Themed collection Polymer Chemistry Pioneering Investigators 2021

This themed issue of Polymer Chemistry highlights the work of pioneering investigators in the polymer chemistry field. Associate Editors Emily Pentzer and Holger Frey introduce the issue.

Borylation strategies to make AB Suzuki–Miyaura monomers for use in catalyst-transfer polymerization with nickel or palladium catalysts.

The development of the polymer self-assembly method “in situ nanoparticlization of conjugated polymers” is discussed in this Perspective.

Stimuli-responsive polymers with self-propagating degradation capacity being sensitive to acids, bases, fluoride ions, and hydrogen peroxide are reviewed, exhibiting self-accelerated degradation behavior.

Minireview focused on poly(ε-lysine) and its derivatives via ring-opening polymerization of biorenewable cyclic lysine.

Recent exploitations of stimuli-responsive polymers as ophthalmic drug delivery systems for the treatment of eye diseases are summarized and discussed.

This minireview summarizes the recent development of healable structural color nanocomposites from the perspective of the construction strategies.

The development and applications of an organocatalyzed living radical polymerization via halogen-bonding catalysis, i.e., reversible complexation mediated polymerization (RCMP), are highlighted.

The use of renewable terpene-based monomers for the preparation of sustainable functional polymers is highlighted.

Photocatalytic reversible deactivation radical polymerization (RDRP) permits the use of sustainable solar light for spatiotemporal regulation of radical polymerization under mild conditions.

Deep integration of nucleic acids with synthetic polymers are rapidly becoming the basis of many useful technologies.

This review describes the latest polymeric systems used as boron transporters for boron neutron capture therapy.

Semiflexible polymers are excellent scaffolds for the presentation of a wide variety of (bio)molecules. This manuscript reviews advantages and challenges of the most common conjugation strategies for the major classes of semiflexible polymers.

Quinoidal π-Conjugated polymers with open shell character represent an intriguing class of macromolecules in terms of both fundamental research and practical applications.

Recently, nonconventional luminescent polymers (NLPs) have emerged as the most sought-after alternative luminescent materials. This review provides a thorough description of the importance and applications of each class of state-of-the-art NLPs.

This review focuses on the mechanistic approach, the structure–property relationship and applications of ionic polymeric materials.

We report the synthesis of guanidinium-functionalized cationic dendrons with pendant alkyl chains of varying lengths, which are classified as antibacterial cationic molecular umbrellas.

Thermogelling tri-block terpolymers were made from a bifunctional PEG RAFT agent. The critical solution behavior was tunable by alteration of the terpolymer composition, enabling modulation of gelation temperatures and hydrogel viscoelasticity.

We report a shish-kebab-like supramolecular polymer (SKSP) and its light-responsive self-assembly into nanofibers.

Lipid-encased chiral supramolecular polymer nanorods (SPNRs), synthesized by the nanoprecipitation method in water from a hydrophobic naphthalene-diimide derivative, exhibit excellent thermal stability, intense fluorescence and strong CPL.

SI-Zn⁰-ATRP enables the synthesis of chemically different polymer brushes under full ambient conditions, using just microliter volumes of reaction solutions.

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.

Trithiocarbonate end groups on various polymers, including polyvinylpyridines, are reduced rapily and quantitatively using only tris(trimethylsilyl)silane and light.

The rational combination of cascade thiol-maleimide Michael couplings (CTMMC) with iterative exponential chain growth was demonstrated as an efficient way to synthesize palindromic sequence-defined polymers.

A series of ionic amphiphilic alternating copolymers were characterized via SAXS, TEM and DLS to understand how factors such as covalent structure, and solvent environment affect self-assembly.

We report a class of crosslinked metallo-polyelectrolytes as anion exchange membranes with exceptional mechanical flexibility, dimensional stability and ionic conductivity.

Hydrolyzing polylactide-b-polyetherimide-b-polylactide triblock copolymers produces mesoporous polyetherimide thin films with an average pore width of 24 nm.

Photo-controllable capture and release of proteins by glyco-nanostructures.

In a novel synthetic approach, we have prepared sequence-defined waterborne polyurethanes and have studied their (co)-assembly to hydrocolloids; we find that especially the interplay between the sequences promotes the formation of stable micelles.

Polarity-induced effects in dynamic covalent polyimine CANs were studied, revealing a three-step stress relaxation process.

Azobenzene-functionalized crystalline elastomers containing a monomer with reduced aromatic content exhibits enhanced phototropic response.

We document the design, synthesis, and characterization of the first low glass transition temperature, n-type (i.e., preferentially-reduced) radical polymer.

Kinetics of the acid-catalyzed thiol–ene (ACT) reaction were explored over a range of thiol and vinyl functional groups. Its applicability in material synthesis was demonstrated in the design of photopolymerized polymer networks.

Poly(ethylene furanoate) (PEF) films were first produced using thermo-compression. Thereafter, the chemical recyclability was demonstrated in the presence of a thermally stable organocatalyst followed by its repolymerization.

Polypeptoids bearing carboxylic acid groups on the N-substituent are useful building blocks for the construction of peptidomimetic supramolecular assemblies with stimuli-responsive properties.

Monomer composition, geometry, cross-link density, and cross-link distribution are the primary determinants of material properties in thermosetting networks.

We demonstrated the mechanical enhancement behavior of the comb polyurethanes by the topological isomer system between the linear and comb polyurethane. Also, we assumed the mechanical enhancement mechanism by the rheological properties.

An enzyme-responsive FRET nanoprobe was designed and developed based on AIE-driven fluorescent polysaccharide polymersomes to study the real-time delivery aspects in the intracellular compartments in live cancer cells.

A pyridinium-pended conjugated polyelectrolyte with photo-induced amine doping behaviour was designed for multiple applications.

The size and size variability of bis-MPA dendrimers is shown to be smaller by DOSY-¹H NMR than their linear analog, PBBM. This was accomplished using five different solvents and for the first time confirms, experimentally, what has been theorized.

Advanced spectroscopy, microscopy, diffraction and thermal analysis reveal heterogeneity and dynamics in polyamide industrial adhesives; solid-state NMR spectroscopy enable the prediction of their functional properties.

Two zwitterionic calcium complexes L¹CaN(SiMe₃)₂(THF) (1) and L²CaN(SiMe₃)₂ (2) via protolysis reaction were synthesized. At −75 °C, 1 gave a heterotactic sequence enriched polylactide, whilst 2 produced an isotactic sequence enriched polymer.

The self-assembly of amphiphilic miktoarm star copolymers shows hierarchical pathway complexity from molecular building blocks to miktoarm stars to micellar nano-objects to complex hierarchical assemblies.

Amphiphilic random and random block terpolymers bearing PEG chains, crystalline octadecyl groups, and amorphous oleyl groups were designed to control crystallization and microphase separation in the solid state.

PNIPAM-b-PVDF amphiphilic block copolymers were synthesized via RAFT polymerization in dimethyl carbonate. These block copolymers were able to self-assemble into various morphologies such as spherical, crumpled, lamellar and lenticular 2D aggregates.

Organocatalysts facilitate the synthesis of polythionolactones; oxidative crosslinking yields a degradable polymer foam.

We report that photo-cleaving the corona of block copolymer micelles provides well-defined nanoparticles with surface charges accessible for electrostatic modification.

Thermal annealing of sequence-defined, maleimide- and furan-bearing oligomers enables sequence-selective hybridization to afford molecular ladders incorporating Diels–Alder adduct-based rungs.

Alkyl sulfoxide side groups introduce thermo- and oxidation-sensitivity into poly(meth)acrylates, thus realizing new dual-responsive homopolymers based on one functional group.

Oxidative polymerization of naturally-derived guaiazulene with earth-abundant iron oxidants produces a low bandgap polymer for optoelectronic applications.

The ionization of weak polyelectrolytes can be altered by controlling the composition profile of the comonomers along the chain.

Dynamic covalent exchange (DCE) of anhydride moieties is examined in both model compounds and network polymers.

Condition and substrate effects on CTA-differentiation-involving polymerization were explored for logical control of molecular weight.

Poly(vinyl acetate-co-ethylene) latexes are prepared under a broad range of conditions by emulsion polymerization in the presence of a hydrophilic RAFT/MADIX macromolecular chain transfer agent.

Polyethylene-like polyphosphoesters crystallized from dilute solution into anisotropic nanoplatelets. As proven by solid-state NMR, the phosphate groups are expelled to the surface and on-surface chemistry was conducted leaving the crystals intact.

Hyper-cross-linking of a core of block polymer micelles produces core cross-linked polymer with a spacious hyper-cross-linked core, which is solution-processible.

Dispersity and crystallinity affect the dimensions of lamellar structures formed by amphiphilic block co-oligomers in water as well as the reproducibility of sample formation; spherical and cylindrical morphologies are less affected.

The ring-opening polymerization of cyclic ketene acetals (CKAs) and vinyl monomers is an elegant method to produce degradable copolymers. Owing to DFT calculations, we are now able to better understand the reactivity of CKAs & common vinyl monomers.

The order of Ag(I)–S < Ag(I)–Se < Ag(I)–Te bond strength was confirmed by single-molecule force spectroscopy (SMFS) with quantum chemical studies.

The T_g of semifluorinated polyarylenes made via DAP is varied between 35–195 °C depending on side chain, but solubilities are much less side chain dependent. This is explained by interactions between alkoxyphenyl and tetrafluorobenzene units.

The ring-opening polymerization of α-substituted N-methylated N-carboxy anhydrides is reported. The polymerization was tested using various amino acids and initiators, and was found to be limited by the steric demand of N-methylated compared to conventional amino acids.

Shear-thinning hydrogels that utilize thiol-Michael chain-extension and free radical polymerization have a tunable stretchability.

Diarylethylene (DTE) bearing polyimides showed reversible photochromic behaviors and photoluminescence “on/off” effects, expanded application conditions of photochromic polymers and enhanced tolerance as electronic devices in extreme environments.

Pentafluorophenyl-single chain polymer nanoparticles are readily conjugated with functional amines enabling facile SCNP modification, adjustment of physicochemical properties, and even protein mimicry.

Herein, we present the synthesis of catechol functionalized sequence-defined glycomacromolecules that can covalently block the binding site of lectins and bacterial adhesins.

Polyurethane-based mastics, industrially obtained via a prepolymerization/crosslinking process, benefit from catalyst selection at both stages.

Dual drug-based hyperbranched polymer micelles simultaneously containing methotrexate and chlorambucil were constructed for synergistic cancer chemotherapy.

Computational and experimental verification of a second-order rate expression for polysulfones synthesized using diphenyldichloro sulfone versus a third-order rate expression for polysulfones synthesized using diphenyldifluoro sulfone.

An electrochemical variant of organocatalyzed atom transfer radical polymerization (O-ATRP) is developed and investigated.

A complete set of model trimers and their synthetic kinetics are established to guide the synthesis of diverse sequence-defined polymers.