Themed collection Polymer Chemistry Lectureship Winners

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

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.

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.

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.

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.

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.

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).

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.

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.

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.

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.

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.

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.

Herein, we report the preparation of nucleobase-containing synthetic amphiphilic diblock copolymers using RAFT polymerization.

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.

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.

In this study, we compared three different hybrid gold nanoparticle shapes (spherical, rod and star) for photothermal therapy and the delivery of doxorubicin.

Dextran aldehyde was functionalised with up to 38 wt% catechin and the resulting conjugate demonstrated cytotoxic efficacy against neuroblastoma cells.

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.

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.

Investigation on the reactivity and the controlling ability of a series of amide-functionalized alkoxyamines based on the SG1 nitroxide is reported.

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.

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.

Halochromic polyamide6-based fabrics with drastically reduced dye-leaching through blend electrospinning of PA6 with dye-functionalized copolymer.

Polymer coatings on silica cores as well as fluorescent protein binding and fluorescent lifetime analysis.

A muscle-like metallo-supramolecular polymer based on a solvent-driven [c2]daisy chain has been prepared from an amino-modified pillar[5]arene. The integration of terpyridine moieties on both ends of the [c2]daisy chain and the stiff architecture of pillar[5]arene units facilitated the efficient formation of the metallo-supramolecular polymer.

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.

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 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.

In this work, we studied the influence of the structure of macromolecular ligands on the relaxivity of gadolinium contrast agents constructed as nanoparticle systems.

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.