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| Open AccessSequence-selective dynamic covalent assembly of information-bearing oligomers
Dynamic covalent interactions have been employed to mediate molecular self-assembly reactions but often do not converge to a thermodynamic equilibrium and yield a mixture of kinetically trapped species. Here, the authors show a sequence-selective, dynamic covalent self-assembly process that mitigates kinetic trapping to afford biomimetic molecular ladders with covalent rungs.
- Samuel C. Leguizamon
- & Timothy F. Scott
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Article
| Open AccessBiobased chiral semi-crystalline or amorphous high-performance polyamides and their scalable stereoselective synthesis
Bio‐based compounds often suffer from high production cost and low performance when used to synthesise macromolecules. Here the authors show the conversion of (+)‐3‐ carene, a by‐product of the cellulose industry, into its ε‐lactams and then to polyamides with high‐performance thermal properties.
- Paul N. Stockmann
- , Daniel Van Opdenbosch
- & Volker Sieber
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Article
| Open AccessA simple and versatile nickel platform for the generation of branched high molecular weight polyolefins
High-performance transition metal catalysts are a major driving force in academic and industrial polyolefin research. Here the authors show the synthesis and (co)polymerization studies of a simple and versatile α-imino-ketone nickel system, which is thermally stable and highly active during ethylene polymerization.
- Tao Liang
- , Shabnam B. Goudari
- & Changle Chen
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Article
| Open AccessHigh-density information storage in an absolutely defined aperiodic sequence of monodisperse copolyester
Synthesis of a polymer composed of a large discrete number of chemically distinct monomers in an absolutely defined aperiodic sequence remains a challenge in polymer chemistry. Here the authors show copolymers of α-hydroxy acids, poly(phenyllactic-co-lactic acid), built via a cross-convergent method of four dyads of monomers.
- Jung Min Lee
- , Mo Beom Koo
- & Kyoung Taek Kim
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Article
| Open AccessPhotoresponsive spiro-polymers generated in situ by C–H-activated polyspiroannulation
Photoresponsive polymers are receiving great attention due to the increasing demands on smart optical and biological materials. Here, the authors report a C–H-activated polyspiroannulation route to in situ generate photoresponsive spiro-polymers with potential applications in photopatterning and silicon photonics techniques.
- Ting Han
- , Zhanshi Yao
- & Ben Zhong Tang
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Article
| Open AccessEnzyme-mimetic self-catalyzed polymerization of polypeptide helices
The folding-dependent catalytic behavior of enzymes is of fundamental biological importance, yet mechanistically underexplored. Here, the authors show that an α-helix, commonly found in proteins, can facilitate its own growth through the self-catalyzed polymerization of N-carboxyanhydride in solvents with low polarity.
- Ziyuan Song
- , Hailin Fu
- & Jianjun Cheng
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Article
| Open AccessAnisotropic polymer nanoparticles with controlled dimensions from the morphological transformation of isotropic seeds
Understanding and controlling self-assembly processes at multiple length scales is essential to design and create advanced materials. Here the authors report a method for the production of highly anisotropic nanoparticles with controlled dimensions based on the morphological transformation of initially isotropic seeds, driven by supramolecular bonding.
- Zan Hua
- , Joseph R. Jones
- & Rachel K. O’Reilly
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Article
| Open AccessOne-shot preparation of topologically chimeric nanofibers via a gradient supramolecular copolymerization
Supramolecular polymers can form highly accessible polymeric nanomaterials. Here the authors report the facile preparation of supramolecular copolymers involving segregated secondary structures by cooling non-polar solutions containing two monomers that individually afford helically folded and linearly extended secondary structures.
- Yuichi Kitamoto
- , Ziyan Pan
- & Shiki Yagai
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Article
| Open AccessPhoto-editable macromolecular information
Light-induced alteration of macromolecular information plays a central role in biology and is known to influence health and aging. Here the authors show that light can trigger sequence variations in abiotic information-containing polymers that possess photo-sensitive monomers
- Niklas Felix König
- , Abdelaziz Al Ouahabi
- & Jean-François Lutz
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Article
| Open AccessVisualization and design of the functional group distribution during statistical copolymerization
Understanding the functional group distribution in a polymer chain has been difficult, but this information can be very useful. Here the authors visualize the monomer distribution in individual polymer chains by combining experimental and theoretical analysis of the construction of functionality-chain length distributions.
- Paul H. M. Van Steenberge
- , Ondrej Sedlacek
- & Dagmar R. D’hooge
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Article
| Open AccessFast and selective organocatalytic ring-opening polymerization by fluorinated alcohol without a cocatalyst
Polymerizations promoted by organic catalysts can produce polymeric materials without any metallic residues contamination. Here the authors show a fluorinated alcohol based catalytic system for polypeptide synthesis from α-amino acid N-carboxyanhydride, fulfilling cocatalyst and metal free conditions with high rate and selectivity.
- Wei Zhao
- , Yanfeng Lv
- & Nikos Hadjichristidis
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Article
| Open AccessHighly efficient dandelion-like near-infrared light photoinitiator for free radical and thiol-ene photopolymerizations
Photo-induced polymerizations are being utilized to design and fabricate macromolecular structures with spatial and temporal control. Here the authors use a near-infrared light free-radical photoinitiator consisting of oxime-ester coumarin functionalities on the surface of upconversion nanoparticles for free-radical and thiol-ene photopolymerizations.
- Zhiquan Li
- , Xiucheng Zou
- & Yusuf Yagci
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Article
| Open AccessHighly branched poly(β-amino ester) delivery of minicircle DNA for transfection of neurodegenerative disease related cells
Therapeutics delivery by using non-viral vectors presents several challenges in the design of an appropriate polymeric structure. Here, the authors report a series of highly branched, biodegradable polymers which show high transfection efficiency in human multipotent adipose derived stem cells and primary astrocytes.
- Shuai Liu
- , Yongsheng Gao
- & Wenxin Wang
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Article
| Open AccessEasy access to oxygenated block polymers via switchable catalysis
Multiblock oxygenated polyols often show better properties than the constituent polyols, but their synthesis can be complex and difficult. Here a switchable catalysis concept is described which allows for the efficient preparation of multiblock poly(ether-b-ester) materials starting from mixtures of common monomers.
- Tim Stößer
- , Gregory S. Sulley
- & Charlotte K. Williams
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Article
| Open AccessUniform shape monodisperse single chain nanocrystals by living aqueous catalytic polymerization
The formation of polymer nanoparticles with a uniform size and shape, beyond spheres, is an unresolved problem. Here the authors show a living aqueous catalytic polymerization forming single crystal particles grown by a single active site and composed of a single ultra high molecular weight polyethylene chain.
- Manuel Schnitte
- , Anne Staiger
- & Stefan Mecking
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Article
| Open AccessPoly(bis-arylimidazoliums) possessing high hydroxide ion exchange capacity and high alkaline stability
The hydroxide anion exchange polymers are key materials of solid polymer electrolyte devices that operate under alkaline conditions. Here the authors show the rational design of such polymers that exhibit high ion exchange capacity and exceptional stability under highly caustic conditions.
- Jiantao Fan
- , Sapir Willdorf-Cohen
- & Steven Holdcroft
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Article
| Open AccessSynthesis of an aromatic N-heterocycle derived from biomass and its use as a polymer feedstock
Aromatic N-heterocyclic compounds are important chemicals, but produced from petroleum. Here the authors show a pyridazine-based compound 6-(4-hydroxy-3-methoxyphenyl)pyridazin-3(2H)-one, used as polymer feedstocks, can be synthesized by a Friedel-Crafts reaction from biomass starting materials.
- Yu Qi
- , Jinyan Wang
- & Xigao Jian
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Article
| Open AccessEnzymatic synthesis of lignin derivable pyridine based polyesters for the substitution of petroleum derived plastics
The increasing concern of global plastic pollution has led to an increase in the production and characterization of bio-based and biodegradable alternatives. Here the authors show the synthesis of a series of fully bio-based alternatives based on 2,4-, 2,5-, and 2,6- pyridinedicarboxylic acids, via enzymatic catalysis.
- Alessandro Pellis
- , James W. Comerford
- & Thomas J. Farmer
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Article
| Open AccessScalable preparation of alternating block copolymer particles with inverse bicontinuous mesophases
Block copolymer particles with controlled morphologies play a vital role in materials science and nanotechnology. Here the authors show a scalable preparation of amphiphilic alternating block polymer particles with inverse bicontinuous mesophases via polymerization-induced self-assembly.
- Fei Lv
- , Zesheng An
- & Peiyi Wu
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Article
| Open AccessMetal-free dehydropolymerisation of phosphine-boranes using cyclic (alkyl)(amino)carbenes as hydrogen acceptors
Polymers featuring p-block elements other than carbon are of interest for a range of applications, but access to highly-substituted examples remains challenging. Here the authors demonstrate that cyclic (alkyl)(amino)carbenes can mediate the dehydropolymerisation of phosphine-boranes, leading to the construction of P-disubstituted polyphosphinoboranes.
- Nicola L. Oldroyd
- , Saurabh S. Chitnis
- & Ian Manners
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Article
| Open AccessHemozoin-catalyzed precipitation polymerization as an assay for malaria diagnosis
Methods to diagnose malaria are of interest but can be costly or not sensitive enough to detect low levels of parasitemia. Here the authors report an ultrasensitive method by using hemozoin (a biomarker of all Plasmodium species) to catalyse the polymerization of N-isopropylacrylamide.
- Omar Rifaie-Graham
- , Jonas Pollard
- & Nico Bruns
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Article
| Open AccessUltra-strong long-chain polyamide elastomers with programmable supramolecular interactions and oriented crystalline microstructures
Long-chain polyamides could bridge the gap between traditional polyamides and polyethylenes. Here the authors show the preparation of diamide diene monomers derived from natural resources coupled by thiol-ene addition copolymerization to form long-chain amide-containing polymers for the synthesis of ultra-strong elastomers.
- Lingzhi Song
- , Tianyu Zhu
- & Chuanbing Tang
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Article
| Open AccessMagnetic field alignment of stable proton-conducting channels in an electrolyte membrane
Proton exchange membranes with short-pathway through-plane proton conductivity are attractive for proton exchange membrane fuel cells. Here the authors align proton conducting channels orthogonal to the plane of composite proton exchange membranes using a magnetic field for improved fuel cell performance.
- Xin Liu
- , Yi Li
- & Michael D. Guiver
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Article
| Open AccessCatalytic inverse vulcanization
Inverse vulcanization allows stable polymers to be made from elemental sulfur, but development is restricted by cross-linkers and the elevated temperatures required. Here the authors report a catalytic method for a wide range of cross-linkers and found a reduced reaction temperature and reaction time is required.
- Xiaofeng Wu
- , Jessica A. Smith
- & Tom Hasell
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Article
| Open AccessElectroactive materials with tunable response based on block copolymer self-assembly
Ferroelectric polymers are key building blocks for flexible electronic devices, but lack functionality and ability to tune their ferroelectric response. Here the authors show a method to introduce functionality in ferroelectric polymers while preserving ferroelectricity and tune the ferroelectric response by incorporating insulating polymer chains.
- Ivan Terzic
- , Niels L. Meereboer
- & Katja Loos
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Article
| Open AccessA highly active Ni(II)-triadamantylphosphine catalyst for ultrahigh-molecular-weight polyethylene synthesis
Ultra-high molecular weight polyethylene is a desirable commodity. Here the authors show that a tri-1-adamantylphosphine-nickel complex, when exposed to alkyl aluminium activators, polymerizes ethylene to ultrahigh-molecular-weight polyethylene with initial activities reaching 3.8 million turnovers/h at 10 °C.
- Andrew L. Kocen
- , Maurice Brookhart
- & Olafs Daugulis
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Article
| Open AccessDirect access to poly(glycidyl azide) and its copolymers through anionic (co-)polymerization of glycidyl azide
Poly(glycidyl azide) is an excellent energetic binder or plasticizer, however its production relies on post-modificaiton strategies. Here, the authors directly produced Poly(glycidyl azide) via anionic ring-opening polymerization of glycidyl azide monomer, which is additionally co-polymerized with CO2 and epoxides.
- Senthil K. Boopathi
- , Nikos Hadjichristidis
- & Xiaoshuang Feng
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Article
| Open AccessBlocking-cyclization technique for precise synthesis of cyclic polymers with regulated topology
Cyclic polymers can be usually accessed by ring-expansion and ring-closure approaches. Here, the authors report an alternative blocking-cyclization technique which enables the tunable synthesis of multicyclic polymers via commercial Ru-based Grubbs catalysts and conventional ring-opening metathesis polymerisation.
- Jie Chen
- , Hongfei Li
- & Meiran Xie
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Article
| Open AccessLithium hexamethyldisilazide initiated superfast ring opening polymerization of alpha-amino acid N-carboxyanhydrides
Ring-opening polymerizations of α-amino acid N-carboxyanhydrides to form polypeptides are usually sensitive to moisture, slow and can undergo side reactions. Here the authors use lithium hexamethyldisilazide to initiate α-amino acid N-carboxyanhydride polymerizations that is very fast and can be conducted in an open vessel.
- Yueming Wu
- , Danfeng Zhang
- & Runhui Liu
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Article
| Open AccessAn AIEgen-based 3D covalent organic framework for white light-emitting diodes
3D covalent organic frameworks (COF) show interesting hierarchical arrangements of nanopores and open sites but their synthesis remains challenging. Here the authors report a fluorescent AIEgen-based 3D COF and demonstrate application as a coating material for white LEDs and for sensing of picric acid
- Huimin Ding
- , Jian Li
- & Cheng Wang
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Article
| Open AccessMacromolecular-clustered facial amphiphilic antimicrobials
Bacterial infections and antibiotic resistance are an increasing concern for the world. Here the authors report a class of cationic antimicrobial polymers that cluster local facial amphiphilicity from repeating units to enhance interactions with bacterial membranes without requiring a high unfavorable entropic loss.
- Md Anisur Rahman
- , Marpe Bam
- & Chuanbing Tang
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Review Article
| Open AccessMetallo-polyelectrolytes as a class of ionic macromolecules for functional materials
Polyelectrolytes are a class of macromolecules containing charged groups. Here the authors review properties and functions of metallo-polyelectrolytes to shed light on how to harness fundamental physiochemical properties for applications in biomedical sciences and advanced materials.
- Tianyu Zhu
- , Ye Sha
- & Chuanbing Tang
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Article
| Open AccessDesigned synthesis of stable light-emitting two-dimensional sp2 carbon-conjugated covalent organic frameworks
Topological connection of organic chromophores is an attractive way to design light-emitting covalent organic frameworks but the synthesis of stable light-emitting frameworks remains challenging. Here the authors report the designed synthesis of sp2 carbon conjugated frameworks that combine stability with light-emitting activity
- Enquan Jin
- , Juan Li
- & Donglin Jiang
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Article
| Open AccessChiral self-sorted multifunctional supramolecular biocoordination polymers and their applications in sensors
Chiral supramolecules may be used in chiral recognition, sensing and catalysis. Here the authors selectively synthesized homochiral and heterochiral supramolecular biocoordination polymers of naphthalene diimide ligands with alanine termini and Zn ions.
- Xiaobo Shang
- , Inho Song
- & Joon Hak Oh
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Article
| Open AccessHighly-sensitive optical organic vapor sensor through polymeric swelling induced variation of fluorescent intensity
Traditional optical organic vapor sensors with solvatochromic shift mechanisms have lower sensitivity due to weak intermolecular interactions. Here, the authors report a general strategy to prepare a higher sensitivity optical organic vapor sensor through polymeric swelling-induced variation of fluorescent intensity.
- Xiangyu Jiang
- , Hanfei Gao
- & Lei Jiang
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Article
| Open AccessThe photoregulation of a mechanochemical polymer scission
Control over mechanochemical polymer scission by external stimuli may offer an avenue to further advance the fields of polymer chemistry, mechanochemistry, and materials science. Here the authors show light regulating the mechanochemical behavior of a diarylethene-conjugated Diels–Alder adduct.
- Jumpei Kida
- , Keiichi Imato
- & Hideyuki Otsuka
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Article
| Open AccessPost-polymerisation functionalisation of conjugated polymer backbones and its application in multi-functional emissive nanoparticles
Functionalisation of conjugated polymers is essential for performance in many applications, yet there are limited approaches to achieve this. Here the authors developed a method for the direct postpolymerisation modification of the aromatic backbone of conjugated polymers and used them to create multifunctional semiconducting nanoparticles.
- Adam Creamer
- , Christopher S. Wood
- & Martin Heeney
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Article
| Open AccessFacile transformation of imine covalent organic frameworks into ultrastable crystalline porous aromatic frameworks
Despite recent success in developing new covalent organic frameworks (COFs) materials, synthesis of chemically stable COFs still remains challenging. Here the authors demonstrate a facile strategy that transforms imine-linked COFs into robust porous aromatic frameworks by kinetically fixing the reversible imine linkage via an aza-Diels-Alder cycloaddition reaction.
- Xinle Li
- , Changlin Zhang
- & Yi Liu
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Article
| Open AccessBottle-grade polyethylene furanoate from ring-opening polymerisation of cyclic oligomers
The synthesis of polyethylene furanoate, a promising renewable resource-based bioplastic, still has challenges. Here the authors show that bottle-grade polyethylene furanoate can be obtained within minutes from ring-opening polymerisation of its cyclic oligomers, thereby avoiding degradation and discolouration.
- Jan-Georg Rosenboom
- , Diana Kay Hohl
- & Massimo Morbidelli
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Article
| Open AccessUnraveling substituent effects on the glass transition temperatures of biorenewable polyesters
Biorenewable feedstocks allow the design of polymers with targeted properties and functionalities. Here the authors report a series of high glass transition temperature sugar-based polyesters and investigate how substituents affect their thermal properties.
- Xiaopeng Yu
- , Junteng Jia
- & Robert A. DiStasio Jr.
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Article
| Open AccessAdding chemically selective subtraction to multi-material 3D additive manufacturing
Subtractive manufacturing of microstructures is important for many applications, yet photoresists for 3D laser lithography allow only removal after development under harsh cleavage conditions. Here, the authors introduce a set of chemoselective cleavable photoresists allowing the orthogonal cleavage of microstructures under mild conditions.
- David Gräfe
- , Andreas Wickberg
- & Christopher Barner-Kowollik
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Article
| Open AccessSynthesis of polymers with on-demand sequence structures via dually switchable and interconvertible polymerizations
The synthesis of polymers with on-demand sequence structures is difficult but highly desirable. Here the authors show a dual switchable and controlled interconvertible polymerization involving two orthogonal polymerizations that are switched ON/OFF independent of each other with an external stimulus.
- Ze Zhang
- , Tian-You Zeng
- & Ye-Zi You
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Article
| Open AccessChemical synthesis of perfectly isotactic and high melting bacterial poly(3-hydroxybutyrate) from bio-sourced racemic cyclic diolide
Bacterial poly(3-hydroxybutyrate) possesses physical and mechanical properties suitable for substituting high-performance petroleum plastics but current production is costly and slow. Here the authors produce poly(3-hydroxybutyrate) with similar properties via ring-opening polymerization of bio-derived racemic cyclic diolide.
- Xiaoyan Tang
- & Eugene Y.-X. Chen
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Article
| Open AccessPrecise synthesis of sulfur-containing polymers via cooperative dual organocatalysts with high activity
Sulfur-containing polymers are useful commodities, but there is still a big challenge to produce such polymers in a controlled fashion. Here the authors show a metal-free living copolymerization between carbonyl sulfide and epoxides via cooperative catalysis.
- Cheng-Jian Zhang
- , Hai-Lin Wu
- & Xing-Hong Zhang
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Article
| Open AccessSulfenate anions as organocatalysts for benzylic chloromethyl coupling polymerization via C=C bond formation
Polymerization reactions are often catalysed by metal compounds and hence there are concerns surrounding toxicity, cost and environmental friendliness. Here the authors show sulfenate anions as organocatalysts for benzylic chloromethyl-coupling polymerization reactions to form poly(stilbene)s.
- Minyan Li
- , Simon Berritt
- & Patrick J. Walsh
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Article
| Open AccessCross-coupling polycondensation via C–O or C–N bond cleavage
π-Conjugated polymers are useful commodities as they are used in the fabrication of organic photovoltaic devices, light-emitting diodes and field effect transistors. Here the authors describe the polycondensation of bifunctional aryl ethers or aryl ammonium salts with aromatic dimetallic compounds through cleavage of inert C–O/C–N bonds.
- Ze-Kun Yang
- , Ning-Xin Xu
- & Masanobu Uchiyama
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Article
| Open AccessStereoselective photoredox ring-opening polymerization of O-carboxyanhydrides
The stereoselective synthesis of polyesters has been achieved via various methods; however, all routes show limited side-chain group functionality. Here the authors synthesize stereoblock polyesters by photoredox ring-opening polymerization of racemic O-carboxyanhydrides that have abundant side-chain functionality.
- Quanyou Feng
- , Lei Yang
- & Rong Tong
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Article
| Open AccessChiral induction in covalent organic frameworks
Controlling chirality and function in metal organic frameworks has been an achievement, but very difficult to carry out in covalent organic frameworks. Here the authors show chiral covalent organic frameworks that are crystallized from achiral precursors by chiral catalytic induction.
- Xing Han
- , Jie Zhang
- & Yong Cui
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Article
| Open AccessEncapsulation of catalyst in block copolymer micelles for the polymerization of ethylene in aqueous medium
Olefin and emulsion polymerizations are incompatible due to the water sensitivity of olefin polymerization catalysts and thus direct synthesis of semi-crystalline polyolefin latexes is difficult. Here, the authors encapsulate a catalyst precursor in micelles which act as nanoreactors for ethylene polymerization in water.
- Camille Boucher-Jacobs
- , Muhammad Rabnawaz
- & Damien Guironnet