Article
Polymer Science
Niamh Bayliss, Gokhan Yilmaz, Alexander Plucinski, C. Remzi Becer, Bernhard V. K. J. Schmidt
Summary: Aqueous two-phase systems (ATPS) have gained attention in polymer chemistry due to their biocompatibility and applications in biomaterials and biology. This study investigated ATPS formed from poly(N,N-diethylacrylamide) (PDEA) with dextran and poly(ethylene glycol), and observed a significant shift in PDEA's cloud point temperature in the ATPS compared to pure aqueous solutions. This effect on thermoresponsive behavior opens up new possibilities for water-based polymer systems in areas such as multicompartment hydrogels or biotechnology.
Article
Polymer Science
Elaine Halligan, Shuo Zhuo, Declan Mary Colbert, Mohamad Alsaadi, Billy Shu Hieng Tie, Gilberto S. N. Bezerra, Gavin Keane, Luke M. Geever
Summary: Four-dimensional (4D) printing is a form of 3D printing technology that utilizes additional stimulus and stimulus-responsive materials, such as temperature-sensitive polymers like poly-N-vinylcaprolactam. This study aims to alter the phase transition temperature of poly-N-vinylcaprolactam hydrogels by incorporating two additional monomers, vinylacetate and N-vinylpyrrolidone, through photopolymerization. The findings show that the inclusion of N-vinylpyrrolidone increases the lower critical solution temperature above the physiological range, while the incorporation of vinylacetate decreases it to allow for self-assembly of 4D-printed objects at room temperature.
Article
Polymer Science
Chia-Hsin Ko, Cristiane Henschel, Geethu P. Meledam, Martin A. Schroer, Peter Mueller-Buschbaum, Andre Laschewsky, Christine M. Papadakis
Summary: The temperature-dependent phase behavior and self-assembly behavior of a thermoresponsive amphiphilic diblock copolymer in aqueous solution were studied, revealing a lower critical solution temperature (LCST) behavior at 31.1 degrees Celsius and the formation of different structures of micelles.
Article
Polymer Science
Anton A. A. Smith, Caitlin L. Maikawa, Hector Lopez Hernandez, Eric A. Appel
Summary: The properties of thermogelling tri-block copolymers can be tuned by altering the random terpolymer compositions, allowing for controlled modulation of thermogel properties. By controlling the lower critical solution temperature (LCST) of the pendant blocks, the heterogeneity of the pendant terpolymer blocks can be reflected in the concentration dependence of their critical solution behavior.
Article
Polymer Science
Lorenzo Marsili, Michele Dal Bo, Giorgio Eisele, Ivan Donati, Federico Berti, Giuseppe Toffoli
Summary: Poly-N-Vinylcaprolactam (PNVCL) is a thermoresponsive polymer with a lower critical solution temperature (LCST) between 25 and 50 degrees C, making it suitable for biomedical and environmental applications. PNVCL-COOH polymers were prepared via free radical polymerization to investigate their structural properties and LCST, which were found to be influenced by molecular mass. The behavior of the polymer in different solution environments, such as aqueous buffers, NaCl solutions and human plasma, was also studied.
Article
Pharmacology & Pharmacy
Svetlana V. Kurmaz, Vladislav M. Ignatiev, Nina S. Emel'yanova, Dmitry A. Konev, Vladimir V. Kurmaz, Anastasiya A. Balakina, Alexey A. Terentyev
Summary: In this study, nanosized systems of DOX based on micelle-like particles of amphiphilic thermosensitive copolymers were investigated. The formation of hydrogen bonds between the copolymer units and DOX was confirmed through experimental data and quantum-chemical modeling. The encapsulated DOX showed easier oxidation and somewhat more difficult reduction compared to free DOX in electrochemical studies. The copolymer compositions containing 5 and 15 wt% DOX exhibited active accumulation in cell nuclei without causing visual changes in cell morphology.
Review
Pharmacology & Pharmacy
Lorenzo Marsili, Michele Dal Bo, Federico Berti, Giuseppe Toffoli
Summary: Microgels are soft, porous, and deformable particles with an internal gel structure that are swollen by a solvent, making them potential candidates for drug delivery systems. Recent advancements in biodegradable polymer fabrication have led to new strategies in combining synthetic and natural-origin polymers with inorganic nanoparticles for controlled drug release. The use of chitosan-grafted-poly-(N-vinylcaprolactam) microgels in drug delivery and oncology applications is reviewed in this study.
Article
Polymer Science
Naoki Ozawa, Ji Ha Lee, Isamu Akiba, Tomoki Nishimura
Summary: Polymer architecture has a significant influence on the morphology of polymer self-assemblies. However, there is limited understanding of how changes in macromolecular architecture affect the structures of self-assemblies and the conformation of polymer chains within them. In this study, we examined the self-assembly behavior of four different amphiphilic copolymers with varying chain configurations. We found that changes in macromolecular architecture can result in the formation of different nanostructures, and the conformation of polymer chains within the self-assemblies also varies.
Article
Polymer Science
Elaine Halligan, Billy Shu Hieng Tie, Declan Mary Colbert, Mohamad Alsaadi, Shuo Zhuo, Gavin Keane, Luke M. Geever
Summary: This study presents the preparation of hydrogels based on Poly (N-vinylcaprolactam) with diethylene glycol diacrylate using the photopolymerization technique. The structure of the polymers is investigated using FTIR spectroscopy, and their characteristics are further examined using DSC and swelling analysis. The study aims to determine the properties of the polymer and its effects on the phase transition.
Article
Polymer Science
Albert Prause, Michelle Hechenbichler, Robert F. Schmidt, Miriam Simon, Sylvain Prevost, Leide P. Cavalcanti, Yeshayahu Talmon, Andre Laschewsky, Michael Gradzielski
Summary: Temperature control of rheological properties of aqueous solutions can be achieved by the addition of temperature-responsive amphiphilic polymers. In this study, three sets of acrylamide-based block copolymers with different architectures were explored, and their viscosities showed a substantial increase with increasing temperature. The changes in rheological properties were correlated with the mesoscopic organization of the systems.
Article
Polymer Science
Lauren E. E. Ball, Gabriela Garbonova, Rueben Pfukwa, Bert Klumperman
Summary: Responsive triblock copolymers were synthesized and studied for their potential use in drug delivery systems in biomedical research.
Article
Chemistry, Physical
Jingcong Xu, Volker Abetz
Summary: Graft copolymers with POEGMA backbones and PNIPAM side chains were synthesized using photoiniferter RAFT polymerization, showing unique temperature-dependent behaviors in aqueous solutions. The thermoresponsive properties were affected by the introduced end-groups, and post-polymerization modification further expanded the potential applications.
Article
Chemistry, Multidisciplinary
Michelle Hechenbichler, Albert Prause, Michael Gradzielski, Andre Laschewsky
Summary: A nonionic double hydrophilic block copolymer is synthesized using RAFT, with one hydrophilic and one thermoresponsive block. The copolymer acts as a polymeric surfactant at low temperatures, forming hairy micelles, and as an associative telechelic polymer at elevated temperatures, forming large dynamic aggregates, especially in a microemulsion.
Article
Polymer Science
Sara R. Nahra, Mauricio P. Oliveira, Erenilda Ferreira de Macedo, Carolina Ramos Hurtado, Dayane B. Tada, Lilia M. Guerrini, Eduardo Antonielli, Gerlon de Almeida Ribeiro Oliveira, Luciano Morais Liao, Fernando H. Cristovan
Summary: This study evaluated the physical-chemical properties and promotion of cell proliferation of blends of poly(N-vinylcaprolactam), poly(N-vinylcaprolactam-co-butylacrylate) with poly(3-hexylthiophene). The results showed that the addition of P3HT improved cytocompatibility and promoted cell proliferation.
JOURNAL OF APPLIED POLYMER SCIENCE
(2022)
Article
Polymer Science
Migle Babelyte, Laura Peciulyte, Vesta Navikaite-Snipaitiene, Joana Bendoraitiene, Volodymyr Samaryk, Ramune Rutkaite
Summary: Thermoresponsive chitosan-graft-poly(N-isopropylacrylamide) copolymers with different compositions were synthesized. The chemical structure of the copolymers was confirmed and their lower critical solution temperature (LCST) behavior was assessed. Copolymers with a certain content of poly(N-isopropylacrylamide) side chains demonstrated LCST behavior and could potentially be used in drug delivery systems or tissue engineering.
Article
Chemistry, Physical
Xuetong Li, Alba Villar-Yanez, Charlene Ngassam Tounzoua, Jordi Benet-Buchholz, Bruno Grignard, Carles Bo, Christophe Detrembleur, Arjan W. Kleij
Summary: We have developed a silver-catalyzed cascade conversion method for the selective formation of keto-functionalized cyclic carbonates using modular alkyne-1,n-diols and carbon dioxide. This method is characterized by its operational simplicity, excellent scope of carbonate-based heterocycles, and mild reaction conditions.
Article
Polymer Science
Florent Monie, Bruno Grignard, Christophe Detrembleur
Summary: This study reports an approach to fabricate self-blown nonisocyanate polyurethane (NIPU) foams by utilizing the divergent chemistries of amines with cyclic carbonates, creating the polymer network and thiolactone, and delivering in situ a thiol that generates the blowing agent (CO2) by reaction with a cyclic carbonate. The foams can be easily repurposed into films or structural composites by thermal treatment, showing recyclability. This facile and robust process offers new possibilities for designing more sustainable PU foams and provides options for end-of-life repurposing.
Article
Chemistry, Physical
Antoine Brege, Bruno Grignard, Raphael Mereau, Christophe Detrembleur, Christine Jerome, Thierry Tassaing
Summary: This review examines the state-of-the-art routes for synthesizing CO2-based (a)cyclic carbonates and polycarbonates from alcohol substrates. The first section focuses on the synthesis of organic carbonates from alcohol carbonation, discussing different strategies and substrates used. The second section discusses the formation of polycarbonates through direct copolymerization of CO2 with diols, as well as the ring-opening polymerization route. Finally, the polycondensation processes involving CO2-based dimethyl and diphenyl carbonates with aliphatic and aromatic diols are described.
Review
Chemistry, Multidisciplinary
Charlene Ngassam Tounzoua, Bruno Grignard, Christophe Detrembleur
Summary: This Review summarizes the recent advances in the synthesis of exovinylene cyclic carbonates, which can be produced from renewable and inexhaustible carbon dioxide as an alternative to fossil resources. The article focuses on describing the catalysts needed for their preparation and discussing the unique reactivity of these CO2-based heterocycles for the construction of diverse organic building blocks and (functional) polymers. The challenges and the future perspectives in the field are also discussed.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Fabiana Siragusa, Jeremy Demarteau, Thomas Habets, Ion Olazabal, Koen Robeyns, Gwilherm Evano, Raphael Mereau, Thierry Tassaing, Bruno Grignard, Haritz Sardon, Christophe Detrembleur
Summary: In this study, a new depolymerization method for step-growth polymers is reported, which can be degraded into their native precursor or added-value offspring, while generating hemiacetal cyclic carbonate. The specific functionalities in the polymer trigger degradation at a certain temperature and in the presence of an organic base catalyst, and can be fully degraded within 2 hours without the need for solution conditions.
Article
Chemistry, Multidisciplinary
Ashish Raj, Satyannarayana Panchireddy, Bruno Grignard, Christophe Detrembleur, Jean-Francois Gohy
Summary: A sustainable bio-based solid-state electrolyte was developed based on carbonated soybean oil, which exhibited good ion conductivity and electrochemical stability at both room temperature and high temperature, and showed promising performance in lithium batteries.
Article
Chemistry, Multidisciplinary
Fabiana Siragusa, Thomas Habets, Raphael Mereau, Gwilherm Evano, Bruno Grignard, Christophe Detrembleur
Summary: Designing easily degradable polymers is crucial to reduce the accumulation of post-consumer plastic waste. In this study, regioregular polycarbonates prepared by organocatalyzed copolymerization were chemically recycled, providing a feasible method for the synthesis of novel degradable polymers.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Maxime Bourguignon, Bruno Grignard, Christophe Detrembleur
Summary: This article reports a simple and scalable process for preparing non-isocyanate polyurethane (NIPU) foams. The process replaces the previous use of toxic isocyanate-based chemistry with a more sustainable variant that forms CO2 through the hydrolysis of a comonomer. The process allows for the production of greener polyurethane foams using readily available low-cost starting materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Anna Pierrard, Abdelhafid Aqil, Christophe Detrembleur, Christine Jerome
Summary: This study investigates isocyanate-free formulations for poly(propylene glycol) polyurethane elastomers and examines two curing approaches. The results show that both methods provide highly cross-linked polymer networks with excellent mechanical properties. The developed UV-activated formulation is suitable for 3D printing.
Article
Materials Science, Multidisciplinary
Alvaro Gomez-Lopez, Bruno Grignard, Inigo Calvo, Christophe Detrembleur, Haritz Sardon
Summary: By combining NH2-PHU-NH2, epoxy resin, and thiol compound, high-shear strength PHU-epoxy hybrid adhesives can be developed and cured at room temperature in short times. These adhesives exhibit superior toughness without compromising lap-shear strength and shear resistance under load and temperature, making them suitable for high-demand applications in the automotive industry.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Chemistry, Multidisciplinary
Fabiana Siragusa, Thomas Habets, Raphael Mereau, Gwilherm Evano, Bruno Grignard, Christophe Detrembleur
Summary: This study presents a new type of degradable polymer that can be easily and completely degraded into its monomers under mild conditions through catalyst-free aminolysis. The recovered monomers can then be used for polymer synthesis, offering a closed-loop recycling scenario. This work is of great significance for addressing the accumulation of post-consumer plastic waste and providing building blocks for the synthesis of novel degradable polymers.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Polymer Science
Bruno Grignard, Pieter Mampuys, Julien Escudero, Dario Masullo, Filip Lemiere, Bert U. W. Maes, Christophe Detrembleur
Summary: This study investigates the catalyst-free synthesis of urethanes from masked isocyanates and soft nucleophiles. The method achieves high functional group tolerance and has been successfully applied to construct regioregular functional polyurethanes.
Article
Polymer Science
Thomas Habets, Fabiana Siragusa, Alejandro J. Mueller, Quentin Grossman, Davide Ruffoni, Bruno Grignard, Christophe Detrembleur
Summary: This study presents a facile and efficient method for constructing copolymers containing both oxazolidone and thiocarbonate linkages. The one-pot terpolymerization process can be conducted at room temperature without the need for catalysts. The resulting copolymers have high solubility and can be used as adhesives. Additionally, a simple thermal treatment can achieve quantitative dehydration and the pendant double bonds allow for facile thiol-ene functionalization.
Article
Materials Science, Multidisciplinary
Abdelhafid Aqil, Farid Ouhib, Christophe Detrembleur, Maryline Moreno-Couranjou
Summary: An atmospheric one-step plasma-based method is reported in this study for the synthesis and deposition of redox-active catechol-rich polymers. The bioinspired films show potential as organic cathode materials for lithium ion batteries, with the influence of coating thickness on their applicative properties being investigated.
MATERIALS ADVANCES
(2021)
Article
Chemistry, Physical
Nagaraj Patil, Andreas Mavrandonakis, Christine Jerome, Christophe Detrembleur, Nerea Casado, David Mecerreyes, Jesus Palma, Rebeca Marcilla
Summary: Aqueous all-polymer batteries (AqPBs) are considered promising solutions for safe, sustainable, and high-performance energy storage applications. The development of such batteries, however, requires precise optimization of both electrodes and the electrolyte composition in order to maintain stable redox activity and deliver optimal voltage output. A specific AqPB system using a poly(imide) (PI) anode and poly(catechol) (PC) cathode has been shown to exhibit tunable cell voltage depending on the salt used in the aqueous electrolyte, achieving a maximum energy/power density of 80.6 W h kg(anode+cathode)(-1)/348 kW kg(anode+cathode)(-1) in Li+/H+, surpassing previously reported AqPB systems.
JOURNAL OF MATERIALS CHEMISTRY A
(2021)
Article
Polymer Science
Paige A. Shaw, Maxime Klausen, Mark Bradley
Summary: A light-responsive polymer capable of controlled release of camptothecin and generation of reactive oxygen species (ROS) was developed, which exhibited high cancer cell killing activity through both camptothecin release and ROS generation.
Article
Polymer Science
Donghui Zhang, Shiqi Liu, Zhihao Cai, Weizhe Luo, Guojian Liu, Runhui Liu
Summary: A straightforward and efficient method for synthesizing NPC monomers has been developed in this study, which enhances the availability of NPC monomers and facilitates the synthesis of polypeptides.
