Article
Engineering, Environmental
Kerui Chen, Wenjian Han, Xin Hu, Yihuan Liu, Yujing Hu, Shuangfei Zhao, Ning Zhu, Zheng Fang, Kai Guo
Summary: A microreactor-based enzymatic and metal-catalytic cascade reaction platform was developed for the synthesis of bottlebrush polymers. By using a continuous flow chemo-enzymatic strategy, well-defined bottlebrush polymers with fast kinetics and narrow molecular weight distribution were successfully prepared.
CHEMICAL ENGINEERING JOURNAL
(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
Polymer Science
William R. Archer, Grace E. Dinges, Piper L. MacNicol, Michael D. Schulz
Summary: In this study, bottlebrush polymers with polyaziridine brushes and a polynorbornene backbone were synthesized by a grafting-through approach. Dynamic light scattering (DLS) was used to investigate the aggregation behavior of macromonomers and the growth of bottlebrush chains during the polymerization process.
Article
Polymer Science
Harry W. Gibson, Mason A. Rouser, Daniel Schoonover
Summary: A new method for synthesizing bottlebrush copolymers is introduced using crown ether-containing polyester and viologen in styrene solution, which allows for control over the structure and composition of the resulting polymers.
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
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)
Article
Polymer Science
James McQuade, Mya I. Serrano, Frieder Jakle
Summary: The incorporation of main group elements into polymers enables the synthesis of functional materials with unique molecular structures and chemical properties. Ring-opening metathesis polymerization (ROMP) is a versatile method for generating new main group element-functionalized materials.
Article
Polymer Science
Brandon R. Clarke, Gregory N. Tew
Summary: This article reports a method to overcome crosslinking in commercial poly(ethylene glycol) (PEG) caused by diol impurities, allowing for good control over the molecular weight of bottlebrush polymers. PEG-based bottlebrush networks were successfully synthesized through ring-opening metathesis polymerization, achieving high conversions and low sol fractions (<2%). The crystallinity and mechanical properties of these networks were further modified by solvent swelling. The synthesis methods highlighted in this study demonstrate the potential of bottlebrush network architecture in the rational design of new materials.
JOURNAL OF POLYMER SCIENCE
(2022)
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
Polymer Science
Anqi Fang, Shaohui Lin, Flora T. T. Ng, Qinmin Pan
Summary: This research successfully synthesized core-shell bottlebrush polymer poly(PCL-b-PEG) with a more regular chain arrangement and better thermal stability compared to linear block polymers.
JOURNAL OF MACROMOLECULAR SCIENCE PART A-PURE AND APPLIED CHEMISTRY
(2022)
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
Nanoscience & Nanotechnology
Andrew Kerr, Satu Hakkinen, Stephen C. L. Hall, Paul Kirkman, Paul O'Hora, Timothy Smith, Christian J. Kinane, Andrew Caruana, Sebastien Perrier
Summary: Surface-tethered polymers have been evaluated as friction modifier additives in oil, and important structure-property relationships for this application have been revealed. The experimental results showed that these polymers can significantly reduce friction coefficient at low treatment rates.
ACS APPLIED MATERIALS & INTERFACES
(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
Junkun Fan, Ning Ren, Chongyin Zhang, Mao Li, Xinyuan Zhu, Gangsheng Tong
Summary: This study reports the synthesis of hyperbranched polyolefins using a one-pot process and a bi-functional acyclic olefin as a chain-transfer agent. The method provides a new route for the synthesis of functional hyperbranched polyolefin materials.
Article
Chemistry, Multidisciplinary
Yumeng Zhu, William R. Archer, Katlyn F. Morales, Michael D. Schulz, Yin Wang, John B. Matson
Summary: Inducing high levels of reactive oxygen species (ROS) in tumor cells is a cancer therapy method called chemodynamic therapy (CDT). In this study, a peptide-H2S donor conjugate complexed with Fe2+ called AAN-PTC-Fe2+ was developed. AAN tripeptide was specifically cleaved by legumain, an enzyme overexpressed in glioma cells, to release carbonyl sulfide (COS) which hydrolyzed to form H2S. Fe2+ and H2S together increased intracellular ROS levels and decreased viability in C6 glioma cells. AAN-PTC-Fe2+ performed better than temozolomide without cytotoxicity towards H9C2 cardiomyocytes. This study provides an H2S-amplified, enzyme-responsive platform for synergistic cancer treatment.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Zhao Li, Soumil Y. Joshi, Yin Wang, Sanket A. Deshmukh, John B. Matson
Summary: We report three constitutionally isomeric tetrapeptides with different nanostructures that catalyze hydrolysis reactions. Coarse-grained molecular dynamics simulations and machine learning analysis reveal the clusters of specific amino acid residues in hydrophobic pockets along the outer edge of the most efficient nanostructure, providing insights into the observed catalytic rate enhancement. This study demonstrates how subtle molecular-level changes can influence supramolecular nanostructures and catalytic efficiency.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Biochemistry & Molecular Biology
Santu Sarkar, Rajnish Kumar, John B. Matson
Summary: Gasotransmitters, including nitric oxide (NO), carbon monoxide (CO), and hydrogen sulfide (H2S), play important roles in maintaining various physiological processes. However, their clinical applications are limited due to their gaseous nature, short half-life, and broad physiological roles. Hydrogel-based delivery systems offer a potential solution for localized delivery of gasotransmitters. This review highlights the biological importance of gasotransmitters, discusses the fabrication of hydrogel materials, and explores the release behavior and potential therapeutic applications of gasotransmitter-releasing hydrogels. The authors also discuss the future of this field and the challenges that lie ahead.
MACROMOLECULAR BIOSCIENCE
(2023)
Article
Polymer Science
Samantha J. Scannelli, Anshul Paripati, Jeffrey R. Weaver, Clark Vu, Mohammed Alaboalirat, Diego Troya, John B. Matson
Summary: This study investigates the influence of different anchor groups on the activity of ROMP reaction through experiments and calculations. It is found that the HOMO energy of the anchor group is correlated with the propagation rate constant of the catalyst, indicating the significance of anchor group selection in ROMP reaction activity.
Article
Polymer Science
Samantha J. Scannelli, Mohammed Alaboalirat, Diego Troya, John B. Matson
Summary: Ring-opening metathesis polymerization (ROMP) mediated by Grubbs' third-generation catalyst (G3) is widely used to make bottlebrush polymers. This study investigated the effect of anchor groups on the livingness of ROMP, finding a positive correlation between anchor group energy levels and reaction rate constants, suggesting different degrees of livingness among the anchor groups.
Article
Multidisciplinary Sciences
Yumeng Zhu, Yulia Shmidov, Elizabeth A. Harris, Michelle H. Theus, Ronit Bitton, John B. Matson
Summary: In this research, hydrogels that imitate cryptic sites in the native extracellular matrix (ECM) were synthesized using switch peptides. The inert matrix undergoes a transformation into a bioadhesive synthetic ECM in response to enzymes on endothelial cells' surface. Cryptic sites are short signaling peptides that are hidden within the native ECM. Enzymatic cleavage of an ECM protein reveals these hidden peptide sequences, which interact with surface receptors to control cell behavior. Materials that mimic this dynamic interplay between cells and their surroundings via cryptic sites could enable application of this endogenous signaling phenomenon in synthetic ECM hydrogels.
NATURE COMMUNICATIONS
(2023)
Article
Polymer Science
Cody T. T. Bezik, Erica M. M. Redline, Jeffrey C. C. Foster, Amalie L. L. Frischknecht
Summary: This work investigates the influence of blend composition, network architecture, and hydrogen bonding on the material properties of crosslinked epoxy networks. The study finds that the introduction of hydrogen bonding significantly enhances the glass transition temperature (T(g)) of binary blend networks with lightly crosslinked systems. It also demonstrates that hydrogen bonding generally enhances Young's modulus (Y) and allows access to desirable dynamic behavior such as self-healing.
Article
Polymer Science
Jeffrey C. Foster, Joshua T. Damron, Honghai Zhang
Summary: Controlling the monomer sequence of synthetic polymers is a major challenge in polymer science. This study investigates cyclic olefin monomers for ring-opening metathesis polymerization (ROMP) and identifies easily synthesized oxanorbornene imide monomers suitable for single unit addition reactions. The findings enable the synthesis of multiblock copolymers with precise functionalization sites and singly cross-linked four-armed star copolymers.
Article
Polymer Science
Sarah N. Swilley, Evan M. Zajkowski, John B. Matson
Summary: We have developed a polymeric version of Piloty's acid that allows for tuning the release rate of HNO by adjusting the block ratios of PEG-b-poly(Piloty's acid) in a block copolymer system. By increasing the length of the poly(Piloty's acid) block, the HNO release from the block copolymers can vary by up to an order of magnitude. This study has potential implications in the development of HNO-releasing polymers for studying the effects of sustained HNO delivery in biological systems.
Article
Polymer Science
Mohammed Alaboalirat, Samantha J. Scannelli, Hadi Rahmaninejad, Jan-Michael Carrillo, Changwoo Do, John B. Matson, Rana Ashkar
Summary: Bottlebrush polymers are a unique class of macromolecular architectures with diverse applications that depend on their shape and size. This study systematically analyzed the structural and conformational properties of bottlebrush polymers using experimental and computational methods, providing key parameters and validating mean field theories.
Article
Polymer Science
Samantha J. Scannelli, Mohammed Alaboalirat, Diego Troya, John B. Matson
Summary: Norbornene-based monomers are commonly used in ring-opening metathesis polymerization (ROMP) due to their high ring strain. Recent studies have shown that the structure of norbornene derivatives significantly influences polymerization rates, with the anchor group playing a critical role.
Article
Polymer Science
Samantha J. Scannelli, Mohammed Alaboalirat, Diego Troya, John B. Matson
Summary: This study introduces a new anchor group, NBL, for ROMP and evaluates the polymerization rates of different positions of side-chain macromonomers. The results show that macromonomers with side-chains in the meta position have higher polymerization rates. Conversely, macromonomers with side-chains in the ortho position have lower polymerization rates, possibly due to steric interference.
Review
Nanoscience & Nanotechnology
Zhao Li, Yumeng Zhu, John B. Matson
Summary: Stimuli-responsive peptide-based biomaterials, particularly pH-responsive ones, have great potential in drug delivery and tissue engineering. By incorporating pH-responsive amino acids and organic linkers into peptides, they can self-assemble into various nanostructures. These biocompatible and adjustable platforms are ideal for drug release and mimicking the extracellular matrix. This review focuses on the design motifs and mechanisms of pH-responsiveness in self-assembling peptide-based biomaterials, highlighting recent advances in drug delivery and tissue engineering, and discussing future challenges and areas for development.
ACS APPLIED BIO MATERIALS
(2022)
Article
Polymer Science
Mohammed Alaboalirat, Clark Vu, John B. Matson
Summary: The direct-growth technique was used to synthesize macromonomers (MMs) through reversible addition-fragmentation chain transfer (RAFT) polymerization. The monomer type and conversion rate significantly influenced the formation of dimeric and oligomeric bottlebrush polymers.
Article
Chemistry, Multidisciplinary
Hannah D. Cornell, Yumeng Zhu, Stefan Ilic, Naomei E. Lidman, Xiaozhou Yang, John B. Matson, Amanda J. Morris
Summary: The synthetic methods for preparing a novel light-responsive metal-organic framework (MOF) UiO-AZB-F are outlined in this article. Upon exposure to green light, the framework demonstrates controlled release of chemotherapeutic drug cargo while simultaneously breaking down into low toxicity small molecule components.
CHEMICAL COMMUNICATIONS
(2022)