Article
Chemistry, Multidisciplinary
Joji Tanaka, Noel Edward Archer, Michael Jeffery Grant, Wei You
Summary: In this study, RAFT step-growth polymerization was achieved by combining RAFT and step-growth polymerization mechanisms, resulting in backbone repeat units with a pendant RAFT agent that can form molecular brush polymers in a second polymerization step. The cleavable backbone functionality allows the transformation of brushlike polymers into linear chains of uniform size under stimuli.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Green & Sustainable Science & Technology
Xiuxian Zhao, Junhua Sun, Jiachen Ma, Tongyao Liu, Zeyi Guo, Zhen Yang, Wei Yao, Xuchuan Jiang
Summary: Vanadium dioxide (VO2) is considered as a promising material for smart windows. However, its real application is hindered by several limitations. In this study, core-shell structured VO2@PMMA-b-PHFBMA nanoparticles with excellent properties were prepared using a RAFT polymerization method. The addition of a F-containing polymer shell improved the stability and compatibility of the VO2 nanoparticles. Furthermore, a photochromic and hydrophobic copolymer was synthesized and coated onto the VO2 nanoparticles to create an energy-saving composite film. The composite film showed high solar modulation efficiency, making it a highly promising application for smart windows.
SUSTAINABLE MATERIALS AND TECHNOLOGIES
(2022)
Article
Polymer Science
Arne Wolpers, Florian Baffie, Vincent Monteil, Franck D'Agosto
Summary: In this study, a dithiocarbamate chain transfer agent was used to synthesize statistical and diblock copolymers of ethylene and vinyl acetate, achieving various polymer compositions through good chain growth control, including linear diblock copolymers and a three-arm star copolymer.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Biochemistry & Molecular Biology
Tobias A. Bauer, Jan Imschweiler, Christian Muhl, Benjamin Weber, Matthias Barz
Summary: The formation of secondary structures in polypeptides influences their self-assembly behavior, with copolymers containing antiparallel beta-sheets showing a strong tendency to form worm-like micelles. Different secondary structures lead to distinct morphologies in the resulting nanostructures, highlighting the potential of secondary structure-driven self-assembly in synthetic polypeptides.
Article
Polymer Science
Jungyeon Kim, Beatrice Cattoz, Alice H. M. Leung, James D. Parish, C. Remzi Becer
Summary: The synthesis of a new 2-oxazoline monomer and its application in RAFT polymerization are reported in this study. Brush copolymers with different architectures were prepared by adjusting the monomer ratios.
Article
Polymer Science
Sharmaine B. Luk, Milan Maric
Summary: Novel block copolymers were synthesized via nitroxide-mediated polymerization using ethylene glycol dicylopentenyl methacrylate (EGDEMA) and farnesene (Far). The copolymers showed improved mechanical and thermal properties, especially with the addition of functionalized POSS.
Article
Polymer Science
Wenling Guo, Peng Cao, Fengli Dai, Yonggang Li, Rongmin Wang, Pengfei Song, Yufeng He
Summary: The novel antibacterial material, polymer cations-adjustable porous materials (PCaPM), was synthesized by reversible addition-fragmentation chain transfer polymerization (RAFT) and quaternization. PCaPM showed excellent antibacterial activity due to the presence of quaternary ammonium salts groups and had great prospects in various applications.
POLYMERS FOR ADVANCED TECHNOLOGIES
(2022)
Article
Chemistry, Multidisciplinary
Huong Dau, Enkhjargal Tsogtgerel, Krzysztof Matyjaszewski, Eva Harth
Summary: This study develops the PACE process for the synthesis of well-defined polyolefin-polyvinyl block copolymers. Through kinetic studies, the design criteria for catalyst activation in alpha-diimine Pd-II-catalyzed olefin polymerizations are established. The prepared polyolefin macroinitiators or macro-mediators with diverse functional groups enable various controlled polymerization techniques. Different block copolymers with varied architectures, molecular weights, and compositions are successfully prepared using ROP, NMP, and PI-RAFT. The distinct properties of polyolefin-polyacrylamide block copolymers are utilized in polymerization-induced self-assembly for studying nanostructure behaviors.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Patrizia P. Smith, Stephen G. Boyes
Summary: Amphiphilic block copolymers were successfully synthesized using a dual initiator chain transfer agent. Comprehensive kinetics studies provided valuable insights into factors influencing the synthesis of well-defined block copolymers, as well as the ability to produce poly(lactide) blocks of different molecular weights. The role of the chain transfer agent in facilitating the complex and sterically demanding RAFT polymerization of PEGEEMA was also examined through kinetics monitoring.
JOURNAL OF POLYMER SCIENCE
(2021)
Article
Polymer Science
Egor Polozov, Alexandra Grigoreva, Artem Vlasov, Sergey Zaitsev
Summary: The article discusses the application of 1-cyano-1-methylethylmethyl(4-pyridinyl)dithiocarbamate in reversible addition-fragmentation chain transfer (RAFT) polymerization of various monomers, showing good control over some monomers but slightly worse control over others. Polymers with narrow molecular weight distributions were obtained with this RAFT agent.
JOURNAL OF POLYMER RESEARCH
(2021)
Article
Polymer Science
Dimitrios Selianitis, Stergios Pispas
Summary: This work introduces a series of novel multi-responsive hyperbranched copolymers which self-organize in aqueous media. The copolymers, prepared by RAFT polymerization, exhibit responsiveness to changes in solution temperature and pH, and are able to encapsulate hydrophobic drugs like curcumin. These hyperbranched copolymers show potential as candidates for drug delivery and bio-imaging applications, as they demonstrate stability in the presence of serum proteins.
Article
Polymer Science
Glenn K. K. Clothier, Thiago R. Guimaraes, Graeme Moad, Per B. Zetterlund
Summary: The study investigates the synthesis of multiblock copolymers using seeded RAFT emulsion polymerization and how experimental conditions affect the control over molecular weight distribution (MWD). It was found that high T-g values of polymer particles lead to reduced control over MWD via the RAFT mechanism.
Review
Polymer Science
Cyrille Boyer, Masami Kamigaito, Kotaro Satoh, Graeme Moad
Summary: This article surveys the progress in the development of radical-promoted single-unit monomer insertion (SUMI) or reversible deactivation radical addition (RDRA) processes, with a focus on aminoxyl-[nitroxide-] mediated SUMI (NM-SUMI), reversible-addition-fragmentation chain transfer-SUMI (RAFT-SUMI), and atom-transfer radical addition (ATRA). The strategies for achieving selectivity in single unit insertion vs oligomerization and the progress towards discrete oligomer synthesis by consecutive SUMI reactions are discussed. The prospects of using radical-promoted SUMI in the synthesis of sequence-defined polymers are also examined.
PROGRESS IN POLYMER SCIENCE
(2023)
Article
Chemistry, Physical
Yu-Xi Wang, Yang Li, Shi-Hui Qiao, Jing Kang, Zhi-Li Shen, Ning-Ning Zhang, Zesheng An, Xiaosong Wang, Kun Liu
Summary: A staged-thermal-initiation RAFT polymerization method is reported for the synthesis of polymers with high thiol end-group fidelity, which show high efficiencies for grafting to various gold nanoparticles (GNPs). Experimental proof shows that the decrease of end-group fidelity with molecular weight is caused by the gradual decomposition of the initiator. The positive correlation between end-group fidelity of polymers and grafting-to efficiency is illustrated through grafting-to assays for various GNPs.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Polymer Science
Nicholas J. Bongiardina, Shafer M. Soars, Maciej Podgorski, Christopher N. Bowman
Summary: This study evaluated radical-disulfide exchange reactions in thiol-ene-disulfide networks using different thiol and disulfide containing monomers. The results show that the stress relaxation rate in these networks can be controlled by changing the thiol-disulfide stoichiometry or the disulfide type. The combination of different thiol and disulfide monomers also influences the polymerization rate of the thiol-ene reaction.
Article
Chemistry, Multidisciplinary
Matthieu Soete, Kevin De Bruycker, Filip Du Prez
Summary: This article presents a method for rewriting and reading data on synthetic macromolecules. By utilizing a reversible strategy to modify position tags and a novel algorithm, the information encoded in macromolecules can be efficiently modified and decoded. This method simplifies the read-out process, increasing the potential for blind sequencing of macromolecules.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Stephan Maes, Vincent Scholiers, Filip E. Du Prez
Summary: This study presents a method for preparing polymethacrylate-based networks and analyzes the crosslinking behavior under UV irradiation. The decrosslinking of the networks in a reducing environment is also achieved. Preliminary coating experiments demonstrate the potential applicability of the studied materials.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Matthieu Soete, Filip E. Du Prez
Summary: This article reports an alternative and simple strategy for determining the monomer order of uniform oligo(thioether ester)s by random cleavages of ester units within the macromolecular backbone via a basic treatment. This method can be used to decode information stored in the primary structure of oligoesters.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Melissa A. Reith, Irene De Franceschi, Matthieu Soete, Nezha Badi, Resat Aksakal, Filip E. Du Prez
Summary: The study proposes a robust strategy for the synthesis of sequence-defined, discrete star-shaped macromolecules. The iterative approach allows for the preparation of asymmetrically branched macromolecules with high purity and yields, enabling sequence definition, precise insertion of branching points, and orthogonal end-group functionalization.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Chemistry, Multidisciplinary
Filip Van Lijsebetten, Tim Maiheu, Johan M. Winne, Filip E. Du Prez
Summary: A new class of dynamic epoxy resins has been developed to extend the upper temperature limit for on-demand adhesive dismantling. These resins can be triggered at high temperatures and remain bonded over a wide temperature range. They can be used in various applications, including bulk adhesive formulations and dynamic covalent linking to functionalized surfaces.
ADVANCED MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Bianka Golba, Matthieu Soete, Zifu Zhong, Niek Sanders, Filip E. Du Prez, Hannes A. Houck, Bruno G. De Geest
Summary: By modifying polyethylene glycol (PEG) with 1,2,4-triazoline-3,5-diones (TAD) under green light, we achieved both functionality and degradability of the PEG backbone. The TAD-PEG conjugates are degradable in aqueous medium under physiological conditions, with degradation rate depending on pH and temperature. Using TAD-derivatized PEG-lipid, we successfully improved messenger RNA (mRNA) transfection efficiency in vitro, and observed a similar tissue distribution in mice in vivo. These findings open up possibilities for the design of degradable, backbone-functionalized PEG in nanomedicine and beyond.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Tapas Debsharma, Stephanie Engelen, Ives De Baere, Wim Van Paepegem, Filip Du Prez
Summary: Natural fiber-reinforced composites can be made thermally reshapable using a resorcinol-based epoxy resin and fast exchanging siloxane bonds. The stress relaxation time at 220 degrees C is only about 6 seconds. This research demonstrates the potential for sustainable and reshapable composite materials in the form of flax fiber-reinforced composites.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Polymer Science
Stephan Maes, Filip Van Lijsebetten, Johan M. Winne, Filip E. Du Prez
Summary: In this study, it was shown that the introduction of N-sulfonyl urethane bonds leads to dynamic covalent exchange reactions under milder conditions. These exchangeable N-sulfonyl urethane motifs were then incorporated into a cross-linked PU matrix to facilitate plastic flow at lower temperatures. The resulting materials demonstrated good (re)processability and retained their thermal properties.
Article
Nanoscience & Nanotechnology
Hiba Kassem, Lucie Imbernon, Lucas Stricker, Laura Jonckheere, Filip E. Du Prez
Summary: This study introduces a method to produce thermally reprocessable polyurethane foams (PUFs) by using acetoacetyl-formed amides as dynamic units in the foam structure, addressing the recycling issues of end-of-life foams.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Steven C. Gauci, Filip E. Du Prez, Joshua O. Holloway, Hannes A. Houck, Christopher Barner-Kowollik
Summary: This study demonstrates the power of photochemical action plots in understanding the wavelength-resolved photochemistry of two triazolinedione (TAD) substrates. Despite having similar absorption spectra, the TAD substrates exhibit vastly different photoreactivity. By designing a 'hybrid' bisfunctional TAD molecule, the exceptional and site-selective (photo)chemical behavior of both substrates is demonstrated within a single small molecule.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Sisi Chen, Vincent Scholiers, Mengyao Zhang, Jiandong Zhang, Jian Zhu, Filip E. Du Prez, Xiangqiang Pan
Summary: In this study, a new thermally responsive C-Se dynamic covalent chemistry (DCC) was developed based on the transalkylation exchange between selenonium salts and selenides. The incorporation of this DCC into selenide-containing polymer materials allowed for regulated reprocessing capacity and demonstrated good healing ability at elevated temperatures as well as excellent solvent resistance at ambient temperature.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Resat Aksakal, Corentin Tonneaux, Annemiek Uvyn, Mathieu Fossepre, Hatice Turgut, Nezha Badi, Mathieu Surin, Bruno G. De Geest, Filip. E. Du Prez
Summary: Antibody-recruiting molecules are a new type of therapeutic agents that can recruit endogenous antibodies to target cells for elimination. Macromolecular scaffolds with multiple copies of an antibody-binding ligand offer advantages in terms of increased avidity. In this study, we synthesized sequence-defined macromolecules with dinitrophenol (DNP) as a model antibody-recruiting motif and observed enhanced avidity for anti-DNP antibodies with adjacent DNP motifs. These findings provide insights for designing novel antibody-recruiting therapeutic agents.
Article
Polymer Science
Alyssa J. J. Ghielmetti, Christopher Barner-Kowollik, Filip E. E. Du Prez, Hannes A. A. Houck
Summary: The molecular network connectivity in dynamic polymer networks significantly affects material properties and reprocessing conditions. The influence of regioisomerism in light-stabilized dynamic materials has been highlighted. Interchanging regioisomer fractions of substituted naphthalenes with triazolinediones (TADs) in a photo-driven cycloaddition reaction has been demonstrated to affect the cycloreversion kinetics and is important for the design of dynamic covalent materials. The development of completely regioselective TAD/naphthalene systems and the control of cycloreversion kinetics through naphthalene substitution offer new opportunities for the advancement and applications of light-stabilized dynamic materials.
Article
Chemistry, Multidisciplinary
Steven C. Gauci, Filip E. Du Prez, Joshua O. Holloway, Hannes A. Houck, Christopher Barner-Kowollik
Summary: This study demonstrates the power of photochemical action plots by investigating two TAD substrates with similar absorption spectra but vastly different photoreactivity. The design of a hybrid TAD molecule enables the formation of a dual-gated reaction system, showcasing exceptional and site-selective (photo)chemical behavior within a single small molecule.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Joshua O. Holloway, Christian Taplan, Filip E. Du Prez
Summary: This study combines vinylogous urethane (VU) and beta-amino ester chemistry to synthesize covalent adaptable networks (CANs). The thermal and rheological properties of the resulting CANs are extensively analyzed. The study shows that these CANs have good storage modulus and re-processability.
