Article
Chemistry, Multidisciplinary
Haiwang Lai, Changming Jin, Junsu Park, Ryohei Ikura, Yoshinori Takashima, Makoto Ouchi
Summary: In this study, a bulky monomer with an alkyl-substituted trichloro salicylic acid pendant was designed to enable the synthesis of an alternating copolymer of MMA and nBA. The monomer showed low homopolymerization propensity but formed the alternating copolymer with nBA via copolymerization. The 1-Ad units in the copolymer were selectively transformed into MMA via transesterification, resulting in an alternating copolymer of MMA and nBA. Its alternating sequence was confirmed by structural analysis and the copolymer showed superior self-healing ability compared to the corresponding statistical copolymer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Yan-Xin Zhang, Dong Chen, Gao-Fei Hu, Yu-Hong Ma, Wan-Tai Yang
Summary: The alternating copolymerization of hydroxyalkyl vinyl ethers and dialkyl maleates was studied using radical polymerization and RAFT. The effects of comonomer structure, feeding ratios, and monomer concentrations on copolymerization and copolymer structure were systematically investigated. Alternating copolymers were successfully prepared with well-controlled molecular weight and narrow molecular weight distribution.
CHINESE JOURNAL OF POLYMER SCIENCE
(2023)
Article
Chemistry, Multidisciplinary
Philipp Gerdt, Armido Studer
Summary: A method has been developed for the synthesis of functionalized alternating copolymers by reversible deactivation radical polymerization, allowing for the generation of a small library of novel alternating terpolymers with diverse functionalities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Yongyao Lei, Yougen Chen
Summary: Eight novel alternating copolymers were successfully synthesized through the post-polymerization modification of poly(propylene-alt-allyl alcohol)100 (PPAA100), which cannot be accessed using general methodologies. The chemical transformations of the hydroxyl group in PPAA100 resulted in the formation of eight unique head-to-head alternating copolymers with fixed propylene structural units and allyl alcohol derived monomeric units. The obtained polymers were characterized using 1H and 13C NMR and FT-IR spectroscopies, and their thermal properties were investigated.
Article
Chemistry, Multidisciplinary
Qinzhi Quan, Mingyu Ma, Zongtao Wang, Yu Gu, Mao Chen
Summary: An organocatalyzed controlled radical alternating terpolymerization of PFVEs and VEs under visible-light irradiation was developed, allowing the synthesis of a broad scope of fluorinated terpolymers with low dispersities and high chain-end fidelity. This method facilitates tuning the chemical compositions by rationally choosing the type and ratio of comonomers, and also enables temporal control of chain-growth and the preparation of novel fluorinated block copolymers. The versatility of this method was showcased by synthesizing fluorinated alternating terpolymers customized to display a variety of desirable properties for solid polymer electrolyte design, leading to new opportunities in high-performance energy storage devices.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Xiuxiu Qi, Hongmei Yan, Yingxue Li
Summary: This study successfully prepared a pH-sensitive fluorescent polymer using ATRP method, and developed pH-sensitive core-shell nanoparticles as carriers for anticancer drug loading and controlled release by adding hollow mesoporous silicon. The nanocomposites showed high drug loading capacity and fluorescence properties, selectively inhibiting melanoma cells.
Article
Chemistry, Multidisciplinary
Yang Zeng, Qinzhi Quan, Peng Wen, Zexi Zhang, Mao Chen
Summary: In this work, a light-driven organocatalyzed copolymerization method using TFVB was reported for the controlled synthesis of a variety of hybrid fluorine/boron polymers with low dispersities and good chain-end fidelity. The combination of fluorine and boron was shown to provide high-performance copolymer electrolytes with a high lithium-ion transference number, offering new opportunities for engineering high-performance materials for energy storage.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Biochemistry & Molecular Biology
Mateusz Grabowski, Bartlomiej Kost, Agnieszka Bodzioch, Melania Bednarek
Summary: This paper presents a new strategy for preparing block copolymers of polylactide (PLA), using multiple inifer groups to introduce vinyl monomers (VM) into PLA chains. The inifer group tetraphenylethane (TPE) was incorporated into PLA chains using diisocyanate. The ability of PLA-PU to form initiating radicals was demonstrated, and block copolymers PLA/PVM were successfully formed through polymerization of acrylonitrile and styrene using PLA-PU as a macroinifer.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Polymer Science
Harpal S. Dhiraj, Fumi Ishizuka, Maria Saeed, Amr Elshaer, Per B. Zetterlund, Fawaz Aldabbagh
Summary: Higher order morphologies, such as rods and worms, can be formed by combining core-shell nanoparticles with boronic acid moieties under basic conditions. For the first time, it is observed that lactate, an anaerobic metabolite, can bind to the BA moiety of amphiphilic block copolymers at a lower physiological pH of 7.4. Self-assembly experiments show that the resulting nanoparticles have similar structures to those formed by reacting with glucose.
EUROPEAN POLYMER JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Anthony Keyes, Huong Dau, Krzysztof Matyjaszewski, Eva Harth
Summary: A new orthogonal radical/spin coupling technique has been identified in this study, which enables living insertion and controlled radical polymerization of polyolefins. This technique shows broad tolerance for different radical/spin traps and can be used for the synthesis of polyolefin-polyvinyl block copolymers with various segments.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Multidisciplinary
Hiroyuki Kubota, Makoto Ouchi
Summary: The development of polymers with on-demand degradability is crucial for addressing global polymer-waste pollution. In this study, a vinyl ether monomer with an o-nitrobenzyl group was designed and synthesized into an alternating copolymer. This copolymer exhibited rapid degradation upon UV irradiation, without the need for additional reactants or catalysts, while maintaining stability under heat and ambient light. The unique degradability of the o-nitrobenzyl group enabled exclusive photo-degradation of specific segments in a diblock copolymer.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Organic
Samantha Saxer, Omer Erdogan, Cedric Paniagua, Alain Chavanieu, Xavier Garric, Vincent Darcos
Summary: Protein-polymer bioconjugates show great potential in biomedical and life science applications, and a highly efficient, versatile, and facile chemical ligation reaction for the synthesis of macromolecules has been proposed in this article. Additionally, the aggregation behavior of amphiphilic graft copolymers based on poly(ethylene glycol) in water was investigated, and a new protein-polymer bioconjugate was prepared by copper-free click chemistry reaction using azido-functionalized polystyrene copolymers.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Kaixuan Chen, Yang Zhou, Shantao Han, Yinli Liu, Mao Chen
Summary: This study achieved controlled synthesis of fluoropolymers for the first time using a novel fluorinated xanthate agent through a light-driven process. The alternating copolymerization of chlorotrifluoroethylene and vinyl esters/amides was successfully carried out under both batch and flow conditions. A two-step photo-flow platform was established to enable in-situ chain-extension for the continuous synthesis of advanced block copolymers from fluoroethylene.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Review
Chemistry, Multidisciplinary
Wensheng Xie, Lingyun Zhao, Yen Wei, Jinying Yuan
Summary: Enzyme-catalysis-mediated reversible addition-fragmentation chain transfer (Enz-RAFT) polymerization is considered to be a versatile synthetic strategy, with high efficiency, mild conditions, and the ability to control the polymerization process in the presence of oxygen.
CELL REPORTS PHYSICAL SCIENCE
(2021)
Article
Polymer Science
Haiwang Lai, Makoto Ouchi
Summary: This study focuses on the synthesis of backbone-degradable polymers through radical copolymerization, achieving a specific structure through controlled reactions and functionalization of the resulting copolymer by alcoholysis or aminolysis transformations. By adding an excess of a certain monomer to obtain a specific sequence of the copolymer, and carrying out degradation reactions under different conditions, the influence of special structures on polymer properties have been verified.
Article
Multidisciplinary Sciences
Ren Tominaga, Yukihiro Nishimura, Yasuhito Suzuki, Yoshihiro Takeda, Masaru Kotera, Akikazu Matsumoto
Summary: Co-continuous network polymers (CNPs) are a new type of composite material made by filling the continuous pores of a hard epoxy monolith with various low-T-g polymers. The mechanical properties and fractural behavior of CNPs significantly depend on the network structure of the filler polymers, achieving a high strength and toughness through sacrificial fracture mechanism of epoxy-based hard materials with co-continuous network structures.
SCIENTIFIC REPORTS
(2021)
Article
Polymer Science
Yasuhito Suzuki, Yuya Shinagawa, Eri Kato, Ryutaro Mishima, Koji Fukao, Akikazu Matsumoto
Summary: This study investigates the reaction kinetics of bulk polymerization of methyl methacrylate, specifically focusing on the Trommsdorff effect. The research shows that a temperature increase and heterogenization of the polymerization solution occur simultaneously, leading to changes in transmittance. The study discusses phenomena related to the Trommsdorff effect, such as kinetic heterogenization, vitrification, structural changes, and formation of high-molecular-weight polymers.
Article
Materials Science, Biomaterials
Ayako Tsujimoto, Hiroki Uehara, Haruna Yoshida, Misaki Nishio, Kousuke Furuta, Takashi Inui, Akikazu Matsumoto, Shigeaki Morita, Masaru Tanaka, Chie Kojima
Summary: This study explores the tripartite relationship among PEG density, hydration state, and passive tumor targeting property in PEGylated dendrimers. It is the first report to demonstrate the hydration state of a drug carrier and discuss its relationship with biodistribution. Fully PEGylated dendrimers exhibited similar hydration behavior to PEG and passive tumor targeting property, while partially PEGylated dendrimers showed different hydration behavior and lacked the passive tumor targeting property.
MATERIALS SCIENCE & ENGINEERING C-MATERIALS FOR BIOLOGICAL APPLICATIONS
(2021)
Article
Materials Science, Biomaterials
Hiroya Shiba, Misaki Nishio, Mei Sawada, Mamiko Tamaki, Masataka Michigami, Shinya Nakai, Ikuhiko Nakase, Ikuo Fujii, Akikazu Matsumoto, Chie Kojima
Summary: The study demonstrates that Phe- and CHex-modified dendrimers can serve as pH-sensitive drug delivery systems for T cells, enhancing cellular uptake.
JOURNAL OF MATERIALS CHEMISTRY B
(2022)
Article
Chemistry, Physical
Yasuhito Suzuki, Ryutaro Mishima, Akikazu Matsumoto
Summary: This study investigates the reaction kinetics of isothermal bulk polymerization, focusing on the Trommsdorff effect. The data analysis using differential scanning calorimetry reveals that a higher temperature does not always result in a shorter reaction time for completion.
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS
(2022)
Article
Biotechnology & Applied Microbiology
Goshi Kuno, Yu Imaizumi, Akikazu Matsumoto
Summary: This study presents a cost-effective culture method suitable for mass culture of induced pluripotent stem (iPS) cells and provides a detailed analysis of selective detachment of iPS cells. The research findings demonstrate that a specific thickness and composition of polymer coating can achieve high-purity iPS cells, and the temperature variation can be used to control the culture process.
JOURNAL OF BIOSCIENCE AND BIOENGINEERING
(2022)
Article
Polymer Science
Kairi Miyata, Jun Yoshioka, Koji Fukao, Yasuhito Suzuki, Akikazu Matsumoto
Summary: This study investigates the behavior and transitions of copolymers of DiPF with AdA or nBA using DRS. The results reveal the presence of three dynamic processes and identify two glass transition temperatures. The temperature differences between the two processes are consistent with the fraction dependence, with an increase in AdA fraction resulting in larger differences. The physical origins of other processes are also discussed.
Article
Polymer Science
Tatsuya Sakamoto, Yasuhito Suzuki, Akikazu Matsumoto
Summary: The acrylate copolymers consisting of different acrylate monomers were synthesized, and the glass transition temperatures and adhesive properties were precisely controlled by adjusting the comonomer composition. It was found that the adhesion strength decreased during a debonding process by heating for the acrylate copolymers containing the BOC group. The use of thermally latent acids allowed for simultaneous thermal stability during use and quick response for on-demand debonding.
Article
Polymer Science
Kaito Osada, Ryotaro Akahori, Yasuhito Suzuki, Akikazu Matsumoto
Summary: This study proposes the use of thermal acid generators as catalysts to control the reaction rate and working temperature for the deprotection of PBHEMA. The thermal deprotection behavior of sulfonates as well as the additive effect of the thermal acid generators were investigated. The results provide insights into the kinetics and mechanism of the deprotection reaction of PBHEMA in the presence of the thermal acid generators.
POLYMER DEGRADATION AND STABILITY
(2022)
Article
Polymer Science
Chie Kojima, Yasuhito Suzuki, Yuka Ikemoto, Masaru Tanaka, Akikazu Matsumoto
Summary: PEG and PEGylated dendrimers were analyzed for their hydration behaviors using X-ray diffraction and infrared spectroscopy. Different crystal structures were observed in PEG/water mixtures with varying water content. The hydration state of PEGylated dendrimers was found to be different from that of PEG. These findings highlight the importance of comprehensive studies on eutectic mixtures of PEG compounds and water.
Article
Chemistry, Multidisciplinary
Yasuhito Suzuki, Shodai Onozato, Yuya Shinagawa, Akikazu Matsumoto
Summary: It has been demonstrated that nano- or micro-structured polymeric materials have huge potential as advanced materials. However, most of the current fabricating methods have limitations either in cost or in size. In this study, the bulk polymerization of methyl methacrylate in the presence of poly(ethylene glycol) (PEG) was investigated. It was found that phase separation occurs during bulk polymerization, and the resulting microscopic structures of poly(methyl methacrylate) can be controlled by the amount of PEG and the reaction temperature. The addition of PEG also significantly affects the reaction kinetics, leading to a shorter reaction time.
Article
Polymer Science
Ren Tominaga, Yoshihiro Takeda, Masaru Kotera, Yasuhito Suzuki, Akikazu Matsumoto
Summary: In this study, a new type of polymer composites, co-continuous network polymers (CNP), were fabricated by filling the continuous pores of an epoxy monolith with a cross-linked acrylate polymer. The mechanical properties of the materials were found to be dependent on the sizes of the pores and epoxy frame. Increasing the molar ratio of the amino groups to glycidyl groups during the fabrication process led to a coarser co-continuous structure, greatly enhancing the stretching property of the materials. Filling the pores with a rubbery cross-linked acrylate polymer as the second component increased the maximum strength of CNP, regardless of pore size. The boundary between the hard and soft phases of CNP was observed to have gap formation during a tensile test.
Article
Polymer Science
Yasuhito Suzuki, Ryutaro Mishima, Eri Kato, Akikazu Matsumoto
Summary: Relative concentration changes between glassy polymer and small molecules can lead to vitrification. Bulk polymerization, an example of such changes through a chemical reaction, can experience reaction acceleration (Trommsdorff effect) followed by reaction deceleration (glass effect). In this study, we investigated the Trommsdorff and glass effects of methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Using isothermal differential scanning calorimetry (DSC) data, we analyzed the conversion of the monomers as a function of reaction time. We observed apparent phase separation at the onset of the Trommsdorff effect under all experimental conditions. Furthermore, we examined these effects in relation to glass transition and changes in the amorphous structure during bulk polymerization.
Article
Polymer Science
Yasuhito Suzuki, Takahito Kano, Tsuyoshi Tomii, Nagisa Tsuji, Akikazu Matsumoto
Summary: The physical properties of polymers are significantly affected by relaxation processes. In this study, the two relaxations of fumarate-containing polymers were investigated using DSC, solid-state NMR, and X-ray scattering. Even in copolymers, the two relaxations were observed. Tensile tests showed brittleness of PDEF at specific temperatures and structural anisotropy when extended at alpha relaxation temperature.
Article
Pharmacology & Pharmacy
Hiroya Shiba, Tomoka Hirose, Yunshen Fu, Masataka Michigami, Ikuo Fujii, Ikuhiko Nakase, Akikazu Matsumoto, Chie Kojima
Summary: T cells are crucial for immune reactions and their activation is important for cancer immunotherapy. Polyamidoamine (PAMAM) dendrimers modified with 1,2-cyclohexanedicarboxylic acid (CHex) and phenylalanine (Phe) have been shown to effectively interact with different immune cells, including T cells. This study investigated the association between carboxy-terminal Phe-modified dendrimers with different bound numbers of Phe and T cells. The results demonstrated that dendrimers with more than half of the termini conjugating Phe exhibited a higher association with T cells. Dendrimers modified with Phe at 75% density showed the strongest association with T cells, which was related to their interaction with liposomes. Encapsulation of the model drug protoporphyrin IX (PpIX) into carboxy-terminal Phe-modified dendrimers enabled successful drug delivery into T cells.
