Article
Polymer Science
Hanyu Lv, Jiaqi An, Fanfan Li, Yanwu Zhang
Summary: Reversible deactivation radical polymerization (RDRP) is a convenient and efficient technique for synthesizing polymers with precise structure. dl-Methionine is assessed as a control agent in RDRP of styrene and methyl methacrylate, effectively reducing polymer dispersity. The use of dl-Methionine allows for high end fidelities in the synthesis of polymethyl methacrylate-block-polystyrene.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Chemistry, Applied
Henrique T. de Matos, Tiago F. C. Cruz, M. Amelia N. D. A. Lemos, Pedro T. Gomes
Summary: The role of 2-iminopyrrolyl copper(I) complexes in the Reversible-Deactivation Radical Polymerization (RDRP) of methyl methacrylate (MMA) is described. A family of mononuclear and binuclear 2-iminopyrrolyl copper(I) complexes with phosphine ligands were synthesized and characterized. Complex 7 achieved the best results, operating via the interplay of Atom Transfer Radical Polymerization/Organometallic Mediated Radical Polymerization (ATRP/OMRP) mechanisms.
APPLIED ORGANOMETALLIC CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Ruoyu Li, Weina Kong, Zesheng An
Summary: This Minireview discusses the key roles enzymes play in reversible deactivation radical polymerization (Enz-RDRP) and highlights their applications in surface brush fabrication, sensing, polymerization-induced self-assembly, and high-throughput synthesis. The authors also reflect on the challenges and future directions of this emerging area.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Polymer Science
Graeme Moad
Summary: This paper discusses the development of the term 'reversible-deactivation radical polymerization (RDRP)' and highlights the significance of the paper that introduced this term.
POLYMER INTERNATIONAL
(2023)
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
Chemistry, Multidisciplinary
Wachara Benchaphanthawee, Chi-How Peng
Summary: Cobalt mediated radical polymerization (CMRP) plays a crucial role in controlling the polymerization of less active monomers, such as vinyl acetate, with the control mechanisms being correlated to the redox potential of cobalt complexes. The hybridization of CMRP and atom transfer radical polymerization (ATRP) allows for the direct synthesis of block copolymers in one pot. CMRP also enables the control of isotacticities and crystalline properties in polymers.
Article
Chemistry, Physical
Jonas Blahnik, Sebastian Krickl, Klaus Schmid, Eva Mueller, John Lupton, Werner Kunz
Summary: This article presents a free-radical polymerization method in a mesostructured system without surfactants or other auxiliary agents. The aim is to study the impact of surfactant-free mesostructuring on polymerization kinetics and derived polymers.
JOURNAL OF COLLOID AND INTERFACE SCIENCE
(2023)
Article
Polymer Science
Dmitrii V. Ludin, Nadezhda V. Illarionova, Ekaterina V. Bobrina, Konstantin A. Kozhanov, Ivan D. Grishin, Sergey D. Zaitsev, Igor L. Fedushkin
Summary: Polymerization of styrene with tributylborane in the presence of various p-quinones was investigated. It was found that the semi-quinone macroradical can regenerate the chain despite the dual nature of p-quinone and the presence of tributylborane. The reaction is insensitive to external conditions and can exhibit reversible-deactivation radical polymerization.
MACROMOLECULAR RESEARCH
(2023)
Review
Chemistry, Applied
Sharmaine B. Luk, Lorena A. Azevedo, Milan Maric
Summary: Dienes such as isoprene and butadiene are commonly used to give rubbery properties to polymeric materials. With a shift towards using renewable resources, bio-based monomers have been targeted as replacements for petroleum-based dienes in polymer production. Recent advancements in reversible deactivation radical polymerization (RDRP) have enabled the application of bio-based dienes in making polymeric materials with controlled microstructures and chain lengths.
REACTIVE & FUNCTIONAL POLYMERS
(2021)
Article
Polymer Science
Shehla Mushtaq, Muhammad Asad Abbas, Habib Nasir, Azhar Mahmood, Mudassir Iqbal, Hussnain A. Janjua, Qamar Malik, Nasir M. Ahmad
Summary: The study focuses on mitigating the detrimental effects of algae biofouling on manufacturing processes by developing environmentally friendly active antialgal cationic amphiphilic copolymers. Increasing PDMAEMA concentration enhances the copolymers' antialgal performance, reducing algae adhesion. Copolymers with higher DMAEMA concentration exhibit stronger hydrophilicity and lower adhesion to Dictyosphaerium algae.
JOURNAL OF APPLIED POLYMER SCIENCE
(2022)
Review
Chemistry, Multidisciplinary
Ali Bagheri, Christopher M. Fellows, Cyrille Boyer
Summary: 3D printing technology has revolutionized the fabrication of advanced materials, but the challenge remains in printing polymer materials with post-printing transformability. Traditional radical polymerization used in photopolymerization-based 3D printing offers limited control over chain growth and architecture, unlike the reversible deactivation radical polymerization which allows for network homogeneity tuning and the production of reactivatable species for subsequent processes. RDRP-based networks have advantages over conventionally formed networks in terms of controllability and post-synthetic transformations.
Review
Chemistry, Multidisciplinary
Zilong Wu, Cyrille Boyer
Summary: Near-infrared (NIR) light-induced reversible deactivation radical polymerization (NIR-RDRP) is an effective technique for preparing functional polymer materials using light energy. This review comprehensively summarizes the mechanisms and applications of NIR-RDRP systems.
Article
Materials Science, Multidisciplinary
Shuo Li, Ruchira Colaco, Anne Staubitz
Summary: Diazocine-functionalized initiators were synthesized for controlled radical polymerizations, and their efficiency in polymerizations of methyl acrylate and methacrylate was tested. The initiation of the reactions required high amounts of reducing agents and catalysts. Additionally, violet light irradiation during the reactions caused retardation or termination of the anilide compound.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Chemistry, Physical
Maria del Prado Garrido, Ana Maria Borreguero, Francisco Javier Redondo, David Padilla, Manuel Carmona, Maria Jesus Ramos, Juan Francisco Rodriguez
Summary: In this study, St-MMA particles with PEGMA and/or GMA brushes were synthesized and found to effectively remove bilirubin by improving the BSA immobilization capacity and reducing processing time. Attachment of BSA to the particles reduced bilirubin concentration in plasma from levels that threaten patient survival to levels close to those of healthy individuals.
Article
Thermodynamics
Jihe Zhao, Xuefeng Gui, Wenhai Zhang, Shudong Lin, Yuanyuan Tu, Jiwen Hu, Daguang He, Xiaohua Huang
Summary: This study investigated the thermal risk associated with styrene-methyl methacrylate bulk copolymerization, highlighting the impact of initiator concentration on exothermic behavior. The study also calculated kinetic parameters for safety considerations in storage and transportation. Overall, it provides important insights for safety assessments in industry using this copolymerization process.
THERMOCHIMICA ACTA
(2021)
Article
Chemistry, Multidisciplinary
Kriti Kapil, Grzegorz Szczepaniak, Michael R. R. Martinez, Hironobu Murata, Arman Moini Jazani, Jaepil Jeong, Subha R. R. Das, Krzysztof Matyjaszewski
Summary: In this study, hyperbranched polymethacrylates were synthesized by green-light-induced atom transfer radical polymerization (ATRP) under biologically relevant conditions. By using a water-soluble SBA inibramer as a inducer during the copolymerization of methacrylate monomers, well-defined branched polymethacrylates can be obtained in less than 30 minutes with predetermined molecular weights, tunable degree of branching, and low dispersity values (1.14 <= D <= 1.33). Moreover, SBA inibramer enables the synthesis of bioconjugates with a well-controlled branched architecture.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Multidisciplinary
Jing Lyu, Yinghao Li, Zishan Li, Piotr Polanowski, Jeremiasz K. Jeszka, Krzysztof Matyjaszewski, Wenxin Wang
Summary: This article presents a minireview on the most important modelling techniques and their applications in free radical polymerization (FRP) and reversible-deactivation radical polymerization (RDRP) of multivinyl monomers (MVMs). The combination of experiments and modelling can provide valuable assets for polymer researchers, inspiring new thinking for future MVMs experiment optimization and product design.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Julian Sobieski, Illia Ruzhylo, Grzegorz Szczepaniak, Adam Gorczynski, Krzysztof Matyjaszewski, Eric Manoury, Rinaldo Poli
Summary: Simple synthetic routes for the regioselective deuteration of tris[2-(dimethylamino)ethyl]amine (Me6TREN) variants are described. Formation of imine with formaldehyde-d(2) from tris(2-aminoethyl)amine (TREN) and subsequent reduction with NaBD4 resulted in N[CH2CH2N(CD3)(2)](3) or d(18)-Me6TREN in 79% yield. A trisubstitution protocol from 2-bromo-N,N-dimethylacetamide and ammonium carbonate, followed by reduction of the N(CH2CONMe2)(3) intermediate with lithium aluminum deuteride, afforded N[CH2CD2N(CH3)(2)](3) or (d(6)-arm)-Me6TREN in three steps and 52% overall yield. A similar protocol using 2-bromo-N,N-dimethyl-d(2)-acetamide, obtained from d(4)-acetic acid in two steps, and reduction of the N(CD2CONMe2)(3) intermediate with lithium aluminum hydride, resulted in N[CD2CH2N(CH3)(2)](3) or (d(6)-cap)-Me6TREN in four steps and 13% overall yield.
Article
Polymer Science
Dirk J. Schild, Juliana Bem, Grzegorz Szczepaniak, Arman Moini Jazani, Krzysztof Matyjaszewski
Summary: We report a photoinduced initiators for continuous activator regeneration atom transfer radical polymerization (PICAR ATRP) using sodium pyruvate and blue light (λ(max) = 456 nm). Water-soluble oligo(ethylene oxide) methyl ether methacrylate (OEOMA(500)) was polymerized under biologically relevant conditions. Well-defined polymers with high molecular weights and low dispersity were synthesized in less than 60 min using Cu/Fe dual catalysis and without deoxygenation.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Abdelhak Lachguar, Uchchhal Bandyopadhyay, Mehdi Ech-Chariy, Sandrine Vincendeau, Catherine Audin, Jean-Claude Daran, Eric Manoury, Rinaldo Poli, Eric Deydier
Summary: This study presents a new solvent-less reaction method to convert benzylic, allylic, ferrocenyl or tertiary alcohols into S-thioesters, which are stable precursors of corresponding thiols. The reaction involves reactions in neat thioacetic acid in the presence of tetrafluoroboric acid, and increasing the HBF4 concentration can enhance the reaction rate. Control experiments and DFT calculations provide insights into the mechanism of the reaction and the formation of intermediate products.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Xiaolei Hu, Grzegorz Szczepaniak, Anna Lewandowska-Andralojc, Jaepil Jeong, Bingda Li, Hironobu Murata, Rongguan Yin, Arman Moini Jazani, Subha R. Das, Krzysztof Matyjaszewski
Summary: This article introduces the first example of fully oxygen-tolerant red/NIR-light-mediated photoinduced atom transfer radical polymerization under biologically relevant conditions, using commercially available methylene blue as the catalyst. The method exhibits excellent oxygen tolerance and enables high-throughput synthesis of well-defined polymers and DNA-polymer bioconjugates in a short time.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Kostas Parkatzidis, Nghia P. Truong, Krzysztof Matyjaszewski, Athina Anastasaki
Summary: This paper introduces a photocatalytic ATRP depolymerization method, which significantly reduces the reaction temperature while enabling temporal regulation and high monomer recovery through the use of low-toxicity catalysts and visible light irradiation. The depolymerization rate can be modulated by simply turning the light on and off, and the method is compatible with various polymers and light sources while preserving the end-group fidelity.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jaepil Jeong, Xiaolei Hu, Hironobu Murata, Grzegorz Szczepaniak, Marta Rachwalak, Anna Kietrys, Subha R. R. Das, Krzysztof Matyjaszewski
Summary: Combining synthetic polymers with RNA allows for creating RNA-based materials with unique functions. By developing an acylation reagent, we achieved the direct incorporation of an atom transfer radical polymerization (ATRP) initiator into both synthetic oligoribonucleotides and natural biomass RNA. This approach enables the grafting of polymer chains from RNA and the synthesis of RNA-polymer hybrids with narrow molecular weight distributions, including RNA bottlebrushes, hydrogels, and stimuli-responsive materials.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Martin Cvek, Arman Moini Jazani, Julian Sobieski, Thaiskang Jamatia, Krzysztof Matyjaszewski
Summary: ZnO nanocrystals were successfully synthesized and used as a heterogeneous co-catalyst in mechano- and photoATRP. The photoATRP with ZnO exhibited faster reaction kinetics compared to mechanoATRP and did not require excess ligand. This study demonstrated the versatility and robustness of ZnO-cocatalyzed photoATRP for various monomers.
Article
Chemistry, Multidisciplinary
So Young An, Xinsheng Wu, Yuqi Zhao, Tong Liu, Rongguan Yin, Jung Hyun Ahn, Lynn M. Walker, Jay F. Whitacre, Krzysztof Matyjaszewski
Summary: This study synthesized bottlebrush polymers with poly(ethylene oxide) (PEO) side chains by ring-opening metathesis polymerization. These polymers can act as solid polymer electrolytes with impressive ionic conductivity and excellent electrochemical performance. The new design paradigm provides a new avenue for developing stable and conductive polymer electrolytes for lithium-metal batteries.
Article
Chemistry, Inorganic & Nuclear
Ambra Maria Fiore, Valentina Petrelli, Christophe Fliedel, Eric Manoury, Piero Mastrorilli, Rinaldo Poli
Summary: The solution behavior of complex [Rh(COD)(& mu;-OAc)](2) in dichloromethane has been investigated in the absence and presence of PPN+OAc- using multinuclear NMR spectroscopy. The addition of PPN+OAc- results in the generation of [Rh(COD)(OAc)(2)](-) through equilibration. Rapid exchange between different Rh complexes and acetate ligands is observed at room temperature, but freezing the exchange at lower temperatures allows for the coalescence of certain NMR resonances.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Maxime Michelas, Jean-Claude Daran, Alix Sournia-Saquet, Christophe Fliedel, Rinaldo Poli
Summary: The addition of benzoyl peroxide to [Co-II(acac)(2)] selectively produces [Co-III(acac)(2)(O2CPh)], a mononuclear Co-III complex with an octahedral coordination geometry. This compound can serve as a thermal initiator for radical polymerisation. Addition of ligands (L = py, NEt3) induces chelate ring opening and formation of different isomers. The addition of py strengthens the Co-III-O2CPh bond and lowers the initiator efficiency, while the addition of NEt3 quenches the benzoate radical.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Multidisciplinary
Illia Ruzhylo, Sandrine Vincendeau, Philippe Dauban, Eric Manoury, Rinaldo Poli, Agnes Labande
Summary: A series of heteroleptic dirhodium(ii) complexes have been evaluated for the redox-responsive decomposition of diazo substrates prone to chemoselectivity issues. The counter-anion of oxidized ferrocenyl-containing complexes was found to influence the chemoselectivity, with SbF6- and BAr4F- resulting in greater differences compared to BF4-. The correlation between ferrocenyl substituents and chemoselectivity switch was not obvious, but introducing a saturated tether drastically decreased the difference. Changing the electronic properties of only one ligand on dirhodium, by oxidation of its ferrocenyl part, had a marked influence on reaction selectivity.
NEW JOURNAL OF CHEMISTRY
(2023)
Article
Chemistry, Multidisciplinary
Chantal J. Abou-Fayssal, Christophe Fliedel, Rinaldo Poli, Anders Riisager, Karine Philippot, Eric Manoury
Summary: This study introduces a method to improve the confinement of rhodium nanoparticles (RhNPs) in nanoreactors by introducing phosphine oxide as anchoring groups in the hydrophobic core of amphiphilic star-block copolymers. The RhNP-loaded latex exhibits excellent catalytic activity and recyclability, making it a promising candidate for aqueous biphasic catalysis.
MATERIALS TODAY CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
Pardeep Dahiya, Nidhi Garg, Rinaldo Poli, Basker Sundararaju
Summary: To achieve the goal of a carbon-free energy economy, a well-defined air-stable Cp*Co(III) catalyst has been developed for the transfer hydrogenation of quinoline derivatives and the oxidative dehydrogenation of cyclic amines in water. These findings provide new avenues for studying environmentally benign cobalt catalysts for hydrogenation and dehydrogenation reactions.
DALTON TRANSACTIONS
(2023)