Article
Chemistry, Physical
Xabier Lopez de Pariza, Tim Erdmann, Pedro L. Arrechea, Leron Perez, Charles Dausse, Nathaniel H. Park, James L. Hedrick, Haritz Sardon
Summary: Conducting polymerizations under continuous-flow conditions has advantages over batch experimentation, especially in the synthesis of polyurethanes, allowing for rapid and precise control over material properties and improving process monitoring and control to minimize batch-to-batch variations.
CHEMISTRY OF MATERIALS
(2021)
Article
Polymer Science
Atsushi Sawamoto, Shin-nosuke Nishimura, Nobuyuki Higashi, Tomoyuki Koga
Summary: Controlling the thermoresponsive behavior of bio-based synthetic polymers is crucial for the development of smart functional materials. The synthesis of amino acid-derived vinyl polymers with different hydropathies and their thermal responses in water are reported, providing important insights for the precise design of stimuli-responsive bio-based polymers.
Article
Polymer Science
Shaoxiang Liu, Qilong Li, Yingying Li, Jiandong Zhang, Xiangqiang Pan, Jian Zhu, Xiulin Zhu
Summary: The synthesis of selenium-containing monomer polystyrene by reversible addition-fragmentation chain transfer polymerization, as well as the structure changes during redox cycling, were studied. The properties of the polymer before and after oxidation were investigated, and a selenium-containing polymer was successfully used to fabricate inverse opal photonic crystals for use as a redox-responsive sensor, showcasing new perspectives in modulating photonic crystals.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Chemistry, Inorganic & Nuclear
Nam Young Ahn, Jooyeon Lee, Wonjune Yeo, Hyojin Park, Jiyun Nam, Min Kim, Myungeun Seo
Summary: We have developed a synthetic method for decorating the surface of metal-organic frameworks (MOFs) with polymers through postsynthetic modification. By reacting well-defined polymers with reversibly deactivated radical species at their chain end with vinyl-functionalized MOFs in the presence of a radical initiator, we can form a C-C bond between the polymer end and the functional group at the MOF ligand. We have successfully achieved four polymer@MOF composites through this method.
INORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Mineto Uchiyama, Daichi Watanabe, Yuhei Tanaka, Kotaro Satoh, Masami Kamigaito
Summary: In this study, we achieved dual control of the optical activity and molecular weight of poly(BzF) by using thioether-based reversible chain-transfer agents, beta-amino acid derivatives as chiral additives, and aluminum chloride as a catalyst for asymmetric cationic polymerization. The asymmetric moderately living cationic polymerization led to an increase in molecular weight and specific optical rotation, and asymmetric block polymers consisting of opposite absolute configurational segments were synthesized using both enantiomers sequentially as chiral additives. The optical activity of poly(BzF) originated from the threo-diisotactic structure, which occurred by regio-, trans-, and enantioselective propagation, as revealed by comprehensive analysis of the polymerization products and the model reaction.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2022)
Article
Polymer Science
Yang Du, Shuai Jia, Ying Chen, Li Zhang, Jianbo Tan
Summary: The study presents an efficient strategy for preparing type I photoinitiator-functionalized block copolymer nanoparticles, which can be used as heterogeneous photoinitiators to generate hydrogels and further controlled in properties and functionalities by using different nanoparticles.
Article
Polymer Science
Dilhan Kandemir, Serter Luleburgaz, Ufuk Saim Gunay, Hakan Durmaz, Volkan Kumbaraci
Summary: This study introduces an organocatalyst-mediated method for the synthesis of poly(disulfide), which is rapid, robust, and practical. By screening various organocatalysts, the best catalyst with a low loading amount was identified to produce poly(disulfide) with varying molecular weights in just 1 minute. The optimum conditions for polymerization were determined using triphenylphosphine as the suitable catalyst. Moreover, successful synthesis of poly(disulfide) with molecular weights up to 85.6 kDa was achieved. The study also attempted a catalyst-free approach and found that polymer synthesis is possible under certain conditions, with increasing temperature leading to higher molecular weights.
Article
Chemistry, Multidisciplinary
Eleanor Raphael, Matthew J. Derry, Michael Hippler, Steven P. Armes
Summary: Polymerization-induced self-assembly (PISA) is used to design hydrogen-bonded poly(stearyl methacrylate)-poly(benzyl methacrylate) [PSMA-PBzMA] worm gels, with the ability to tune the storage modulus (G') by adjusting the proportion of end-groups on the PSMA chains. Two complementary routes are employed for achieving this tunability. SAXS and rheology studies offer detailed insights into the inter-worm interactions and physical behavior of these hydrogen-bonded worm gels.
Article
Polymer Science
Sany Chea, Kristin Schade, Stefan Reinicke, Regina Bleul, Ruben R. Rosencrantz
Summary: The base pairing and melting behavior of oligonucleotides can be utilized to develop smart thermoresponsive and programmable materials. In this study, complementary cytidine (C) and guanosine (G) monomers were blockcopolymerized using RAFT polymerization technique with hydrophilic macro chain transfer agent. The hydrogen bond interactions between C-C, G-G, and C-G were investigated, and the self-assembly of these bioinspired compounds showed potential for future drug delivery systems.
Article
Polymer Science
Hao Ge, Wencheng Shi, Chen He, Anchao Feng, San H. Thang
Summary: A series of core crosslinked star-shaped poly (styrene-b-isoprene-b-styrene) (SISs) and linear triblock SISs were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Both the star-shaped and linear SISs exhibited good tensile properties and a certain phase separation structure, demonstrating the characteristics of thermoplastic elastomers.
Article
Polymer Science
Arunjunai R. S. Santha Kumar, Stephanie Allison-Logan, John R. Finnegan, Nikhil K. Singha, Muthupandian Ashokkumar, Greg Qiao
Summary: The effect of ionic liquids on RAFT polymerization was investigated, and a considerable increase in the polymerization rate constants in ionic liquids was observed. Block copolymers with varying block ratios were synthesized with precise control over their molecular weight and chain-end fidelity provided by the photoiniferter polymerization in ionic liquids was described using MALDI-ToF MS analysis.
Article
Polymer Science
Jiawei Chen, Wenbing Wang, Yao Pan, Dan Peng, Yougui Li, Chen Zou
Summary: In this study, direct copolymerization of plant oil-based copolymer monomers with ethylene was achieved using a dienyl phosphoribosulfonyl palladium catalyst (PO-Pd). Addition, ureido-pyrimidinone (UPy) functionalization was performed using the hydroxyl group of the polymer. The incorporation of biomass groups effectively modifies the surface and mechanical properties of the copolymers, and these newly developed polymers are ideal tougheners for gutter oil due to their excellent tunability of the self-complementary hydrogen bonding network (UPy).
Article
Polymer Science
Alexandros E. Alexakis, Olivia R. Wilson, Eva Malmström
Summary: The combination of RAFT polymerization and PISA can produce monodisperse nanolatexes. This study demonstrates the synthesis of reproducible bimodal nanolatexes by extending protonated PDMAEMA with MMA in water and provides the first imaging data. The bimodality is induced by the hydrophilic Z-group of the RAFT agent, which has been reported to cause bimodal molecular weight distributions in RAFT-mediated PISA. The advantages of such nanolatexes in coating applications are briefly explored, including their one-pot synthesis, higher contact angle against water when adsorbed on cellulose filter paper, and morphological arrangement dependent on the drying protocol.
Article
Chemistry, Multidisciplinary
Anne-Catherine Lehnen, Johannes Gurke, Alain M. Bapolisi, Martin Reifarth, Marek Bekir, Matthias Hartlieb
Summary: XPI-RAFT is introduced as a fast and versatile photo-polymerization strategy. It enables efficient chain extension directly by irradiation and decouples photo-activation from polymerization control, making it an elegant tool for the synthesis of defined and complex macromolecules.
Article
Chemistry, Multidisciplinary
Jun He, Ying Chen, Li Zhang, Jianbo Tan
Summary: In this study, stimulus-responsive vesicles are prepared by photoinitiated RAFT seeded emulsion polymerization. The obtained vesicles can transform into different shapes and be used for controlled release of cargos in the presence of reactive oxygen species.
CHINESE CHEMICAL LETTERS
(2023)
Article
Polymer Science
Yawei Su, Yikun Jiang, Liping Liu, Yujie Xie, Shichang Chen, Yongjun Wang, Rachel K. O'Reilly, Zaizai Tong
Summary: By reducing the hydrogen bond strength, we have overcome the external constraints encountered in living crystallization-driven self-assembly (CDSA), leading to controlled size and spatially defined compositions of nanoparticles.
Article
Polymer Science
Zehua Li, Amanda K. Pearce, Jianzhong Du, Andrew P. Dove, Rachel K. O'Reilly
Summary: Crystallization-driven self-assembly technique was used to prepare monodisperse cationic cylindrical nanoparticles with controllable sizes, which showed promising antibacterial activity and enhanced mechanical properties in nanocomposite hydrogels.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Chemistry, Physical
Garrett A. Taggart, Aynur Guliyeva, Kyunghee Kim, Glenn P. A. Yap, Darrin J. Pochan, Thomas H. Epps III, Eric D. Bloch
Summary: Porous coordination cages (PCCs) are a unique class of molecular adsorbents that have gained attention due to their potential solubility and various applications. However, the characterization of PCC behavior in solution has been challenging. In this study, the combination of DOSY NMR, TEM, and cryo-TEM was used to confirm the persistence of soluble PCCs in different solutions.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Kyle C. H. Chin, Jianxun Cui, Robert M. O'Dea, Thomas H. Epps III, Andrew J. Boydston
Summary: By using bioderivable photoresins derived from lignin deconstruction, we successfully manufactured thermoplastic parts with highly tunable thermal and mechanical properties, overcoming the difficulties in traditional vat photopolymerization 3D printing. These bioresins, formulated from two monomers obtainable from lignin, generated printed parts ranging from soft elastomers to rigid plastics. The parts exhibited thermoplastic behavior and were largely soluble in common organic solvents, expanding the application and repurposing of 3D-printed parts.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Darien K. Nguyen, Panagiotis Dimitrakellis, Michael R. Talley, Robert M. O'Dea, Thomas H. Epps III, Mary P. Watson, Dionisios G. Vlachos
Summary: We introduce a method of oxidizing long aliphatic alkanes using non-thermal, atmospheric plasma processing as an eco-friendly route for organic synthesis. By employing pulsed dielectric barrier discharge in He/O2 gas mixtures, we could convert n-octadecane into C18 secondary alcohols and ketones, with a maximum molar yield of 29.2%. Longer treatment times and higher power inputs resulted in the formation of dialcohols, diketones, and higher molecular weight oxygenates. We also observed the production of lighter hydrocarbon products and decarboxylation to CO2 at longer treatment times and higher power inputs. The highest energy yield of 5.48 x 10-8 mol/J was achieved at short treatment times and high powers, accompanied by higher selectivity to primary oxygenates. We propose direct hydroxylation of alkyl radicals and disproportionation reactions as the main pathways to alcohols and ketones. This study shows the potential of catalyst-free plasma discharges for functionalizing long hydrocarbon molecules at ambient conditions.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Chemistry, Multidisciplinary
Amrita Sikder, Amanda K. Pearce, C. M. Santosh Kumar, Rachel K. O'Reilly
Summary: This study reports a rational design to fabricate antibacterial supramolecular nanoparticles with variable shape, size, and cationic group density. The systematic variation of structural parameters allowed the researchers to understand the role of each parameter in the overall antibacterial properties.
MATERIALS HORIZONS
(2023)
Article
Chemistry, Multidisciplinary
Stephen D. P. Fielden, Matthew J. Derry, Alisha J. Miller, Paul D. Topham, Rachel K. O'Reilly
Summary: Biological cells are surrounded by phospholipid membranes to retain their contents. The fusion of phospholipid membranes mediates the movement of material within and between cells, allowing mixing of contents or excretion of material. While biological membrane fusion is well-studied, the controlled fusion of polymer-based membranes is largely unexplored. In this study, triggered polymersome fusion was demonstrated using out-of-equilibrium polymersomes formed by ring-opening metathesis polymerization-induced self-assembly, which persist until a specific chemical signal triggers their fusion. This research is important for developing communication methods between polymersomes and emulating life-like behaviors in synthetic nanotechnology.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Zaizai Tong, Yujie Xie, Maria C. Arno, Yifan Zhang, Ian Manners, Rachel K. O'Reilly, Andrew P. Dove
Summary: The successful use of a seeded growth approach enables the preparation of nanoparticles with controlled dimensions and spatially defined functionality. By controlling core chemistry, 2D platelet micelles with compositionally distinct segmented cores are obtained, which can be selectively hydrolytically degraded.
Article
Polymer Science
Priyanka M. Ketkar, Nicholas F. Pietra, Andrew G. Korovich, Louis A. Madsen, Thomas H. Epps III
Summary: This study presents a quantitative framework to describe the local polymer and ion dynamics in nanostructured block polymer electrolytes, which is validated through nuclear magnetic resonance spectroscopy measurements. The framework considers various factors such as polymer architecture, segmental mixing, chain stretching, and confinement to accurately capture the local dynamics. It provides insights into ion diffusion and conductivity at the local level and shows good agreement with experimental results.
Article
Polymer Science
Nicholas F. Pietra, Andrew G. Korovich, Priyanka M. Ketkar, Thomas H. Epps III, Louis A. Madsen
Summary: Block polymers have the potential to be used as solid-state battery electrolytes due to their optimized conductive and mechanical properties. This study investigates the role of molecular structure on ion transport and local ion dynamics in a polystyrene-block-poly(oligo-oxyethylene methacrylate) (PS-b-POEM) electrolyte doped with various lithium salts. The results show that increasing the size of the anion delocalizes the anion charge, reducing the coupling between salt ions while increasing the coupling between ions and polymer chain motions. This creates a more mobile overall environment.
Editorial Material
Polymer Science
Ty Christoff-Tempesta, Thomas H. H. Epps
Summary: Ionic liquids (ILs) have unique physicochemical properties that make them a promising medium for advanced recycling of polymers. They can solubilize plastics waste and biopolymers, deconstruct polymers at reduced temperatures, and minimize unwanted side reactions. The use of ILs in advanced recycling offers potential environmental benefits, such as reduced chemical escape and decreased energy demands.
Review
Chemistry, Multidisciplinary
Tianwei Yan, Alex H. H. Balzer, Katie M. M. Herbert, Thomas H. H. Epps III, LaShanda T. J. Korley
Summary: The circularity of polymeric materials is a global issue that impacts society due to undesirable end-of-life outcomes and waste accumulation. Recycling and repurposing are attractive solutions, but are hindered by poor property retention and heterogeneities in waste streams. Dynamic covalent chemistry allows for tailored reversible bonds to address recycling challenges. This review highlights key features of dynamic covalent chemistries, synthetic progress in new and existing polymers, and the influence of covalent bonds and polymer network structure on thermomechanical properties. It also examines the economic and environmental impacts of dynamic covalent polymeric materials in closed-loop processing.
Correction
Chemistry, Multidisciplinary
Amrita Sikder, Amanda K. Pearce, C. M. Santosh Kumar, Rachel K. O'Reilly
Summary: This study demonstrates the synthesis of diversified supramolecular nanostructures through templated assembly and investigates the role of multivalency, shape, size, and functional group density on antibacterial activity.
MATERIALS HORIZONS
(2023)
Article
Chemistry, Physical
Garrett A. Taggart, Aynur Guliyeva, Kyunghee Kim, Glenn P. A. Yap, Darrin J. Pochan, Thomas H. Epps III, Eric D. Bloch
Summary: As a unique class of molecular adsorbents, porous coordination cages (PCCs) have attracted interest due to their solubility, which allows for various applications. The understanding of cage behavior in solution is crucial for expanding the utility of soluble PCCs. However, the characterization of PCCs in solution has been limited, and there is a lack of definitive evidence. In this study, the combined use of DOSY NMR, TEM, and cryo-TEM is explored to confirm the persistence of soluble PCCs in various solutions.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Materials Science, Multidisciplinary
Sampanna V. V. Mhatre, Jignesh S. S. Mahajan, Thomas H. H. Epps, LaShanda T. J. Korley
Summary: This study compares lignin-derivable materials with petroleum-derived materials and identifies biobased alternatives for non-isocyanate polyurethane (NIPU) thermosets. The study shows that variations in methoxy content and bridging-carbon substitution have significant effects on the thermomechanical properties of NIPU networks.
MATERIALS ADVANCES
(2023)
