Article
Biochemistry & Molecular Biology
Alvaro Leonel Robles Grana, Hortensia Maldonado-Textle, Jose Roman Torres-Lubian, Claude St Thomas, Ramon Diaz de Leon, Jose Luis Olivares-Romero, Luis Valencia, Francisco Javier Enriquez-Medrano
Summary: This study demonstrates the efficient control of polymerization of methacrylic monomers using a symmetrical trithiocarbonate chain transfer agent in the RAFT process. However, an atypical behavior is observed in the polymerization of MMA, where high initiator/CTA molar ratios are required to achieve predictable molecular weights without affecting dispersity.
Article
Polymer Science
Deborah Schmitt, Salma M. Abdel-Hafez, Marco Tummeley, Volker Schunemann, Marc Schneider, Volker Presser, Markus Gallei
Summary: The controlled functionalization of surfaces is crucial for various applications. Surface-initiated living anionic polymerization (SI-LAP) offers adjustable and uniform functionalization. This study investigates the SI-LAP of different methacrylate monomers on porous polystyrene microparticles, and discusses the reaction kinetics and living character of the polymerization.
Article
Chemistry, Multidisciplinary
Nicolas Baulu, Marvin Langlais, Robert Ngo, Julien Thuilliez, Francois Jean-Baptiste-dit-Dominique, Franck D'Agosto, Christophe Boisson
Summary: In this study, block copolymers were successfully produced by combining anionic polymerization and coordinative chain transfer polymerization. Different polymer structures were obtained by combining different polymers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Lorella Izzo, Paola Lisa, Olga Sacco, Stefania Pragliola
Summary: In this study, PPO and PEPK di-block copolymers were successfully prepared using i-PrONa/i-Bu3Al as an anionic catalytic system. The copolymers showed almost 100% monomer conversion and controlled block lengths, with molecular weights close to theoretical values. The copolymer synthesis process was found to be efficient, with remarkable calorimetric properties and unique optical features.
Article
Polymer Science
Tian Zhang, Eamonn D. Conrad, Derek P. Gates
Summary: The living anionic polymerization of phosphaalkene has been used to synthesize a series of PMP homopolymers and PMP/S block copolymers. The samples showed monodispersity, narrow dispersities, and specific transition temperatures in their DSC chromatograms.
Article
Polymer Science
Wei Cao, Liangxiao Tan, Hong Wang, Jiayin Yuan
Summary: Dual-cationic PIL homopolymers carrying both imidazolium and 1,2,4-triazolium moieties were synthesized by exploiting the reactivity difference, leading to the expansion of their application spectrum.
Article
Polymer Science
Min Su, Yu-Jing Sheng, Yu-Jiao Chen, Tao Li, Quan-Xi Shi, Hang Xiao, Meng-Qin Pu, Hongli Bao, Wen-Ming Wan
Summary: A versatile living polymerization method is reported, which allows the precise synthesis of narrow distributed polystyrenes through the introduction of a well-established all-in-one covalent-anionic-radical Barbier strategy, using a wide variety of organohalides as initiators under mild conditions.
Article
Polymer Science
Robert Mundil, Alexander Zhigunov, Mariusz Uchman
Summary: In this study, we synthesized and self-assembled mPEG-block-PDL-block-PMMA triblock terpolymers using a metal-free catalytic system, which showed better polymerization control compared to sequential copolymerization. The blocks were found to be incompatible, leading to their self-assembly into multicompartment micelles in water.
EUROPEAN POLYMER JOURNAL
(2022)
Article
Chemistry, Multidisciplinary
Taha Behroozi Kohlan, Asu Ece Atespare, Mehmet Yildiz, Yusuf Ziya Menceloglu, Serkan Unal, Bekir Dizman
Summary: This article reports the synthesis and characterization of 2-oxazoline monomers and a range of POZ copolymers. By adjusting the composition, molecular weight, and side chain of the copolymers, a library of tailorable amphiphilic copolymers suitable for multiple applications is obtained.
Article
Chemistry, Multidisciplinary
S. Saravanan, Anashwara Babu, Ronald Merckx, Zifu Zhong, Mageshwari Anandan, Venkatramaiah Nutalapati, Bruno G. De Geest, Richard Hoogenboom, Valentin Victor Jerca, Samarendra Maji
Summary: Temperature is a crucial parameter in various applications, and it has significant effects on cellular activity and molecular processes. However, the use of anthrapyrazolone moiety as a fluorescent probe for temperature sensing has been neglected. In this study, polymeric thermometers were developed by investigating the fluorescence properties of different polymer compositions, showing promising potential for intracellular temperature measurements.
MATERIALS CHEMISTRY FRONTIERS
(2023)
Article
Polymer Science
Hiroaki Shimomoto, Itsuki Katashima, Hirokazu Murakami, Tomomichi Itoh, Eiji Ihara
Summary: Diazoacetates with various alkyl groups were polymerized to produce atactic poly(alkoxycarbonylmethylene)s (PACMs) using Pd-based initiating systems, and the effect of alkyl side-chain structure on thermophysical properties was investigated. It was found that using linear and branched side chains with different alkyl chain lengths did not significantly increase the melting point (T (m)) of PACMs. However, incorporating an amide-linkage in the middle of linear alkyl chains effectively raised T (m) due to hydrogen bonding interactions. The spacer length between the ester and amide linkages was crucial for increasing T (m), with the highest T (m) of around 130 degrees C achieved using a C4 spacer length and outer alkyl chain lengths of C7 and C9.
Article
Polymer Science
Meng-Qin Pu, Min Su, Yu-Jiao Chen, Xiao-Li Sun, Wen-Ming Wan
Summary: This study demonstrates the compatibility of Barbier covalent-anionic-radical polymerization (CARP) with air and divinylbenzene (DVB). Narrow distributed polystyrenes with D as low as 1.09 are successfully prepared under mild conditions in air. Additionally, poly(para-divinylbenzene) with D of 1.29, which exhibits versatile postpolymerization modification properties, can be prepared using Barbier CARP of DVB. This work expands the method library for the preparation of polymers with low D without requiring rigorous conditions.
Article
Polymer Science
Shin Inagaki, Tomoya Higashihara
Summary: A novel ABC-type triblock copolymer, consisting of PMMA, P3HT, and PS, was synthesized by the bilateral CuAAC reaction, resulting in a high yield.
Article
Chemistry, Multidisciplinary
Maki Amano, Mineto Uchiyama, Kotaro Satoh, Masami Kamigaito
Summary: This work describes the use of exo-olefin compounds as chain-transfer agents for sulfur-free reversible addition-fragmentation chain transfer (RAFT) radical polymerization. The authors synthesized a series of exo-olefin compounds and successfully polymerized methacrylates in homogeneous solution. More electron-donating substituents were found to produce polymers with narrower molecular weight distributions. Continuous monomer addition method further improved the control of molecular weight and enabled the synthesis of sulfur-free, colorless multiblock copolymers.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Physical
Jessica Bassi da Silva, Peter Haddow, Marcos Luciano Bruschi, Michael Thomas Cook
Summary: This article investigates graft copolymers with brush-like architectures containing thermoresponsive monomers. The study explores the chemical structure of the thermoresponsive polymer and its impact on phase behavior and rheological properties. The materials show potential for temperature-responsive applications in the field of medical materials.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Engineering, Chemical
Tetsuya Yamamoto, Osamu Tonomura, Aichiro Nagaki
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
(2020)
Article
Chemistry, Applied
Yosuke Ashikari, Kei Maekawa, Masahiro Takumi, Noriyuki Tomiyasu, Chiemi Fujita, Kiyoshi Matsuyama, Riichi Miyamoto, Hongzhi Bai, Aiichiro Nagaki
Summary: A novel strategy involving hierarchical bimodal porous silica gel supported palladium column reactors has been demonstrated to increase the unit-time-productivity of flow synthesis. The reactors, with low pressure drop due to the significantly large surface area of HBPSG, enable high-volume production. Flow synthesis of the precursor of adapalene, a pharmaceutical compound, was achieved at a rate of 5 g/h, over 10-fold greater productivity than previous approaches.
Article
Chemistry, Multidisciplinary
Naresh Bhuma, Ludivine Lebedel, Hiroki Yamashita, Yutaka Shimizu, Zahra Abada, Ana Arda, Jerome Desire, Bastien Michelet, Agnes Martin-Mingot, Ali Abou-Hassan, Masahiro Takumi, Jerome Marrot, Jesus Jimenez-Barbero, Aiichiro Nagaki, Yves Bleriot, Sebastien Thibaudeau
Summary: Ferrier's research in 1962 on the transformation of glycals into unsaturated glycosyl derivatives involved an alpha,beta unsaturated glycosyl cation. Through NMR-based structural analysis and DFT calculations, this elusive ionic species was characterized, leading to the synthesis of unsaturated nitrogen-containing C-aryl glycosides and C-alkyl glycosides under different conditions.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Review
Chemistry, Multidisciplinary
Aiichiro Nagaki, Yosuke Ashikari, Masahiro Takumi, Takashi Tamaki
Summary: This review showcases our approach to various synthetic reactions mediated by organolithium reagents based on flash chemistry conducted in flow reactors, particularly utilizing space-integration of the flow reactions.
Review
Chemistry, Organic
Yosuke Ashikari, Aiichiro Nagaki
Summary: This short review covers various aryl-aryl cross-coupling reactions carried out in flow, focusing on the metal species of the aryl nucleophiles used.
SYNTHESIS-STUTTGART
(2021)
Article
Chemistry, Multidisciplinary
Yosuke Ashikari, Takashi Tamaki, Tomoko Kawaguchi, Mai Furusawa, Yuya Yonekura, Susumu Ishikawa, Yusuke Takahashi, Yoko Aizawa, Aiichiro Nagaki
Summary: A chemoselectivity switchable microflow reaction has been developed to generate reactive and unstable intermediates, enabling the selection of different intermediates for polymerization. These reactions can produce polymers that are not achievable through typical polymerization reactions.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Organic
Takashi Tamaki, Aiichiro Nagaki
Summary: This study focused on transforming the commonly heterogeneous synthesis of phosphate esters into homogeneous synthesis, achieving high productivity in flow systems. Results showed that accelerating the reaction rate can further increase productivity. Additionally, the synthesis of the Akiyama-Terada catalyst was successfully completed in a short period.
TETRAHEDRON LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Masahiro Takumi, Hodaka Sakaue, Aiichiro Nagaki
Summary: A novel flow electrochemical reactor has been developed to achieve electrolysis within a few seconds and enable reaction with nucleophiles before the decomposition of short-lived carbocations. Furthermore, continuous operation based on this system allows for rapid synthesis of pharmaceutical precursors on demand.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Chemistry, Organic
Kyoko Mandai, Tetsuya Yamamoto, Hiroki Mandai, Aiichiro Nagaki
Summary: This study discovered that the reaction rate of cyclohexene epoxidation can be enhanced by using air as an oxidant without the need for added catalysts. A continuous flow reactor constructed with readily available stainless steel parts and devices was utilized, demonstrating a significant improvement in reaction time and high productivity. The efficient mass transfer between the liquid phase and air was the key factor in achieving the highly selective epoxide production.
BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Kazuhiro Okamoto, Ryosuke Higuma, Kensuke Muta, Keita Fukumoto, Yuta Tsuchihashi, Yosuke Ashikari, Aiichiro Nagaki
Summary: In this study, H-D exchange of one methylene proton was achieved in various dihalomethanes. Highly unstable carbenoid intermediate generation and its decomposition were successfully controlled under high flow-rate conditions. Monofunctionalization of diiodomethane afforded various building blocks, and diverted functionalization of monodeuterated diiodomethane produced products with isotope labeling and monodeuteration.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Organic
Yuichi Nakahara, Yuta Endo, Kazutoshi Takahashi, Tomoko Kawaguchi, Keisuke Kato, Yutaka Matsuda, Aiichiro Nagaki
Summary: Protein PEGylation is a bioconjugation technology that enhances therapeutic efficacy and in vivo half-life of proteins. The traditional batch-mode reaction can result in heterogeneous mixture of PEGylated proteins. To overcome this, a manufacturing strategy utilizing structural analysis and continuous-flow-mode reaction was examined. This strategy can achieve mono-PEGylation of different proteins within seconds, enabling gram-scale manufacturing without generating aggregates.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Kensuke Muta, Kazuhiro Okamoto, Aiichiro Nagaki
Summary: A novel approach using a jacketed syringe pump was developed for the formylation of organolithium species in a continuous-flow system under ambient pressure. Highly volatile organic compounds were used as formylating agents, enabling successful continuous operation for over 30 minutes.
Article
Chemistry, Multidisciplinary
Masahiro Takumi, Hodaka Sakaue, Daiki Shibasaki, Aiichiro Nagaki
Summary: This study demonstrates the rapid synthesis of unstable compounds using a fast electrochemical reactor, enabling easy access to various chemical reactions.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Multidisciplinary
Yosuke Ashikari, Kei Maekawa, Mai Ishibashi, Chiemi Fujita, Kiyonari Shiosaki, Hongzhi Bai, Kiyoshi Matsuyama, Aiichiro Nagaki
Summary: This study introduces a novel heterogeneous palladium catalyst for Suzuki-Miyaura cross-coupling and demonstrates its synthetic availability in batch and flow reactions. The research also includes the application of this catalyst in hydrogenative reduction reactions in flow, showcasing a sequential operation of coupling and hydrogenation reactions within 1 hour.
GREEN PROCESSING AND SYNTHESIS
(2021)
Review
Chemistry, Organic
Takashi Tamaki, Aiichiro Nagaki
Summary: This article discusses the importance of organic synthesis in creating functional materials and the role of chemoselective reactions in synthesizing complex compounds. Microreactors have more efficient heat and mass transfer compared to macro systems, leading to better chemoselectivity according to reaction kinetics.
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN
(2021)
