Themed collection Polymer Chemistry Lectureship Winners
SARA ATRP or SET-LRP. End of controversy?
A debate has proceeded in the literature regarding the mechanism of reversible-deactivation radical polymerization in the presence of Cu0.
Integrated motion of molecular machines in supramolecular polymeric scaffolds
Here we highlight the recent progress in the field of integrated motion of molecular machines in supramolecular polymeric scaffolds.
Polymer conjugation of proteins as a synthetic post-translational modification to impact their stability and activity
This review article discusses the impact of polymer modification on bioconjugate performance, including both activity and stability, with a focus on how the polymer structure and functionality impact these parameters.
Blocked isocyanates: from analytical and experimental considerations to non-polyurethane applications
In this review we aim to provide an introductory guide to blocked isocyanates, through discussion on different examples of blocking groups, along with experimental considerations for their application.
Synthesis and polymerization of boronic acid containing monomers
This mini-review summarizes the most commonly used methods for the synthesis of phenylboronic acid-(co)polymers ranging from simple straightforward polymerization to complex post-polymerization modification.
Enhancing the therapeutic effects of polyphenols with macromolecules
A review of key macromolecular systems employed to stabilise polyphenols, including direct polymerisation of polyphenol monomers and conjugation with macromolecules.
Layer-by-layer preparation of polyelectrolyte multilayer membranes for separation
Polymer membranes prepared by layer-by-layer depostition provide a highly promising platform for the development of an efficient and sustainable technique for separation.
Recent trends in the design of anticancer polymer prodrug nanocarriers
Nanocarriers based on polymer prodrugs have attracted much attention to perform drug delivery, especially in cancer therapy.
Recent advances in the design of bioconjugates from controlled/living radical polymerization
A comprehensive review of the recent advances in the synthesis of well-defined bioconjugates from controlled/living radical polymerization, including proteins, peptides and oligonucleotides, is presented and outlines work up to early 2010.
Substituent effects in iniferter photopolymerization: can bond homolysis be enhanced by electronics?
Substituent effects on the dithiobenzoate moiety of RAFT iniferters are investigated. Donating groups accelerate the iniferter process, while withdrawing groups slow it. The unique efficiency of the methoxydithiobenzoate iniferter was uncovered.
Tailoring polymer dispersity by mixing chain transfer agents in PET-RAFT polymerization
Here we report a simple and versatile batch methodology to tailor polymer dispersity utilizing PET-RAFT polymerization.
Photolabile protecting groups: a strategy for making primary amine polymers by RAFT
Photolabile amine protecting groups are combined with RAFT polymerization to create well-defined amine containing polymers, which is typically a challenge for RAFT polymerization.
Palladium-polymer nanoreactors for the aqueous asymmetric synthesis of therapeutic flavonoids
Polymeric core–shell micelles incorporating a chiral palladium pyridinooxazoline catalyst are presented as nanoreactors for the aqueous asymmetric synthesis of flavanones, a class of flavonoids, with therapeutic properties.
Pillararene-based chiral 3D polymer network for heterogeneous asymmetric catalysis
We report the preparation of a chiral 3D polymer network endowed with ability of heterogeneous asymmetric catalysis and good recyclability based on pillararene and (R,R)-tetraaryl-1,3-dioxolane-4,5-dimethanol derivatives.
Temperature programed photo-induced RAFT polymerization of stereo-block copolymers of poly(vinyl acetate)
Stereo-triblock copolymers of poly(vinyl acetate) are synthesized with controlled molecular weights based on a temperature-programed photo-induced RAFT in HFIP.
RAFT-mediated, visible light-initiated single unit monomer insertion and its application in the synthesis of sequence-defined polymers
In this communication, we report a catalyst-free methodology for single unit monomer insertion (SUMI) into reversible addition–fragmentation chain transfer (RAFT) agents initiated by low intensity visible light.
Triazolinedione-“clicked” poly(phosphoester)s: systematic adjustment of thermal properties
The thermal properties of halogen-free flame retardant poly(phosphoester)s from acyclic diene metathesis polycondensation have been optimized by a systematic post-modification using 1,2,4-triazoline-3,5-dione derivatives.
RAFT iniferter polymerization in miniemulsion using visible light
Methodology for the successful implementation of RAFT (4-cyano-4[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid (CDTPA)) iniferter polymerization of butyl methacrylate in miniemulsion using visible light (green light; λmax = 530 nm) has been developed.
Cyclohexyl-substituted poly(phosphonate)-copolymers with adjustable glass transition temperatures
2-Cyclohexyl-2-oxo-1,3,2-dioxaphospholane (cyHexPPn), a new monomer for the anionic ring-opening polymerization to poly(ethylene alkyl phosphonate)s is presented.
Poly(N-isopropylacrylamide) coated gold nanoparticles as colourimetric temperature and salt sensors
Thermoresponsive PNIPAM coated AuNPs having dual stabilisation by the polymer chains and the charges, has been utilised for the development of temperature and salt sensors.
Self-healing, malleable and creep limiting materials using both supramolecular and reversible covalent linkages
A combination of supramolecular and dynamic covalent linkages were used to create creep limited self-healing materials.
Facile construction of fluorescent polymeric aggregates with various morphologies by self-assembly of supramolecular amphiphilic graft copolymers
Facile construction of fluorescent polymeric aggregates with various morphologies was realized by self-assembly of supramolecular amphiphilic graft copolymers.
Thermoresponsive polymeric temperature sensors with broad sensing regimes
Polymeric temperature sensors with a broad sensing regime in aqueous solution have been developed.
A double supramolecular crosslinked polymer gel exhibiting macroscale expansion and contraction behavior and multistimuli responsiveness
Here we report a novel supramolecular polymer gel containing two types of physical crosslinks that are orthogonal to each other. It shows macroscale expansion and contraction behavior and multistimuli responsiveness.
Accelerated living cationic ring-opening polymerization of a methyl ester functionalized 2-oxazoline monomer
Kinetic studies on the homo- and copolymerization of 2-methoxycarboxyethyl-2-oxazoline with 2-methyl-2-oxazoline and 2-ethyl-2-oxazoline is discussed.
Photoredox catalyst-mediated atom transfer radical addition for polymer functionalization under visible light
A facile method for post-functionalization of polymers with side olefin groups was developed by visible light-mediated atom transfer radical addition (ATRA) employing a photoredox catalyst, fac-Ir(ppy)3.
Spatial and temporal control of drug release through pH and alternating magnetic field induced breakage of Schiff base bonds
A novel theranostic controlled drug delivery platform that binds the drug to the nanocarrier by utilising Schiff base bonds to achieve high spatial and temporal control over drug release.
Polymerization-Induced Self-Assembly (PISA) – control over the morphology of nanoparticles for drug delivery applications
Polymerization-Induced Self-Assembly (PISA) – control over the morphology of nanoparticles for drug delivery applications.
A triple thermoresponsive schizophrenic diblock copolymer
This article describes a new class of triple thermoresponsive ‘schizophrenic’ diblock copolymer that undergoes transitions from conventional micelles (or vesicles) via unimers to reverse micelles (or vesicles) and finally to a precipitated state upon heating.
polymer formed by the combination of crown ether-based and charge-transfer molecular recognition
We report a supramolecular polymer constructed from two heteroditopic monomers driven by the combination of crown ether-based and charge-transfer molecular recognition.
Direct nitroxide mediated (co)polymerization of
4-vinylphenylboronic acid as route towards sugar sensors
The synthesis of well-defined poly(4-vinylphenylboronic acid) is demonstrated by nitroxide mediated polymerization of this unprotected monomer. This polymer is shown to be both pH and sugar responsive while incorporation of solvatochromic dyes led to sensors.
PMMA based soluble polymeric temperature sensors based on
UCST transition and solvatochromic dyes
The UCST transition of dye-functionalized poly(methyl methacrylate)s results in UV/vis and fluorescent thermometers with a broad linear response in aqueous ethanol.
Moisture tolerant cationic RAFT polymerization of vinyl ethers
Cationic RAFT of vinyl ethers was performed without reagent purification and under ambient conditions by utilizing a PCCP acid initiator with a HBD catalyst. Despite inherent nucleophiles, the system retained high chain end fidelity and modularity.
A general model for the ideal chain length distributions of polymers made with reversible deactivation
A general model is developed for the distribution of polymers made with reversible deactivation. The model is applied to a range of experimental systems including RAFT, cationic and ATRP.
Tuning the molecular weight distributions of vinylketone-based polymers using RAFT photopolymerization and UV photodegradation
The choice and mixture of chain transfer agent in reversible addition/fragmentation chain transfer polymerization has been used to modulate the dispersity and architecture of vinyl ketone polymers and their copolymers.
Achieving molecular weight distribution shape control and broad dispersities using RAFT polymerizations
Metered additions of chain transfer agents are used to control molecular weight distribution (MWD) features in reversible addition-fragmentation chain-transfer polymerizations, giving polymers with tailored MWD shapes and dispersities as high as 6.2.
Dynamic covalent chemistry for architecture changing interpenetrated and single networks
Dynamic single and interpenetrated materials were developed, with post polymerization network exchange enhancing the material properties.
Sustainable thermoplastic elastomers produced via cationic RAFT polymerization
Cationic polymerization enables production of sustainable thermoplastic elastomers constructed from renewable vinyl ethers and -p-methoxystyrene with properties consistent with their petroleum-derived counterparts.
Photocontrolled cationic degenerate chain transfer polymerizations via thioacetal initiators
Photocontrolled cationic polymerizations controlled through a degenerate chain transfer process and photocatalyst turnover to recap propagating chains.
Controlling the crystal structure of precisely spaced polyethylene-like polyphosphoesters
We report the synthesis and crystallization behavior of polyethylene-like polyphosphates with a precise spacing of 20, 30, and 40 methylene groups between each phosphate group, which determined the crystal structure, lamellar, and crystal thickness.
Predictive design of polymer molecular weight distributions in anionic polymerization
Polymer molecular weight distributions are targeted through kinetic modeled with high fidelity based on the temporal control of chain initiation in anionic polymerizations.
Dual-dynamic interpenetrated networks tuned through macromolecular architecture
Controlled polymerization is used to make well defined polymers that are assembled into dynamic interpenetrated network materials. Self-healing, toughness and stress relaxation are imparted into the material through the dynamic linkages.
A cocktail of vitamins for aqueous RAFT polymerization in an open-to-air microtiter plate
We report a highly biocompatible photoinitiation strategy based on Vitamin B2 and Vitamin C. This two-component photoinitiator enables RAFT polymerization to be conducted in high throughput in an open-to-air microtiter plate.
Hydrolytically-degradable homo- and copolymers of a strained exocyclic hemiacetal ester
We report the cationic ring-opening homo- and copolymerization of the 7-membered exocyclic hemiacetal ester 7-methoxyoxepan-2-one (MOPO) to afford poly(7-methoxyoxepan-2-one) [poly(MOPO)] and its copolymers with isobutyl vinyl ether (IBVE).
Self-catalysed folding of single chain nanoparticles (SCNPs) by NHC-mediated intramolecular benzoin condensation
A self-catalysed folding strategy to form single chain nanoparticles (SCNPs) was developed via an intramolecular N-heterocyclic carbene (NHC)-mediated benzoin condensation.
Giant polymersomes from non-assisted film hydration of phosphate-based block copolymers
Polybutadiene-block-poly(ethyl ethylene phosphate) can reproducibly self-assemble in large number into giant unilamellar vesicles (GUVs) by non-assisted film hydration, representing a stepping stone for better liposomes – substitutes towards the generation of artificial cells.
Reversible ionically-crosslinked single chain nanoparticles as bioinspired and recyclable nanoreactors for N-heterocyclic carbene organocatalysis
The intrinsic advantages of poly(ionic liquid)s (PILs), based on their high chemical activity and flexible structure, have been harnessed by exploring their applicability as catalytic single chain nanoparticles (SCNPs).
Tuning thermoresponsive network materials through macromolecular architecture and dynamic thiol-Michael chemistry
Synthesis of precision polymers crosslinked with dynamic thiol-Michael adducts is developed, and the materials are characterized to determine structure–property relationships.
Self-stabilized, hydrophobic or PEGylated paclitaxel polymer prodrug nanoparticles for cancer therapy
Facile derivatization of paclitaxel (Ptx) and subsequent “drug-initiated” synthesis of well-defined Ptx-polymer prodrugs was performed from nitroxide-mediated polymerization or reversible addition–fragmentation chain transfer polymerization.
Temperature responsive poly(phosphonate) copolymers: from single chains to macroscopic coacervates
Detailed investigation of the LCST phase separation mechanism of poly(ethylene alkyl phosphonate)- copolymers is presented.
Surface-attached poly(phosphoester)-hydrogels with benzophenone groups
Photo-reactive poly(phosphoester)s (PPEs) forming surface-attached PPE-networks and hydrogels are presented.
The application of blocked isocyanate chemistry in the development of tunable thermoresponsive crosslinkers
The synthesis of a novel monomer, methacryloyl pyrazole, and its subsequent reaction with diisocyanates to produce thermoresponsive crosslinkers is reported.
Dual stimuli responsive self-healing and malleable materials based on dynamic thiol-Michael chemistry
Thiol-maleimide adducts are incorporated as crosslinkers into polymer networks and act as pH-responsive and thermoresponsive dynamic crosslinkers, imparting malleability and self-healing properties into the material.
Understanding the CDSA of poly(lactide) containing triblock copolymers
Using crystallization driven assembly (CDSA) the simple preparation of well-defined tuneable 1D and 2D structures based on poly(lactide) triblock copolymers is demonstrated.
Structure–cytotoxicity relationship of drug-initiated polymer prodrug nanoparticles
Cladribine (CdA)-based polymer prodrug nanoparticles were obtained by “drug-initiated” RAFT polymerization of squalenyl methacrylate (SqMA) from two different CdA-bearing chain transfer agents (CTAs) to evaluate the influence of the nature of the linkage between CdA and the CTA, and the bulkiness of the polymer, on the drug release and the biological performance.
The hydrolytic behavior of N,N′-(dimethylamino)ethyl acrylate-functionalized polymeric stars
Well-defined N,N′-(dimethylamino)ethyl acrylate (DMAEA) functionalized polymeric stars have been synthesized via an arm-first approach.
Oxygen tolerant photopolymerization for ultralow volumes
A benchtop approach is developed for the synthesis of various polymeric architectures using an aqueous Reversible Addition–Fragmentation chain Transfer (RAFT) photopolymerization technique.
Grafting challenging monomers from proteins using aqueous ICAR ATRP under bio-relevant conditions
Aqueous ICAR ATRP was applied to graft well defined acrylamide, N,N-dimethylacrylamide and N-vinylimidazole homo and block copolymers from a model protein initiator (bovine serum albumin (BSA)) under bio-relevant conditions.
Comparison of photo- and thermally initiated polymerization-induced self-assembly: a lack of end group fidelity drives the formation of higher order morphologies
We demonstrate that the PISA of identical block copolymers by either a photo or thermally initiated approach leads to structures that are both chemically and morphologically distinct.
Application of oxygen tolerant PET-RAFT to polymerization-induced self-assembly
The inhibitory effects of molecular oxygen in PET-RAFT polymerization can be overcome by the addition of singlet oxygen quenchers. This oxygen tolerant approach is compatible with a range of organic solvents and can be used to synthesize nanoparticles according to a PISA process.
The living anionic polymerization of activated aziridines: a systematic study of reaction conditions and kinetics
The living anionic polymerization of sulfonyl aziridines is systematically studied by variation of solvents, temperatures, gegenions, and novel initiators.
Versatile oligomers and polymers from flavonoids – a new approach to synthesis
Antioxidant oligomers and polymers have been prepared from two flavonoids, catechin and quercetin, using a new facile technique.
Probing the causes of thermal hysteresis using tunable Nagg micelles with linear and brush-like thermoresponsive coronas
Self-assembled thermoresponsive polymers in aqueous solution have great potential as smart, switchable materials for use in biomedical applications.
Gadolinium-functionalized nanoparticles for application as magnetic resonance imaging contrast agents via polymerization-induced self-assembly
Polymerization-induced self-assembly (PISA) is an easily applied synthetic technique for the preparation of polymer nanoparticles with various shapes and at high concentrations.
Synthesis of novel boronic acid-decorated poly(2-oxazoline)s showing triple-stimuli responsive behavior
The synthesis of novel boronic-acid decorated poly(2-oxazoline)s showing a glucose- and pH dependent thermal transition is reported.
Visible and sunlight driven RAFT photopolymerization accelerated by amines: kinetics and mechanism
RAFT polymerization using only tertiary amines under visible light or sunlight is studied, to determine the kinetics of polymerization, and the system is applied to various monomers giving well-defined homo and block copolymers.
A logic gate for external regulation of photopolymerization
The use of photocatalysts for visible light mediated reversible deactivation radical polymerization (RDRP) provides an efficient route for the synthesis of well-defined polymers with spatial, temporal and sequence control.
Pillararene-based amphiphilic supramolecular brush copolymers: fabrication, controllable self-assembly and application in self-imaging targeted drug delivery
Here we construct the first pillararene-based amphiphilic supramolecular brush copolymer, which can be utilized as a targeting self-imaging drug delivery vehicle.
CO2/pH-responsive particles with built-in fluorescence read-out
A novel fluorescent monomer was synthesized to probe the state of CO2-responsive cross-linked polymer particles.
N-Ferrocenylsulfonyl-2-methylaziridine: the first ferrocene monomer for the anionic (co)polymerization of aziridines
N-Ferrocenylsulfonyl-2-methylaziridine (fcMAz) is the first aziridine-based monomer functionalized at the sulfonamide and the first organometallic aziridine for the anionic ROP. It was polymerized to homo and copolymers (block or statistical) with adjustable molecular weights.
About this collection
This collection highlights winners of the Polymer Chemistry Lectureship. This annual award was established in 2015 to honour an early-stage career scientist who has made a significant contribution to the polymer chemistry field.
The 2022 Polymer Chemistry Lectureship was awarded to Dominik Konkolewicz (Miami University). Dominik Konkolewicz earned a Bachelors of Science degree at the University of Sydney (Australia) in 2006, majoring in Chemistry and Mathematics. He continued at the University of Sydney to complete his PhD (2011) working with Dr. Sébastien Perrier on polymerization kinetics and branched polymer synthesis. He went on to complete postdoctoral research at Carnegie Mellon University in Pittsburgh (USA), working with Dr. Krzysztof Matyjaszewski on mechanisms of complex reactions and applications of precisely defined polymers. In 2014, Dominik joined the Department of Chemistry and Biochemistry at Miami University in Oxford OH (USA) as an Assistant Professor, with promotion to Associate Professor in 2019. He will start as full professor in Fall 2022. The Konkolewicz group explores a wide range of topics in Polymer Chemistry, including radical polymerization mechanisms, dynamically bonded polymer materials, light driven reactions, bioconjugates, and polymer based self-assembly. Dominik has published over 130 research articles in polymer chemistry and polymer science, with a particular focus on developing fundamental science to facilitate the design of functional materials.
This collection features articles published in Polymer Chemistry from Dominik Konkolewicz, as well as the seven previous lectureship winners:
2021- Brett Fors, Cornell University, USA
2020 - Rachel O’Reilly, University of Birmingham, UK
2019 - Frederick Wurm, Max Planck Institute for Polymer Research, Germany
2018 - Cyrille Boyer, University of New South Wales, Australia
2017 - Julien Nicolas, Université Paris Sud, France
2016 - Feihe Huang, Zhejiang University, China
2015 - Richard Hoogenboom, Ghent University, Belgium