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.
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.
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.
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.
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.
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.
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).
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.
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.
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.
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.
Side-chain poly(phosphoramidate)s via acyclic diene metathesis polycondensation
Side-chain poly(phosphoramidate)s (PPAs) have been prepared by ADMET polycondensation and compared to structural analogues of poly(phosphoester)s. Thermal properties, stability, and crystallization behavior were analyzed. This is the first example for PPAs prepared by ADMET.
Efficient synthesis of 2-methylene-4-phenyl-1,3-dioxolane, a cyclic ketene acetal for controlling the NMP of methyl methacrylate and conferring tunable degradability
The efficient and reliable synthesis of 2-methylene-4-phenyl-1,3-dioxolane (MPDL) was reported and MPDL was used as a controlling comonomer for nitroxide-mediated polymerization of methyl methacrylate to give degradable copolymers.
Micellar nanoparticles with tuneable morphologies through interactions between nucleobase-containing synthetic polymers in aqueous solution
Herein, we report the preparation of nucleobase-containing synthetic amphiphilic diblock copolymers using RAFT polymerization.
Complexation of thermoresponsive dialkoxynaphthalene end-functionalized poly(oligoethylene glycol acrylate)s with CBPQT4+ in water
The effect of polymer structure and cloud point temperature on the supramolecular assembly of the naphthalene end-groups with cyclobis(paraquat-p-phenylene) (CBPQT4+) is reported.
Use of complementary nucleobase-containing synthetic polymers to prepare complex self-assembled morphologies in water
Amphiphilic block copolymers with synthetic nucleobase-containing blocks as the hydrophobic segments were successfully synthesized using RAFT polymerisation and then self-assembled via solvent switch in aqueous solutions.
Effect of gold nanoparticle shapes for phototherapy and drug delivery
In this study, we compared three different hybrid gold nanoparticle shapes (spherical, rod and star) for photothermal therapy and the delivery of doxorubicin.
Efficient functionalisation of dextran-aldehyde with catechin: potential applications in the treatment of cancer
Dextran aldehyde was functionalised with up to 38 wt% catechin and the resulting conjugate demonstrated cytotoxic efficacy against neuroblastoma cells.
Poly(2-cycloalkyl-2-oxazoline)s: high melting temperature polymers solely based on Debye and Keesom van der Waals interactions
The synthesis of new 2-cycloalkyl-2-oxazoline monomers, namely 2-cyclobutyl (cBuOx), 2-cyclopentyl (cPentOx) and 2-cyclohexyl-2-oxazoline (cHexOx) is described. Polymers thereof are semi-crystalline and reveal unexpectedly high melting transitions.
Solvent-free mechanochemical synthesis of a bicyclononyne tosylate: a fast route towards bioorthogonal clickable poly(2-oxazoline)s
The mechanochemical synthesis of a bicyclononyne tosylate (BCN-OTs) and its subsequent use for the CROP of 2-ethyl-2-oxazoline yielding bioorthogonal clickable poly(2-ethyl-2-oxazoline) is presented.
On the structure–control relationship of amide-functionalized SG1-based alkoxyamines for nitroxide-mediated polymerization and conjugation
Investigation on the reactivity and the controlling ability of a series of amide-functionalized alkoxyamines based on the SG1 nitroxide is reported.
Organo-photocatalysts for photoinduced electron transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization
In this work, we demonstrate the use of organophotoredox catalysts under visible light to perform photoinduced electron transfer-reversible addition fragmentation chain transfer (PET-RAFT) for the polymerization of methacrylate monomers.
Versatile side chain modification via isocyanide-based multicomponent reactions: tuning the LCST of poly(2-oxazoline)s
Poly(2-oxazoline)s are receiving large current interest based on their potential use in biomedical applications. Here we report a novel, straightforward route towards functional poly(2-oxazoline)s by Passerini and Ugi reactions.
Dye immobilization in halochromic nanofibers through blend electrospinning of a dye-containing copolymer and polyamide-6
Halochromic polyamide6-based fabrics with drastically reduced dye-leaching through blend electrospinning of PA6 with dye-functionalized copolymer.
Surface modification of polydopamine coated particles via glycopolymer brush synthesis for protein binding and FLIM testing
Polymer coatings on silica cores as well as fluorescent protein binding and fluorescent lifetime analysis.
Construction of muscle-like metallo-supramolecular polymers from a pillararene-based [c2]daisy chain
A muscle-like metallo-supramolecular polymer based on a solvent-driven [c2]daisy chain has been prepared from an amino-modified pillararene. The integration of terpyridine moieties on both ends of the [c2]daisy chain and the stiff architecture of pillararene units facilitated the efficient formation of the metallo-supramolecular polymer.
Fast and accurate partial hydrolysis of poly(2-ethyl-2-oxazoline) into tailored linear polyethylenimine copolymers
This work reports on defining optimal conditions to achieve tailored P(EtOx-co-EI) copolymers in a fast and reproducible way, utilizing high temperatures and controlled acidic conditions.
Cu(0)-mediated polymerization of hydrophobic acrylates using high-throughput experimentation
In this paper the optimization of the Cu(0)-mediated polymerization of n-butyl acrylate and 2-methoxyethyl acrylate is reported using an automated parallel synthesizer.
A block copolymer-stabilized co-precipitation approach to magnetic iron oxide nanoparticles for potential use as MRI contrast agents
A library of magnetic nanoparticles was generated using in situ co-precipitation of ferrous (Fe2+) and ferric (Fe3+) ions from aqueous solutions in the presence of functional block copolymers.
The precise molecular location of gadolinium atoms has a significant influence on the efficacy of nanoparticulate MRI positive contrast agents
In this work, we studied the influence of the structure of macromolecular ligands on the relaxivity of gadolinium contrast agents constructed as nanoparticle systems.
Dual pH- and temperature-responsive RAFT-based block co-polymer micelles and polymer–protein conjugates with transient solubility
Via a smart combination of temperature-responsive and acid labile acetal monomers, pH-degradable copolymers are obtained with à la carte lower critical solution temperature behaviour that are shown to be suitable for drug delivery and protein conjugation.
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 2020 Polymer Chemistry Lectureship was awarded to Rachel O’Reilly (University of Birmingham). Rachel O’Reilly leads a large interdisciplinary team working at the interface of chemistry, materials and biology. The group has received numerous national and international awards for her polymer and material efforts, including four from the Royal Society of Chemistry (RSC), young researcher medals from the American Chemical Society (ACS) and the International Union of Pure and Applied Chemistry (IUPAC), the world authority on chemical nomenclature and terminology. She has held a number of prestigious fellowships from the ESPRC, Royal Society and Royal Commission for the Exhibition of 1851 and received major grants and research support from the ERC, BP and EPSRC.
She has published over 175 research papers in scientific journals, as well as reviews and book chapters in the fields of polymer synthesis, self-assembly, catalysis and DNA nanotechnology. She has given over 170 invited lectures and was recognised as one of the Royal Society of Chemistry's 175 faces of Chemistry.
This collection features articles published in Polymer Chemistry from Rachel O’Reilly as well as the five previous lectureship winners:
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