Diversification of Acrylamide Polymers via Direct Transamidation of Unactivated Tertiary Amides.

Postpolymerization modification offers a versatile strategy for synthesizing complex macromolecules, yet modifying acrylamide polymers like poly(N,N-dimethylacrylamide) (PDMA) is notoriously challenging due to the inherent stability and low reactivity of amide bonds. In this study, we unveil a novel approach for the direct transamidation of PDMA, leveraging recent advances in the transamidation of unactivated tertiary amide substrates. By exploiting photoiniferter polymerization, we extended this direct transamidation approach to ultrahigh-molecular-weight (UHMW) PDMA, showcasing the unprecedented postpolymerization modification of synthetic polymers exceeding 106 g/mol. We also designed acrylamide copolymers comprising both the moderately reactive N-methyl-N-phenyl tertiary amides, along with the less reactive, fully alkyl-substituted N,N-dimethyl amides inherent to PDMA. This disparate reactivity enabled a sequential, chemoselective transamidation by initially targeting the more reactive pendant aryl amides with less nucleophilic aromatic amines, and second, transamidating the untouched N,N-dimethyl amide moieties with more nucleophilic aliphatic amines, yielding a uniquely diversified acrylamide copolymer. This work not only broadens the scope of postpolymerization modification strategies by pioneering direct transamidation of unactivated amides but also provides a robust platform for the design of intricate macromolecules, particularly in the realm of UHMW polymers.

Bulk Depolymerization of Methacrylate Polymers via Pendent Group Activation.

In this study, we present an efficient approach for the depolymerization of poly(methyl methacrylate) (PMMA) copolymers synthesized via conventional radical polymerization. By incorporating low mol % phthalimide ester-containing monomers during the polymerization process, colorless and transparent polymers closely resembling unfunctionalized PMMA are obtained, which can achieve >95% reversion to methyl methacrylate (MMA). Notably, our catalyst-free bulk depolymerization method exhibits exceptional efficiency, even for high-molecular-weight polymers, including ultrahigh-molecular-weight (106-107 g/mol) PMMA, where near-quantitative depolymerization is achieved. Moreover, this approach yields polymer byproducts of significantly lower molecular weight, distinguishing it from bulk depolymerization methods initiated from chain ends. Furthermore, we extend our investigation to polymethacrylate networks, demonstrating high extents of depolymerization. This innovative depolymerization strategy offers promising opportunities for the development of sustainable polymethacrylate materials, holding great potential for various applications in polymer science.

ß-Triketones as Reactive Handles for Polymer Diversification via Dynamic Catalyst-Free Diketoenamine Click Chemistry.

The spontaneous condensation of amines with ß-triketones (TK), forming ß,ß'-diketoenamines (DKE) and releasing water as the sole byproduct, exhibits many of the hallmarks of "click" reactions. Such characteristics render TKs as a highly advantageous platform for efficient polymer diversification, even in biological contexts. Leveraging reversible addition-fragmentation chain transfer (RAFT) and photoiniferter polymerization of novel TK-containing vinylic monomers, we synthesized polymers containing pendent TKs with excellent control of molecular weights, even in excess of 106 g mol-1. Under mild, catalyst-free conditions, poly(ß-triketone methacrylate) could be modified with a diverse scope of amines containing a plethora of functional groups. The high efficiency of this functionalization approach was further emphasized when grafting-to with poly(ethylene glycol)-amine resulting in bottlebrushes with molecular weights reaching 2.0 × 107 g mol-1. Critically, while the formed DKE linkages are stable under ambient conditions, they undergo catalyst-free, dynamic transamination at elevated temperatures, paving the way for associative covalent adaptable networks. Overall, we introduce pendent triketone moieties into methacrylate and acrylamide polymers, establishing a novel postpolymerization modification technique that facilitates catalyst-free ligation of amines under highly permissible conditions.

Vanadium Alkylidyne Initiated Cyclic Polymer Synthesis: The Importance of a Deprotiovanadacyclobutadiene Moiety.

Reported is the catalytic cyclic polymer synthesis by a 3d transition metal complex: a V(V) alkylidyne, [(dBDI)V≡CtBu(OEt2)] (1-OEt2), supported by the deprotonated ß-diketiminate dBDI2- (dBDI2- = ArNC(CH3)CHC(CH2)NAr, Ar = 2,6-iPr2C6H3). Complex 1-OEt2 is a precatalyst for the polymerization of phenylacetylene (PhCCH) to give cyclic poly(phenylacetylene) (c-PPA), whereas its precursor, complex [(BDI)V≡CtBu(OTf)] (2-OTf; BDI- = [ArNC(CH3)]2CH, Ar = 2,6-iPr2C6H3, OTf = OSO2CF3), and the zwitterion [((C6F5)3B-dBDI)V≡CtBu(OEt2)] (3-OEt2) exhibit low catalytic activity despite having a neopentylidyne ligand. Cyclic polymer topologies were verified by size-exclusion chromatography (SEC) and intrinsic viscosity studies. A component of the mechanism of the cyclic polymerization reaction was probed by isolation and full characterization of 4- and 6-membered metallacycles as model intermediates. Metallacyclobutadiene (MCBD) and deprotiometallacyclobutadiene (dMCBD) complexes (dBDI)V[C(tBu)C(H)C(tBu)] (4-tBu) and (BDI)V[C(tBu)CC(Mes)] (5-Mes), respectively, were synthesized upon reaction with bulkier alkynes, tBu- (tBuCCH) and Mes-acetylene (MesCCH), with 1-OEt2. Furthermore, the reaction of the conjugate acid of 1-OEt2, [(BDI)V≡CtBu(OTf)] (2-OTf), with the conjugated base of phenylacetylene, lithium phenylacetylide (LiCCPh), yields the doubly deprotio-metallacycle complex, [Li(THF)4]{(BDI)V[C(Ph)CC(tBu)CC(Ph)]} (6). Protonation of the doubly deprotio-metallacycle complex 6 yields 6-H+, a catalytically active species toward the polymerization of PhCCH, for which the polymers were also confirmed to be cyclic by SEC studies. Computational mechanistic studies complement the experimental observations and provide insight into the mechanism of cyclic polymer growth. The noninnocence of the supporting dBDI2- ligand and its role in proton shuttling to generate deprotiometallacyclobutadiene (dMCBD) complexes that proposedly culminate in the formation of catalytically active V(III) species are also discussed. This work demonstrates how a dMCBD moiety can react with terminal alkynes to form cyclic polyalkynes.

Hybrid Photoiniferter and Ring-Opening Polymerization Yields One-Pot Anisotropic Nanorods.

Polymerization-induced self-assembly (PISA) has emerged as a scalable one-pot technique to prepare block copolymer (BCP) nanoparticles. Recently, a PISA process, that results in poly(l-lactide)-b-poly(ethylene glycol) BCP nanoparticles coined ring-opening polymerization (ROP)-induced crystallization-driven self-assembly (ROPI-CDSA), was developed. The resulting nanorods demonstrate a strong propensity for aggregation, resulting in the formation of 2D sheets and 3D networks. This article reports the synthesis of poly(N,N-dimethyl acrylamide)-b-poly(l)-lactide BCP nanoparticles by ROPI-CDSA, utilizing a two-step, one-pot approach. A dual-functionalized photoiniferter is first used for controlled radical polymerization of the acrylamido-based monomer, and the resulting polymer serves as a macroinitiator for organocatalyzed ROP to form the solvophobic polyester block. The resulting nanorods are highly stable and display anisotropy at higher molecular weights (>12k Da) and concentrations (>20% solids) than the previous report. This development expands the chemical scope of ROPI-CDSA BCPs and provides readily accessible nanorods made with biocompatible materials.

Selective Electrochemical Modification and Degradation of Polymers.

We demonstrate that electrochemical-induced decarboxylation enables reliable post-polymerization modification and degradation of polymers. Polymers containing N-(acryloxy)phthalimides were subjected to electrochemical decarboxylation under mild conditions, which led to the formation of transient alkyl radicals. By installing these redox-active units, we systematically modified the pendent groups and chain ends of polyacrylates. This approach enabled the production of poly(ethylene-co-methyl acrylate) and poly(propylene-co-methyl acrylate) copolymers, which are difficult to synthesize by direct polymerization. Spectroscopic and chromatographic techniques reveal these transformations are near-quantitative on several polymer systems. Electrochemical decarboxylation also enables the degradation of all-methacrylate poly(N-(methacryloxy)phthalimide-co-methyl methacrylate) copolymers with a degradation efficiency of >95 %. Chain cleavage is achieved through the decarboxylation of the N-hydroxyphthalimide ester and subsequent ß-scission of the backbone radical. Electrochemistry is thus shown to be a powerful tool in selective polymer transformations and controlled macromolecular degradation.

Metallacyclobuta-(2,3)-diene: A Bidentate Ligand for Stream-line Synthesis of First Row Transition Metal Catalysts for Cyclic Polymerization of Phenylacetylene.

Described here is a direct entry to two examples of 3d transition metal catalysts that are active for the cyclic polymerization of phenylacetylene, namely, [(BDI)M{κ2 -C,C-(Me3 SiC3 SiMe3 )}] (2-M) (BDI=[ArNC(CH3 )]2 CH- , Ar=2,6-i Pr2 C6 H3 ; M=Ti, V). Catalysts are prepared in one step by the treatment of [(BDI)MCl2 ] (1-M, M=Ti, V) with 1,3-dilithioallene [Li2 (Me3 SiC3 SiMe3 )]. Complexes 2-M have been spectroscopically and structurally characterized and the polymers that are catalytically formed from phenylacetylene were verified to have a cyclic topology based on a combination of size-exclusion chromatography (SEC) and intrinsic viscosity studies. Two-electron oxidation of 2-V with nitrous oxide (N2 O) cleanly yields a [VV ] alkylidene-alkynyl oxo complex [(BDI)V(=O){κ1 -C-(=C(SiMe3 )CC(SiMe3 ))}] (3), which lends support for how this scaffold in 2-M might be operating in the polymerization of the terminal alkyne. This work demonstrates how alkylidynes can be circumvented using 1,3-dianionic allene as a segue into M-C multiple bonds.

Degradation of Polyacrylates by One-Pot Sequential Dehydrodecarboxylation and Ozonolysis.

We establish a synthetically convenient method to degrade polyacrylate homopolymers. Carboxylic acids are installed along the polymer backbone by partial hydrolysis of the ester side chains, and then, in a one-pot sequential procedure, the carboxylic acids are converted into alkenes and oxidatively cleaved. This process enables the robustness and properties of polyacrylates to be maintained during their usable lifetime. The ability to tune the degree of degradation was demonstrated by varying the carboxylic acid content of the polymers. This method is compatible with a wide range of polymers prepared from vinyl monomers through copolymerization of acrylic acid with different monomers including acrylates, acrylamides, and styrenics.

Poly(Vinyl Ketones): New Directions in Photodegradable Polymers.

Poly(vinyl ketones) (PVKs) have received considerable attention over the past few decades due to their unique photochemistry and photodegradation properties under ultraviolet (UV) light. Many PVKs rapidly undergo photodegradation under UV light. The side-chain carbonyl moieties of PVKs permit photolysis through Norrish type I or Norrish type II reaction mechanisms and can also be readily modified by nucleophilic addition reactions. These unique properties lead to this class of polymers serving as versatile scaffolds for generating functional materials. This review captures the evolution of synthetic routes to access well-defined PVKs, along with their photochemistry and photo-degradation pathways, and discusses recent and potential applications of these photodegradable materials.

Ultrafast Xanthate-Mediated Photoiniferter Polymerization-Induced Self-Assembly (PISA).

Polymerization-induced self-assembly (PISA) is a powerful technique for preparing block copolymer nanostructures. Recently, efforts have been focused on applying photochemistry to promote PISA due to the mild reaction conditions, low cost, and spatiotemporal control that light confers. Despite these advantages, chain-end degradation and long reaction times can mar the efficacy of this process. Herein, we demonstrate the use of ultrafast photoiniferter PISA to produce polymeric nanostructures. By exploiting the rapid photolysis of xanthates, near-quantitative monomer conversion can be achieved within five minutes to prepare micelles, worms, and vesicles at various core-chain lengths, concentrations, or molar compositions.

Janus Cross-links in Supramolecular Networks.

Thermosets composed of cross-linked polymers demonstrate enhanced thermal, solvent, chemical, and dimensional stability as compared to their non-cross-linked counterparts. However, these often-desirable material properties typically come at the expense of reprocessability, recyclability, and healability. One solution to this challenge comes from the construction of polymers that are reversibly cross-linked. We relied on lessons from Nature to present supramolecular polymer networks comprised of cooperative Janus-faced hydrogen bonded cross-links. A triazine-based guanine-cytosine base (GCB) with two complementary faces capable of self-assembly through three hydrogen bonding sites was incorporated into poly(butyl acrylate) to create a reprocessable and recyclable network. Rheological experiments and dynamic mechanical analysis (DMA) were employed to investigate the flow behavior of copolymers with randomly distributed GCB units of varying incorporation. Our studies revealed that the cooperativity of multiple hydrogen bonding faces yields excellent network integrity evidenced by a rubbery plateau that spanned the widest temperature range yet reported for any supramolecular network. To verify that each Janus-faced motif engages in multiple cross-links, we studied the effects of local concentration of the incorporated GCB units within the polymer chain. Mechanical strength improved by colocalizing the GCB within a block copolymer morphology. This enhanced performance revealed that the number of effective cross-links in the network increased with the local concentration of hydrogen bonding units. Overall, this study demonstrates that cooperative noncovalent interactions introduced through Janus-faced hydrogen bonding moieties confers excellent network stability and predictable viscoelastic flow behavior in supramolecular networks.

Photocatalytic Direct Decarboxylation of Carboxylic Acids to Derivatize or Degrade Polymers.

Visible light-mediated direct decarboxylation of carboxylic acids with an acridine photocatalyst is a convenient and powerful method to generate carbon-centered radicals in polymer chains. Advantageously, this process proceeds under mild conditions, without preactivation of the acid groups. We utilize decarboxylation in the presence of a hydrogen atom donor to form statistical acrylate-ethylene and acrylate-propylene copolymers, which are challenging to obtain by direct polymerization. We additionally show that decarboxylation of methacrylic acid units within polymethacrylates can trigger degradation of the polymer backbones. Moreover, a dual catalytic approach, which combines the function of an acridine photocatalyst with that of a cobaloxime catalyst, is leveraged to furnish unique copolymers with pendent alkenes. Our work indicates that direct decarboxylation is a versatile technique for the synthesis of functional materials with tailored compositions and properties.

Tethered Tungsten-Alkylidenes for the Synthesis of Cyclic Polynorbornene via Ring Expansion Metathesis: Unprecedented Stereoselectivity and Trapping of Key Catalytic Intermediates.

This report describes an approach for preparing tethered tungsten-imido alkylidene complexes featuring a tetra-anionic pincer ligand. Treating the tungsten alkylidyne [tBuOCO]W≡CtBu(THF)2 (1) with isocyanates (RNCO; R = tBu, Cy, and Ph) leads to cycloaddition occurring exclusively at the C═N bond to generate the tethered tungsten-imido alkylidenes (6-NR). Unanticipated intermediates reveal themselves, including the discovery of [(O2CtBuC═)W(η2-(N,C)-RNCO)(THF)] (11-R) and an unprecedented decarbonylation product [(tBuOCO)W(≡NR)(tBuCCO)] (14-R), on the pathway to the formation of 6-NR. Complex 11-R is kinetically stable for sterically bulky isocyanate R = tBu (11-tBu) and is isolated and characterized by single-crystal X-ray diffraction. Finally, adding to the short list of catalysts capable of ring expansion metathesis polymerization (REMP), complexes 6-NR and 11-tBu are active for the stereoselective synthesis of cyclic polynorbornene.

Hyperbranched Bisphosphonate-Functional Polymers via Self-Condensing Vinyl Polymerization and Postpolymerization Multicomponent Reactions.

The synthesis of hyperbranched aminobisphosphonic acid polymers via reversible addition-fragmentation chain transfer (RAFT) self-condensing vinyl polymerization is reported. A novel acrylamide-functional chain transfer monomer is synthesized and characterized by 1 H and 13 C NMR spectroscopy, elemental analysis, and mass spectrometry. The monomer is subsequently copolymerized with an acrylamide monomer bearing a pendent amine group to create hyperbranched amine-functional polymers with degrees of branching dictated by changing the reaction stoichiometry. The aminobisphosphonate functional group is introduced via a 3-component Kabachnik-Fields reaction. An alternate functionalization of the amine polymers to create acid-degradable imine hydrogels is also employed. This work demonstrates the application of multicomponent reactions to RAFT-derived hyperbranched polymers and provides a new route to previously inaccessible polymers.

Hybrid Block Copolymer Synthesis by Merging Photoiniferter and Organocatalytic Ring-Opening Polymerizations.

Access to block copolymers from monomers that do not polymerize via a common mechanism requires initiation from a multifunctional species that allows orthogonal polymerization chemistries. We disclose a strategy to provide well-defined polyacrylamido-b-polyether block copolymers by a one-pot combination of photoiniferter polymerization and organocatalytic ring-opening polymerization (ROP) using a hydroxy-functionalized trithiocarbonate photoiniferter as the dual initiator at ambient temperature. Our results reveal good compatibility between the two polymerization systems and highlight that they can be performed in arbitrary order or simultaneously with good retention of the thiocarbonylthio functionality. We also demonstrate selective temporal control over the photoiniferter polymerization during concurrent ROP. We harnessed the efficiency of combining these polymerization systems to provide tailor-made block copolymers from chemically distinct monomers.

Block Copolymer Vitrimers.

In this report, we merge block copolymers with vitrimers in an effort to realize the prospect of higher-order, nanoscale control over associative cross-link exchange and flow. We show the use of controlled polymerization as a vital tool to understand fundamental structure-property effects through the precise control of polymer architecture and molecular weight. Vitrimers derived from self-assembling block copolymers exhibit superior resistance to macroscopic deformation in comparison to their analogs generated from statistical copolymers. Our results suggest that the enhanced creep resistance achieved by control over chain topology in block vitrimers can be used to tune viscoelastic properties. The resistance to macroscopic deformation that arises from a microphase-separated structure in this new class of materials differentiates block vitrimers from their statistical counterparts and introduces the potential of topology-control over viscoelastic flow.

Modular Genetic Code Expansion Platform and PISA Yield Well-Defined Protein-Polymer Assemblies.

We present a modular platform from which biohybrid protein-polymer nanostructures can be generated in a straightforward and facile manner. Specifically, an aqueous polymerization-induced self-assembly (PISA) AB block copolymerization system was derived from a mutant superfolder green fluorescent protein (sfGFP) as the solvophilic, stabilizing A block. By genetically encoding sfGFP with an isobutyryl bromide functionality, we grafted a quintessential atom-transfer radical polymerization initiation site with hydroxypropyl methacrylate (HPMA) to form the solvophobic B block. Monitoring nanostructure formation using dynamic light scattering, gel permeation chromatography, and transmission electron microscopy revealed uniform micellar morphologies. The radii of the micelles increased with increasing HPMA block length, resulting in nanoparticle sizes ranging from 15 to 48 nm. Solvophilic stabilization afforded by the encoded sfGFP makes this an ideal PISA initiator, and we posit this platform has potential for generating complex biohybrid nanostructures for other protein-polymer systems.

Synthesis of functional 1,2-dithiolanes from 1,3-bis-tert-butyl thioethers.

We report the one-step synthesis of diversely substituted functional 1,2-dithiolanes by reacting readily accessible 1,3-bis-tert-butyl thioethers with bromine. The reaction proceeds to completion within minutes under mild conditions, presumably via a sulfonium-mediated ring closure. Using X-ray crystallography and UV-vis spectroscopy, we demonstrate how substituent size and ring substitution pattern can affect the geometry and photophysical properties of 1,2-dithiolanes.

Proapoptotic Peptide Brush Polymer Nanoparticles via Photoinitiated Polymerization-Induced Self-Assembly.

Herein, we report the photoinitiated polymerization-induced self-assembly (photo-PISA) of spherical micelles consisting of proapoptotic peptide-polymer amphiphiles. The one-pot synthetic approach yielded micellar nanoparticles at high concentrations and at scale (150 mg mL-1 ) with tunable peptide loadings up to 48 wt. %. The size of the micellar nanoparticles was tuned by varying the lengths of hydrophobic and hydrophilic building blocks. Critically, the peptide-functionalized nanoparticles imbued the proapoptotic "KLA" peptides (amino acid sequence: KLAKLAKKLAKLAK) with two key properties otherwise not inherent to the sequence: 1) proteolytic resistance compared to the oligopeptide alone; 2) significantly enhanced cell uptake by multivalent display of KLA peptide brushes. The result was demonstrated improved apoptosis efficiency in HeLa cells. These results highlight the potential of photo-PISA in the large-scale synthesis of functional, proteolytically resistant peptide-polymer conjugates for intracellular delivery.

Adaptable Crosslinks in Polymeric Materials: Resolving the Intersection of Thermoplastics and Thermosets.

The classical division of polymeric materials into thermoplastics and thermosets based on covalent network structure often implies that these categories are distinct and irreconcilable. Yet, the past two decades have seen extensive development of materials that bridge this gap through incorporation of dynamic crosslinks, enabling them to behave as both robust networks and moldable plastics. Although their potential utility is significant, the growth of covalent adaptable networks (CANs) has obscured the line between "thermoplastic" and "thermoset" and erected a conceptual barrier to the growing number of new researchers entering this discipline. This Perspective aims to both outline the fundamental theory of CANs and provide a critical assessment of their current status. We emphasize throughout that the unique properties of CANs emerge from the network chemistry, and particularly highlight the role that the crosslink exchange mechanism (i.e., dissociative exchange or associative exchange) plays in the resultant material properties under processing conditions. Predominant focus will be on thermally induced dynamic behavior, as the majority of presently employed exchange chemistries rely on thermal stimulus, and it is simple to apply to bulk materials. Lastly, this Perspective aims to identify current issues and address possible solutions for better fundamental understanding within this field.