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.
Pairing Suzuki–Miyaura cross-coupling and catalyst transfer polymerization
Borylation strategies to make AB Suzuki–Miyaura monomers for use in catalyst-transfer polymerization with nickel or palladium catalysts.
Direct formation of nano-objects via in situ self-assembly of conjugated polymers
The development of the polymer self-assembly method “in situ nanoparticlization of conjugated polymers” is discussed in this Perspective.
Poly(ε-lysine) and its derivatives via ring-opening polymerization of biorenewable cyclic lysine
Minireview focused on poly(ε-lysine) and its derivatives via ring-opening polymerization of biorenewable cyclic lysine.
Advancing the stimuli response of polymer-based drug delivery systems for ocular disease treatment
Recent exploitations of stimuli-responsive polymers as ophthalmic drug delivery systems for the treatment of eye diseases are summarized and discussed.
Bioinspired structural color nanocomposites with healable capability
This minireview summarizes the recent development of healable structural color nanocomposites from the perspective of the construction strategies.
Recent development in halogen-bonding-catalyzed living radical polymerization
The development and applications of an organocatalyzed living radical polymerization via halogen-bonding catalysis, i.e., reversible complexation mediated polymerization (RCMP), are highlighted.
From terpenes to sustainable and functional polymers
The use of renewable terpene-based monomers for the preparation of sustainable functional polymers is highlighted.
Polymers and boron neutron capture therapy (BNCT): a potent combination
This review describes the latest polymeric systems used as boron transporters for boron neutron capture therapy.
Heterogeneous photocatalytic reversible deactivation radical polymerization
Photocatalytic reversible deactivation radical polymerization (RDRP) permits the use of sustainable solar light for spatiotemporal regulation of radical polymerization under mild conditions.
Synthetic approaches for copolymers containing nucleic acids and analogues: challenges and opportunities
Deep integration of nucleic acids with synthetic polymers are rapidly becoming the basis of many useful technologies.
Semiflexible polymer scaffolds: an overview of conjugation strategies
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 conjugated polymers with open-shell character
Quinoidal π-Conjugated polymers with open shell character represent an intriguing class of macromolecules in terms of both fundamental research and practical applications.
Recent advances in the development and applications of nonconventional luminescent polymers
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.
A comprehensive review of the structures and properties of ionic polymeric materials
This review focuses on the mechanistic approach, the structure–property relationship and applications of ionic polymeric materials.
Guanidium-functionalized cationic molecular umbrellas as antibacterial agents
We report the synthesis of guanidinium-functionalized cationic dendrons with pendant alkyl chains of varying lengths, which are classified as antibacterial cationic molecular umbrellas.
Controlling properties of thermogels by tuning critical solution behaviour of ternary copolymers
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.
A shish-kebab-like supramolecular polymer and its light-responsive self-assembly into nanofibers
We report a shish-kebab-like supramolecular polymer (SKSP) and its light-responsive self-assembly into nanofibers.
Confined supramolecular polymers in water with exceptional stability, photoluminescence and chiroptical properties
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.
Mechanism and application of surface-initiated ATRP in the presence of a Zn0 plate
SI-Zn0-ATRP enables the synthesis of chemically different polymer brushes under full ambient conditions, using just microliter volumes of reaction solutions.
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.
Catalyst free removal of trithiocarbonate RAFT CTAs from poly(vinylpyridine)s using tris(trimethylsilyl)silane and light
Trithiocarbonate end groups on various polymers, including polyvinylpyridines, are reduced rapily and quantitatively using only tris(trimethylsilyl)silane and light.
Easily readable palindromic sequence-defined polymers built by cascade thiol-maleimide Michael couplings
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.
Cationic amphiphilic alternating copolymers with tunable morphology
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.
Crosslinked metallo-polyelectrolytes with enhanced flexibility and dimensional stability for anion-exchange membranes
We report a class of crosslinked metallo-polyelectrolytes as anion exchange membranes with exceptional mechanical flexibility, dimensional stability and ionic conductivity.
Photoresponsive Glyco-Nanostructures Integrated from Supramolecular Metallocarbohydrates for the Reversible Capture and Release of Lectins
The effect of polarity on the molecular exchange dynamics in imine-based covalent adaptable networks
Polarity-induced effects in dynamic covalent polyimine CANs were studied, revealing a three-step stress relaxation process.
The contribution of intermolecular forces to phototropic actuation of liquid crystalline elastomers
Azobenzene-functionalized crystalline elastomers containing a monomer with reduced aromatic content exhibits enhanced phototropic response.
Design of an n-type low glass transition temperature radical polymer
We document the design, synthesis, and characterization of the first low glass transition temperature, n-type (i.e., preferentially-reduced) radical polymer.
Expanding the thiol–X toolbox: photoinitiation and materials application of the acid-catalyzed thiol–ene (ACT) reaction
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.
Organocatalyzed closed-loop chemical recycling of thermo-compressed films of poly(ethylene furanoate)
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.
Controlled ring-opening polymerization of N-(3-tert-butoxy-3-oxopropyl) glycine derived N-carboxyanhydrides towards well-defined peptoid-based polyacids
Polypeptoids bearing carboxylic acid groups on the N-substituent are useful building blocks for the construction of peptidomimetic supramolecular assemblies with stimuli-responsive properties.
Effect of backbone and end-group regioisomerism on thermomechanical properties of vanillin-based polyurethane networks
Monomer composition, geometry, cross-link density, and cross-link distribution are the primary determinants of material properties in thermosetting networks.
Clarification of the effects of topological isomers on the mechanical strength of comb polyurethane
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 AIE-driven fluorescent polysaccharide polymersome as an enzyme-responsive FRET nanoprobe to study the real-time delivery aspects in live cells
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 for efficient photocatalytic hydrogen evolution and organic solar cells
A pyridinium-pended conjugated polyelectrolyte with photo-induced amine doping behaviour was designed for multiple applications.
Solution size variation of linear and dendritic bis-MPA analogs using DOSY-1H NMR
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 of polyamide adhesives and prediction of their functional properties with solid-state NMR spectroscopy
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.
Stereoselective polymerization of rac-lactide catalyzed by zwitterionic calcium complexes
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.
Hierarchical self-assembly of miktoarm star copolymers with pathway complexity
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 with PEG, octadecyl, and oleyl pendants for controlled crystallization and microphase separation
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.
Preparation of well-defined 2D-lenticular aggregates by self-assembly of PNIPAM-b-PVDF amphiphilic diblock copolymers in solution
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.
Organocatalytic ring-opening polymerization of thionolactones: anything O can do, S can do better
Organocatalysts facilitate the synthesis of polythionolactones; oxidative crosslinking yields a degradable polymer foam.
Naked micelles: well-defined polymer nanoparticles from photo-cleavable block copolymer micelles
We report that photo-cleaving the corona of block copolymer micelles provides well-defined nanoparticles with surface charges accessible for electrostatic modification.
Temperature-mediated molecular ladder self-assembly employing Diels–Alder cycloaddition
Thermal annealing of sequence-defined, maleimide- and furan-bearing oligomers enables sequence-selective hybridization to afford molecular ladders incorporating Diels–Alder adduct-based rungs.
Thermo- and oxidation-sensitive poly(meth)acrylates based on alkyl sulfoxides: dual-responsive homopolymers from one functional group
Alkyl sulfoxide side groups introduce thermo- and oxidation-sensitivity into poly(meth)acrylates, thus realizing new dual-responsive homopolymers based on one functional group.
Guaiazulene revisited: a new material for green-processed optoelectronics
Oxidative polymerization of naturally-derived guaiazulene with earth-abundant iron oxidants produces a low bandgap polymer for optoelectronic applications.
Gradient and asymmetric copolymers: the role of the copolymer composition profile in the ionization of weak polyelectrolytes
The ionization of weak polyelectrolytes can be altered by controlling the composition profile of the comonomers along the chain.
Dynamic covalent exchange in poly(thioether anhydrides)
Dynamic covalent exchange (DCE) of anhydride moieties is examined in both model compounds and network polymers.
Investigations into CTA-differentiation-involving polymerization of fluorous monomers: exploitation of experimental variances in fine-tuning of molecular weights
Condition and substrate effects on CTA-differentiation-involving polymerization were explored for logical control of molecular weight.
Poly(vinyl acetate-co-ethylene) particles prepared by surfactant-free emulsion polymerization in the presence of a hydrophilic RAFT/MADIX macromolecular chain transfer agent
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.
Defect engineering of polyethylene-like polyphosphoesters: solid-state NMR characterization and surface chemistry of anisotropic polymer nanoplatelets
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.
Core hyper-cross-linked star polymers from block polymer micelle precursors
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.
Effects of crystallinity and dispersity on the self-assembly behavior of block co-oligomers in water
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.
DFT-calculation-assisted prediction of the copolymerization between cyclic ketene acetals and traditional vinyl monomers
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.
Exploring the difference of bonding strength between silver(I) and chalcogenides in block copolymer systems
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.
Semifluorinated, kinked polyarylenes via direct arylation polycondensation
The Tg 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.
Insight into the synthesis of N-methylated polypeptides
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.
Time-dependent covalent network formation in extrudable hydrogels
Shear-thinning hydrogels that utilize thiol-Michael chain-extension and free radical polymerization have a tunable stretchability.
Functional polyimides based on diamine containing diarylethylene moieties and their photochromic mechanism studies
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-based single-chain polymer nanoparticles as a versatile platform towards protein mimicry
Pentafluorophenyl-single chain polymer nanoparticles are readily conjugated with functional amines enabling facile SCNP modification, adjustment of physicochemical properties, and even protein mimicry.
Catechol-functionalized sequence-defined glycomacromolecules as covalent inhibitors of bacterial adhesion
Herein, we present the synthesis of catechol functionalized sequence-defined glycomacromolecules that can covalently block the binding site of lectins and bacterial adhesins.
Identifying competitive tin- or metal-free catalyst combinations to tailor polyurethane prepolymer and network properties
Polyurethane-based mastics, industrially obtained via a prepolymerization/crosslinking process, benefit from catalyst selection at both stages.
A dual drug-based hyperbranched polymer with methotrexate and chlorambucil moieties for synergistic cancer chemotherapy
Dual drug-based hyperbranched polymer micelles simultaneously containing methotrexate and chlorambucil were constructed for synergistic cancer chemotherapy.
Kinetics and mechanisms of polycondensation reactions between aryl halides and bisphenol A
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.
Impacts of performing electrolysis during organocatalyzed atom transfer radical polymerization
An electrochemical variant of organocatalyzed atom transfer radical polymerization (O-ATRP) is developed and investigated.
Sequential and alternating RAFT single unit monomer insertion: model trimers as the guide for discrete oligomer synthesis
A complete set of model trimers and their synthetic kinetics are established to guide the synthesis of diverse sequence-defined polymers.
Optimization of ring-opening metathesis polymerization (ROMP) under physiologically relevant conditions
Ring opening metathesis polymerization (ROMP) is widely considered an excellent living polymerization technique that proceeds rapidly in organic solvents. This work describes the optimization of ROMP under physiologically relevant conditions.
About this collection
Polymer Chemistry is proud to present this 2021 Pioneering Investigators collection. This collection gathers the very best work from mid-career researchers who have firmly established themselves in the field of polymer chemistry and continuously publish creative, innovative work. The 2021 Polymer Chemistry Pioneering Investigators were individually nominated by members of the journal Editorial and Advisory Boards, and previous Pioneering Investigators, in recognition of their achievements as pioneers of the field.
New articles will be added to this collection as they are published.
Congratulations to all those whose work is featured. Join us in celebrating their contributions!