Themed collection Polymer Chemistry Lectureship Winners

A debate has proceeded in the literature regarding the mechanism of reversible-deactivation radical polymerization in the presence of Cu⁰.

Here we highlight the recent progress in the field of integrated motion of molecular machines in supramolecular polymeric scaffolds.

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.

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.

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.

A review of key macromolecular systems employed to stabilise polyphenols, including direct polymerisation of polyphenol monomers and conjugation with macromolecules.

Polymer membranes prepared by layer-by-layer depostition provide a highly promising platform for the development of an efficient and sustainable technique for separation.

Nanocarriers based on polymer prodrugs have attracted much attention to perform drug delivery, especially in cancer therapy.

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 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.

Here we report a simple and versatile batch methodology to tailor polymer dispersity utilizing PET-RAFT polymerization.

Photolabile amine protecting groups are combined with RAFT polymerization to create well-defined amine containing polymers, which is typically a challenge for RAFT polymerization.

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.

We report the preparation of a chiral 3D polymer network endowed with ability of heterogeneous asymmetric catalysis and good recyclability based on pillar[5]arene and (R,R)-tetraaryl-1,3-dioxolane-4,5-dimethanol derivatives.

Stereo-triblock copolymers of poly(vinyl acetate) are synthesized with controlled molecular weights based on a temperature-programed photo-induced RAFT in HFIP.

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.

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.

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; λ_max = 530 nm) has been developed.

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.

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.

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 was realized by self-assembly of supramolecular amphiphilic graft copolymers.

Polymeric temperature sensors with a broad sensing regime in aqueous solution have been developed.

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.

Kinetic studies on the homo- and copolymerization of 2-methoxycarboxyethyl-2-oxazoline with 2-methyl-2-oxazoline and 2-ethyl-2-oxazoline is discussed.

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.

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.

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.

We report a supramolecular polymer constructed from two heteroditopic monomers driven by the combination of crown ether-based and charge-transfer molecular recognition.

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.

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.

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 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.

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.

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 single and interpenetrated materials were developed, with post polymerization network exchange enhancing the material properties.

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 polymerizations controlled through a degenerate chain transfer process and photocatalyst turnover to recap propagating chains.

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.

Polymer molecular weight distributions are targeted through kinetic modeled with high fidelity based on the temporal control of chain initiation in anionic polymerizations.

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.

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.

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).

A self-catalysed folding strategy to form single chain nanoparticles (SCNPs) was developed via an intramolecular N-heterocyclic carbene (NHC)-mediated benzoin condensation.

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.

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).

Synthesis of precision polymers crosslinked with dynamic thiol-Michael adducts is developed, and the materials are characterized to determine structure–property relationships.

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.

Detailed investigation of the LCST phase separation mechanism of poly(ethylene alkyl phosphonate)- copolymers is presented.

Photo-reactive poly(phosphoester)s (PPEs) forming surface-attached PPE-networks and hydrogels are presented.

The synthesis of a novel monomer, methacryloyl pyrazole, and its subsequent reaction with diisocyanates to produce thermoresponsive crosslinkers is reported.

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.

Using crystallization driven assembly (CDSA) the simple preparation of well-defined tuneable 1D and 2D structures based on poly(lactide) triblock copolymers is demonstrated.

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.

Well-defined N,N′-(dimethylamino)ethyl acrylate (DMAEA) functionalized polymeric stars have been synthesized via an arm-first approach.

A benchtop approach is developed for the synthesis of various polymeric architectures using an aqueous Reversible Addition–Fragmentation chain Transfer (RAFT) photopolymerization technique.

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.

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.

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 sulfonyl aziridines is systematically studied by variation of solvents, temperatures, gegenions, and novel initiators.

Antioxidant oligomers and polymers have been prepared from two flavonoids, catechin and quercetin, using a new facile technique.

Self-assembled thermoresponsive polymers in aqueous solution have great potential as smart, switchable materials for use in biomedical applications.

Polymerization-induced self-assembly (PISA) is an easily applied synthetic technique for the preparation of polymer nanoparticles with various shapes and at high concentrations.

The synthesis of novel boronic-acid decorated poly(2-oxazoline)s showing a glucose- and pH dependent thermal transition is reported.

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.

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.

Here we construct the first pillararene-based amphiphilic supramolecular brush copolymer, which can be utilized as a targeting self-imaging drug delivery vehicle.

A novel fluorescent monomer was synthesized to probe the state of CO₂-responsive cross-linked polymer particles.

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.