Article
Chemistry, Multidisciplinary
Phong K. Quach, Jesse H. Hsu, Ivan Keresztes, Brett P. Fors, Tristan H. Lambert
Summary: The ring-opening metathesis polymerization of cyclopropenes using hydrazonium initiators was investigated. The initiators, formed by condensing 2,3-diazabicyclo[2.2.2]octane and an aldehyde, polymerize cyclopropene monomers through a sequence of [3+2] cycloaddition and cycloreversion reactions. The study showed that the monomer to initiator ratio had a positive correlation with the degree of polymerization.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Yujin Cha, JiHyeon Hwang, Luis Ramos, Huina Lin, Tianyu Zhu, Chuanbing Tang
Summary: The synthesis of cyclic cobaltocenium and its application in the synthesis of high-performance copolymers have been reported.
Article
Chemistry, Multidisciplinary
Dmitry S. Belov, Logesh Mathivathanan, Melanie J. Beazley, William Blake Martin, Konstantin V. Bukhryakov
Summary: The study explores the capability of an iron-based catalyst in performing ring-opening metathesis polymerization of olefins, demonstrating that the use of in situ prepared heteroleptic iron catalysts significantly enhances polymerization rate and selectivity.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Applied
Nina Guy, Olivia Giani, Sebastien Blanquer, Julien Pinaud, Jean-Jacques Robin
Summary: Photopolymerization is gaining interest in both industrial and academic fields due to its high reaction kinetics, low emissions of organic solvents, and reduced shrinking stress. This method has mainly been developed for radical polymerization of vinyl monomers and to a lesser extent for ring-opening polymerization (ROP). With the emergence of new initiating systems, the photopolymerization of various cyclic monomers has expanded beyond epoxides, which were the first monomers polymerized by cationic ring-opening polymerization (CROP).
PROGRESS IN ORGANIC COATINGS
(2021)
Article
Polymer Science
Mohammad Yasir, Andreas F. M. Kilbinger
Summary: Norbornene and cyclohexene show different polymerization behaviors using Grubbs' catalysts due to their varying ring strain energy levels; a sequence-selective cascade polymerization of a monomer containing both rings resulted in polymers with moderate molecular weight dispersities and good control over molecular weight.
Article
Chemistry, Multidisciplinary
Zhen Yu, Meng Wang, Xu-Man Chen, Shuai Huang, Hong Yang
Summary: The novel macrobicyclic olefin system shows good selectivity and high stereoselectivity in ROMP, with sacrificial cleavage of the silyloxide bridge providing clean-structured, non-auxiliaried polymers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Honggang Mei, Bingjie Zhao, Huaming Wang, Sixun Zheng
Summary: The preparation of crosslinked PDCPD nanoparticles via ROMP-induced self-assembly approach was reported in this communication. The morphology of the obtained nanoparticles varied from spherical, cylindrical to planar depending on the molecular weights of Macro-CTAs, the concentrations of DCPD and the natures of solvents. The ROMPISA method provides a new and efficient approach to prepare crosslinked polymer nanoparticles.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Federica Sbordone, Juliet Veskova, Bailey Richardson, Phuong Thi Do, Aaron Micallef, Hendrik Frisch
Summary: Biopolymers, such as proteins and nucleic acids, are essential for life, while synthetic polymers have greatly impacted our everyday lives. By combining the functionality of biopolymers with the versatility of synthetic polymers, it is possible to create materials with tailored properties for various applications. However, traditional radical polymerization typically yields non-functional all-carbon backbones, limiting the incorporation of natural polymers into synthetic polymers. In this study, we developed a solid-phase peptide synthesis approach to generate synthetic peptide conjugates that can be readily copolymerized with synthetic comonomers, allowing for the incorporation of defined peptide sequences into the main chain of synthetic polymers. This strategy is compatible with all 20 standard amino acids and uses commonly available chemicals, making it suitable for widespread application.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Federica Sbordone, Juliet Veskova, Bailey Richardson, Phuong Thi Do, Aaron Micallef, Hendrik Frisch
Summary: Biopolymers, such as proteins and nucleic acids, are crucial to life, while synthetic polymers have greatly impacted our daily lives due to their accessibility. By combining the functionality of biopolymers with the durability of synthetic polymers, it is possible to create materials that can be customized for various applications.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Polymer Science
Narumi Miyasako, Shin-ichi Matsuoka, Masato Suzuki
Summary: New ester-functionalized bicyclic aliphatic polymers were successfully synthesized through ring-opening metathesis polymerization (ROMP) of various norbornene lactones and their analogues, followed by hydrogenation. The comparison and discussion of polymerizability and thermal properties between different monomers before and after hydrogenation were conducted. The obtained polymers showed excellent thermal stability and processing deformation suitable for transparent resin materials.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Review
Polymer Science
Jiaxi Xu, Nikos Hadjichristidis
Summary: The incorporation of heteroatom-containing weak bonds along polymer backbones has become a popular tool to accelerate degradation. Many methods have been reported for the synthesis of degradable heteroatom-containing polymers based on step-growth polymerization and chain-growth ring-opening polymerization. Ring-opening metathesis polymerization has emerged as an approach for the synthesis of various types of degradable polymers. This review covers the synthesis of different heteroatom-containing degradable polymers via ring-opening metathesis polymerization and their degradation mechanisms under different conditions.
PROGRESS IN POLYMER SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Taeyang An, Hanseul Ryu, Tae-Lim Choi
Summary: This study presents a versatile approach to improve the alternation and degradability of 2,3-dihydrofuran (DHF) copolymers by carefully controlling the reactivity of both the Ru initiators and the monomers. The DHF copolymers showed outstanding A, B-alternation and could be broken down to a single repeat unit level under acidic conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Ervin Kovacs, Bence Balterer, Nguyen Anh Duc, Gyorgyi Szarka, Michael C. Owen, Attila Domjan, Bela Ivan
Summary: A large number of organic solvents contaminate the environment on a daily basis worldwide. This study demonstrates that benzotrifluoride can be used as a suitable solvent for olefin metathesis reactions, providing high yields and similar or even higher reaction rates compared to dichloromethane.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Polymer Science
Tapas Debsharma, Bernd Schmidt, Andre Laschewsky, Helmut Schlaad
Summary: Polymerization of biomass-derived levoglucosenyl alkyl ethers using the Grubbs catalyst yields thermoplastic polyacetals with specific thermal properties in various solvents. The initiation step of the polymerization process is slow, with catalyst consumption leading to deactivation of chain ends.
Article
Polymer Science
Ankita Mandal, Subhajit Pal, Andreas F. M. Kilbinger
Summary: A new heterocyclic monomer is synthesized via Diels-Alder reaction and exhibits reluctant polymerization in dichloromethane (DCM) but facile polymerization in tetrahydrofuran using Grubbs' third generation catalyst (G3), with excellent control over molecular weight and dispersities. The removal of tert-butoxycarbonyl group from the polymeric backbone yields a water-soluble ring opening metathesis polymerization (ROMP) polymer. In DCM, this monomer can also copolymerize with 2,3-dihydrofuran under catalytic living ROMP conditions to produce backbone degradable polymers. All synthesized polymers are characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. This new method for preparing water-soluble ROMP homopolymers and cost-effective degradable copolymers and block-copolymers may have potential applications in biomedicine.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Polymer Science
Mohammad Yasir, Andreas F. M. Kilbinger
Summary: Norbornene and cyclohexene show different polymerization behaviors using Grubbs' catalysts due to their varying ring strain energy levels; a sequence-selective cascade polymerization of a monomer containing both rings resulted in polymers with moderate molecular weight dispersities and good control over molecular weight.
Article
Polymer Science
Subhajit Pal, Ankita Mandal, Linda Hong, Roberto D. Ortuso, Alke Petri-Fink, Stefan Salentinig, Andreas F. M. Kilbinger
Summary: Native chemical ligation (NCL) is an excellent and efficient method for the chemical synthesis of proteins and peptides from unprotected short peptide fragments. It offers high chemo- and regioselectivity, allowing the synthesis of functional biomacromolecules without protection-deprotection strategies under mild conditions. In this study, the potential of NCL for non-natural polymer conjugation was explored, and diblock and ABA triblock copolymers were synthesized with high efficiency. The successful synthesis of non-natural polymers using NCL was confirmed by size exclusion chromatography and NMR spectroscopy analysis.
Article
Polymer Science
Zhenghao Dong, Peng Liu, Aurelien Crochet, Andreas F. M. Kilbinger
Summary: A new type of tricyclic oxanorbornene monomer with an endomethyl group was developed for living ring-opening metathesis polymerization, showing significantly slower polymerization kinetics due to steric effects. Both monomers exhibited well-controlled molecular weights and dispersities, even with different generations of Grubbs' catalyst. Investigations revealed that steric hindrance only affected the rate of propagation, allowing for the preparation of block copolymers with good molecular weight and dispersity control between fast and slow monomers.
Article
Polymer Science
Ankita Mandal, Indradip Mandal, Andreas F. M. Kilbinger
Summary: Regioselective chain transfer agents, in combination with the PA-ROMP technique, are used to synthesize narrowly dispersed heterotelechelic polymers with excellent control over molecular weight and dispersity. The chain transfer agents show high efficacy in 15 pulses of polymerization, with minimal catalyst decomposition and high degree of chain end functionalization confirmed by H-1 NMR and MALDI-ToF mass spectrometry.
Article
Polymer Science
Ankita Mandal, Indradip Mandal, Andreas F. M. Kilbinger
Summary: In this study, commercially available Vince lactam and its derivatives were copolymerized with 2,3-dihydrofuran (DHF) in a living fashion based on the unique reactivity of Ru Fischer carbene. The resulting copolymers showed complete degradation into small molecules under mildly acidic conditions, indicating uniform incorporation of the DHF units throughout the polymer backbone. The high metathesis activity and regioselectivity of vinyl ethers were further exploited for the synthesis of degradable copolymers using vinyl ethers as effective chain transfer agents. This cost-effective and environmentally friendly synthesis of degradable polymers has potential applications in biomedical and environmental fields.
Article
Polymer Science
Mohammad Yasir, Manvendra Singh, Andreas F. M. Kilbinger
Summary: A mechanistically unique and efficient method for preparing heterotelechelic polymers through ring-opening metathesis polymerization using a single functionalization agent is reported. This method offers simplicity and efficiency, as different functionalization agents can be synthesized from inexpensive commercial starting materials to achieve the synthesis of heterotelechelic polymers.
Article
Polymer Science
Subhajit Pal, Indradip Mandal, Andreas F. M. Kilbinger
Summary: Terminal alkynes display high reactivity toward Ru-carbene metathesis catalysts. However, the bulkiness of the carbene inhibits their homopolymerization. Meanwhile, the high reactivity of alkynes prevents efficient cross propagation with less hindered cycloalkene monomers. Nonetheless, terminal alkynes can rapidly undergo cross-metathesis with vinyl ethers, allowing for efficient cross propagation. This study demonstrates the copolymerization of terminal alkyne derivatives with 2,3-dihydrofuran using Grubbs' third generation catalyst, showing controlled copolymerization and excellent control over molecular weight.
Article
Chemistry, Multidisciplinary
Ankita Mandal, Indradip Mandal, Andreas F. M. Kilbinger
Summary: This article describes a catalytic living ring-opening metathesis copolymerization method that achieves narrow dispersity, excellent molar mass control, and the ability to form block copolymers through a degenerative, reversible, and regioselective exchange of propagating Fischer-carbenes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Indradip Mandal, Ankita Mandal, Andreas F. M. Kilbinger
Summary: This study demonstrates that a monosubstituted 1,3-diene derivative attached to a polymer can act as a macrochain transfer agent in catalytic ring-opening metathesis polymerization. PEG- and PLA-based macrochain transfer agents were synthesized and characterized. Block copolymers with different chain lengths were prepared using a one-pot approach and their structures were confirmed using SEC and DOSY NMR spectroscopy.
Article
Polymer Science
Ankita Mandal, Subhajit Pal, Andreas F. M. Kilbinger
Summary: A new heterocyclic monomer is synthesized via Diels-Alder reaction and exhibits reluctant polymerization in dichloromethane (DCM) but facile polymerization in tetrahydrofuran using Grubbs' third generation catalyst (G3), with excellent control over molecular weight and dispersities. The removal of tert-butoxycarbonyl group from the polymeric backbone yields a water-soluble ring opening metathesis polymerization (ROMP) polymer. In DCM, this monomer can also copolymerize with 2,3-dihydrofuran under catalytic living ROMP conditions to produce backbone degradable polymers. All synthesized polymers are characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. This new method for preparing water-soluble ROMP homopolymers and cost-effective degradable copolymers and block-copolymers may have potential applications in biomedicine.
MACROMOLECULAR RAPID COMMUNICATIONS
(2023)
Article
Polymer Science
Subhajit Pal, Linda Hong, Rafael V. M. Freire, Saquib Farooq, Stefan Salentinig, Andreas F. M. Kilbinger
Summary: Polyaromatic amides have been extensively studied for foldamer design. A chlorophosphonium iodide reagent is developed to enable living polymerization of aromatic amino acid monomers and oligomers in solvents that break hydrogen bonds, expanding the application of aramids.
Article
Polymer Science
Ankita Mandal, Andreas F. M. Kilbinger
Summary: Star polymers have attracted attention due to their distinctive properties. A one-pot synthesis of narrowly dispersed and degradable homoarm and miktoarm star polymers exploiting the catalytic living ring-opening metathesis polymerization mechanism was presented. Various complex polymeric architectures were synthesized using appropriate chain transfer agents.
Article
Polymer Science
Ankita Mandal, Andreas F. M. Kilbinger
Summary: Vinyl ether based macro-chain transfer agents (m-CTAs) are used to synthesize different di or tri-block copolymers under catalytic living ROMP conditions. The m-CTAs, including polystyrene (PS) vinyl ether m-CTA, polycaprolactone (PCL) m-CTA, and polylactide vinyl ether (PLA) m-CTA, are synthesized via ATRP and ROP methods. The synthesized m-CTAs show high regioselectivity and metathesis activity, enabling the synthesis of metathesis-based A-B diblock copolymers with controlled dispersities (D < 1.4). These degradable ROMP polymers prepared under catalytic living ROMP conditions have potential applications in biomedicine.
Article
Chemistry, Multidisciplinary
Indradip Mandal, Andreas F. M. Kilbinger
Summary: Norbornene derivatives are commonly used monomers for synthesizing highly functional polymers. This study reports the use of commercially available styrene and its derivatives as efficient regioselective chain transfer agents (CTAs) for the catalytic synthesis of low ruthenium metathesis polymers, requiring significantly less catalyst than traditional ROMP experiments. The approach enables the synthesis of low molecular weight ROMP polymers with antimicrobial properties on a gram scale, providing a greener and more cost-effective methodology for metathesis-based materials synthesis.
Article
Chemistry, Multidisciplinary
Indradip Mandal, Ankita Mandal, Md Atiur Rahman, Andreas F. M. Kilbinger
Summary: In this study, the metathesis activity of conjugated 1,3 diene derivatives in ring opening metathesis polymerization (ROMP) using Grubbs' 3rd generation catalyst (G3) was investigated. Monosubstituted 1,3 dienes showed similar reactivities towards G3-alkylidenes as norbornene derivatives, making them suitable for chain transfer agents in catalytic ROMP. This unprecedented reactivity allowed for the synthesis of mono-end-functional poly(norborneneimide)s on a large scale. Additionally, more complex architectures such as star-shaped polymers could be synthesized catalytically via ROMP. This method was also utilized for the synthesis of ROMP block copolymers and ROMP-PEG diblock copolymer.
