.2 V more negative reduction potentials than [CuII (TPMA)Br]+ , indicating >3 orders of magnitude higher ATRP activity. [CuI (TPMAPYR )]+ exhibited the highest reported activity for Br-capped acrylate chain ends in DMF, and moderate activity toward C-F bonds at room temperature. ATRP of n-butyl acrylate using only 10-25 part per million loadings of [CuII (TPMANR2 )Br]+ exhibited excellent control.

Atom Transfer Radical Polymerization of Acrylic and Methacrylic Acids: Preparation of Acidic Polymers with Various Architectures.

The preparation of poly(acrylic acid) (PAA) with tailored architecture and morphology is important for the design of advanced polymer materials. Cu-catalyzed atom transfer radical polymerization (ATRP) of AA is challenging due to the tendency of dormant chains to undergo an intramolecular lactonization reaction with consequent loss of chain-end functionalities, as previously reported for ATRP of methacrylic acid (MAA). In addition, AA can coordinate to the Cu catalyst. Moreover, the lower ATRP reactivity of AA relative to MAA enhances side reactions during polymerizations. These issues were overcome by adjusting the composition of the catalytic system, the polymerization setup, and the initiator nature. AA conversion >70-80% was obtained in 5 h, producing PAA with D ≈1.4. Multifunctional water-soluble initiators provided PAA and PMAA with telechelic and star-shaped architectures. Block copolymers of MAA and AA confirmed the retention of chain-end functionalities during ATRPs.

Localized Surface Plasmon Resonance Meets Controlled/Living Radical Polymerization: An Adaptable Strategy for Broadband Light-Regulated Macromolecular Synthesis.

The photophysical process of localized surface plasmon resonance (LSPR) is, for the first time, exploited for broadband photon harvesting in photo-regulated controlled/living radical polymerization. Efficient macromolecular synthesis was achieved under illumination with light wavelengths extending from the visible to the near-infrared regions. Plasmonic Ag nanostructures were in situ generated on Ag3 PO4 photocatalysts in a reversible addition-fragmentation chain transfer (RAFT) system, thereby promoting polymerization of various monomers following a LSPR-mediated electron transfer mechanism. Owing to the LSPR-enhanced broadband photon harvesting, high monomer conversion (>99 %) was achieved under natural sunlight within 0.8 h. The deep penetration of NIR light enabled successful polymerization with reaction vessels screened by opaque barriers. Moreover, by trapping active oxygen species generated in the photocatalytic process, polymerization could be implemented without pre-deoxygenation.

Atom Transfer Radical Polymerization: Billion Times More Active Catalysts and New Initiation Systems.

Approaching 25 years since its invention, atom transfer radical polymerization (ATRP) is established as a powerful technique to prepare precisely defined polymeric materials. This perspective focuses on the relation between structure and activity of ATRP catalysts, and the consequent choice of the initiating system, which are paramount aspects to well-controlled polymerizations. The ATRP mechanism is discussed, including the effect of kinetic and thermodynamic parameters and side reactions affecting the catalyst. The coordination chemistry and activity of copper complexes used in ATRP are reviewed in chronological order, while emphasizing the structure-activity correlation. ATRP-initiating systems are described, from normal ATRP to low ppm Cu systems. Most recent advancements regarding dispersed media and oxygen-tolerant techniques are presented, as well as future opportunities that arise from progressively more active catalysts and deeper mechanistic understanding.

Atom Transfer Radical Polymerization Enabled by Sonochemically Labile Cu-carbonate Species.

Atom transfer radical polymerization (ATRP) has been previously mediated by ultrasound using a low concentration of copper complex in water (sono-ATRP) or by addition of piezoelectric materials in organic solvents (mechano-ATRP). However, these procedures proceeded slowly and yielded polymers contaminated by new chains initiated by hydroxyl radicals or by residual piezoelectrics. Unexpectedly, in the presence of sodium carbonate, rapid sono-ATRP of methyl acrylate in DMSO was achieved (80% conversion in <2 h) with excellent control of molecular weights and low dispersities (Mw/Mn < 1.2). The in situ formed CuII/L-CO3 complex in the the presence of ultrasound generated CuI/L species as activators for ATRP and carbonate radical anions. The latter were scavenged by DMSO that was oxidized to dimethyl sulfone. This simple and robust process employs low-intensity ultrasound, air-stable CuII/L catalysts, and carbonate or bicarbonate salts (washing soda or baking soda) to prepare well-defined polyacrylates.

Redox-switchable atom transfer radical polymerization.

Temporal control in atom transfer radical polymerization (ATRP) relies on modulating the oxidation state of a copper catalyst, as polymer chains are activated by L/CuI and deactivated by L/CuII. (Re)generation of L/CuI activator has been achieved by applying a multitude of external stimuli. However, switching the Cu catalyst off by oxidizing to L/CuII through external chemical stimuli has not yet been investigated. A redox switchable ATRP was developed in which an oxidizing agent was used to oxidize L/CuI activator to L/CuII, thus halting the polymerization. A ferrocenium salt or oxygen were used to switch off the Cu catalyst, whereas ascorbic acid was used to switch the catalyst on by (re)generating L/CuI. The redox switches efficiently modulated the oxidation state of the catalyst without sacrificing control over polymerization.