Article
Chemistry, Multidisciplinary
Thomas J. Neal, Nicholas J. W. Penfold, Steven P. Armes
Summary: This study reports a new aqueous polymerization-induced self-assembly (PISA) formulation that utilizes a reverse sequence approach to prepare hydrophobic blocks and produce charge-stabilized latex particles. The latex is then converted into smaller sterically stabilized diblock copolymer nanoparticles, which exhibit thermoresponsive behavior.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Jia-Wei Li, Miao Chen, Ze Zhang, Cai-Yuan Pan, Wen-Jian Zhang, Chun-Yan Hong
Summary: The composition and structure of polymers greatly impact their performance, and copolymerization of different monomers can result in polymers with diverse compositions. However, copolymerization of monomers with extremely different structures is quite challenging due to varied polymerization mechanisms.
Article
Polymer Science
Shuai Jia, Li Zhang, Ying Chen, Jianbo Tan
Summary: Photoinitiated polymerization-induced self-assembly (photo-PISA) is a scalable method for preparing block copolymer nanoparticles at room temperature. In this study, alpha,omega-functionalized polymers with a photoinitiator end group and a RAFT end group were synthesized and used as macromolecular photoinitiators/chain transfer agents in aqueous photo-PISA. The study found that near quantitative monomer conversion could be achieved within a short time, and moderate RAFT controllability was obtained. The effects of different factors on the morphologies of block copolymer nanoparticles were also investigated.
Article
Chemistry, Multidisciplinary
Jing Wan, Bo Fan, Kevin Putera, Jinhee Kim, Mark M. Banaszak Holl, San H. Thang
Summary: A sequential one-pot synthesis of hierarchically self-assembled polymer colloids with diverse morphologies has been achieved via aqueous PISA, overcoming the limitations of traditional methods. This approach provides a scalable method for the production of colloidal molecules and other hierarchical nanostructures, with the potential to enrich the complexity of morphology and enable diverse functions of nano-objects.
Article
Chemistry, Multidisciplinary
Frederic Grabowski, Vladislav S. Petrovskii, Fabian Fink, Dan Eugen Demco, Sonja Herres-Pawlis, Igor I. Potemkin, Andrij Pich
Summary: This article presents a computer simulation-driven experimental synthesis approach to fabricate programmable soft colloidal macromolecular structures through supramolecular self-assembly and polymerization of tailored monomers. The study demonstrates that the morphology of microgels can be tuned from spherical to raspberry-like or dumbbell-like by adjusting the loading of pyrazole-modified monomers. The work provides a quantitative and predictive method for guiding microgel design and can be extended to other colloidal systems and soft materials.
Article
Chemistry, Physical
Stephanie Boullanger, Emmanuel Contal, Cedric C. Buron, Lydie Viau
Summary: Pyrrole-functionalized imidazolium surfactants with different alkyl chain lengths were synthesized and their aggregation properties in water were investigated. It was found that these surfactants exhibited lower critical micellar concentration compared to their non-functionalized analogues. The structure of the aggregates formed and the preparation of water-stable polypyrrole nanoparticles were also studied.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Review
Polymer Science
Chengjian Zhang, Xiaowei Geng, Xinghong Zhang, Yves Gnanou, Xiaoshuang Feng
Summary: Sensitivity to environmental concerns and the demand for metal-free polymeric materials have driven research towards breakthroughs in organocatalytic polymerizations. Triethyl borane (TEB) has been discovered as an exceptional Lewis acid, serving to generate ate complexes and activate epoxides. Lewis pairs consisting of alkyl boranes combined with onium salts or organic bases have demonstrated unprecedented versatility for (co)polymerizations of oxygenated monomers, producing various oxygenated polymers. This review summarizes the progress made in TEB-mediated polymerization systems and proposes future challenges in organocatalytic synthesis.
PROGRESS IN POLYMER SCIENCE
(2023)
Article
Polymer Science
Hyun Jin Kim, Fumi Ishizuka, Rhiannon P. Kuchel, Shunsuke Chatani, Hiroshi Niino, Per B. Zetterlund
Summary: Nanodimensional polymeric worms were synthesized using polymerization-induced self-assembly (PISA), with the core segment lightly crosslinked to potentially enable various applications.
Article
Chemistry, Physical
Sanaz Sabaghi, Pedram Fatehi
Summary: In this study, cationic kraft lignin (CKL) polymers with different degrees of grafting were synthesized to investigate the impact of chain extension on the physicochemical behavior of CKL in an aqueous solution. The results showed that the architecture of cationic monomers significantly influenced the structure, rheological properties, and adsorption performance of CKLs on a solid surface, with more observable effects at higher grafting ratios.
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
(2021)
Article
Polymer Science
Djallal Ikkene, Jean-Luc Six, Khalid Ferji
Summary: Polymerization-induced self-assembly (PISA) is a promising platform technology for producing polymeric nano-objects, offering advantages over solvent switch methods. Aqueous dispersion reversible addition fragmentation chain transfer PISA (aqueous dispersion RAFT PISA) has gained popularity due to its green chemical process and high efficiency in producing various morphologies. This review provides a comprehensive summary of recent works on aqueous dispersion RAFT PISA, including different RAFT activation techniques, hydrophilic steric stabilizers, and monomers used. It aims to serve as an overview for experts and a toolbox for non-experts interested in exploring this robust and efficient route for producing block copolymer-based nano-objects for specific applications.
EUROPEAN POLYMER JOURNAL
(2023)
Article
Polymer Science
Dongdong Liu, Shuaiqi Yang, Shaojie Peng, Ying Chen, Li Zhang, Jianbo Tan
Summary: This study reports the first simultaneous synthesis and self-assembly of bottlebrush block copolymers at room temperature using photoinitiated polymerization-induced self-assembly (photo-PISA) with multifunctional macromolecular chain transfer agents (macro-CTAs). The bottlebrush block copolymers promote the formation of higher-order morphologies and exhibit a higher polymerization rate compared to linear block copolymers. The obtained bottlebrush block copolymer vesicles are used as seeds for further chain extension and formation of multicompartment nanoparticles with a sponge internal structure. This study expands polymer architectures employed in PISA and provides a new strategy for synthesizing polymer nanoparticles with unique structures.
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Polymer Science
Honggui Chen, Xiang Zhang, Ziyu Lin, Rui Zhang, Bingran Yu, Yang Li, Fu-Jian Xu
Summary: This study reports a simple one-step polymerization method for in situ preparation of hydrogels in aqueous solutions, where water-miscible monomers are copolymerized to enhance the mechanical properties of the hydrogels. This strategy provides an effective approach to design mechanically enhanced hydrogels for a wide range of applications.
MACROMOLECULAR RAPID COMMUNICATIONS
(2021)
Article
Chemistry, Multidisciplinary
Ali Khalil, Christine Gerardin-Charbonnier, Hubert Chapuis, Khalid Ferji, Jean-Luc Six
Summary: This study presents a multistep synthesis of novel (meth)acrylate monomers based on gallic acid (GA) and the production of bio-based polymers with antioxidant properties. Through photo-mediated RAFT polymerization with evaluation of two trithiocarbonate-type chain transfer agents (CTAs), protected GA-based polymers were synthesized and deprotected to yield polymeric chains with free gallic acid moiety for antioxidant activity. The research demonstrates the potential of these free GA-based polymers through DPPH free radical scavenging and inhibition of methyl linoleate oxidation.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2021)
Article
Chemistry, Multidisciplinary
Matthew J. Rymaruk, Cate T. O'Brien, Csilla Gyorgy, Bastien Darmau, James Jennings, Oleksandr O. Mykhaylyk, Steven P. Armes
Summary: Polymerization-induced self-assembly (PISA) is used to prepare lyotropic phases with diblock copolymer nano-objects in non-polar media. Through NMR and X-ray scattering studies, the copolymer compositions and phase transitions during benzyl methacrylate polymerization are revealed. The hexagonal cylinder phase undergoes an order-disorder transition upon heating to 150 degrees C, forming a pure hexagonally close-packed (HCP) phase upon cooling to 20 degrees C.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Multidisciplinary
Nankai An, Xi Chen, Mingxin Zheng, Jinying Yuan
Summary: Monodisperse fluorinated nanospheres with regulated diameter (100-200 nm) and low PDI (<0.05) were prepared through polymerization-induced self-assembly (PISA). Colloidal self-assembly induced by solvent evaporation formed mono/multilayered 2D and large-scale ordered 3D lattices. This work demonstrates the promising application of PISA in colloidal self-assembly.
CHEMICAL COMMUNICATIONS
(2023)
Article
Polymer Science
Xin Luo, Zesheng An
MACROMOLECULAR RAPID COMMUNICATIONS
(2020)
Article
Chemistry, Multidisciplinary
Ruoyu Li, Zesheng An
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2020)
Article
Chemistry, Multidisciplinary
Zaiwang Zhao, Xiao Wang, Xinxin Jing, Yujuan Zhao, Kun Lan, Wei Zhang, Linlin Duan, Dingyi Guo, Changyao Wang, Liang Peng, Xingmiao Zhang, Zesheng An, Wei Li, Zhihong Nie, Chunhai Fan, Dongyuan Zhao
Summary: Ultrafine organic-inorganic hybrid nanoparticles were successfully synthesized using a thermo-kinetics-mediated copolymer monomicelle approach, leading to nanoparticles with monodisperse, uniform size and high thermodynamic stability. These nanoparticles demonstrated excellent uniformity and toughness, showing promise for a wide range of potential applications.
ADVANCED MATERIALS
(2021)
Article
Polymer Science
Ruo-Yu Li, Ze-Sheng An
Summary: This study demonstrates the oxygen tolerance of surfactant-free or ab initio photoenzymatic reversible addition-fragmenatation chain transfer (RAFT) emulsion polymerization for various monomers, producing well-defined amphiphilic block copolymers with ultrahigh molecular weight. The controlled character of surfactant-free emulsion polymerization and the synthesis of low-dispersity hydrophobic polymers in ab initio emulsion polymerization were confirmed through kinetic studies, chain extension studies, and GPC analyses. Temporal control and extension of suitable monomers for photoenzymatic RAFT polymerization from hydrophilic to hydrophobic monomers were also achieved in this study.
CHINESE JOURNAL OF POLYMER SCIENCE
(2021)
Article
Chemistry, Physical
Yu-Xi Wang, Yang Li, Shi-Hui Qiao, Jing Kang, Zhi-Li Shen, Ning-Ning Zhang, Zesheng An, Xiaosong Wang, Kun Liu
Summary: A staged-thermal-initiation RAFT polymerization method is reported for the synthesis of polymers with high thiol end-group fidelity, which show high efficiencies for grafting to various gold nanoparticles (GNPs). Experimental proof shows that the decrease of end-group fidelity with molecular weight is caused by the gradual decomposition of the initiator. The positive correlation between end-group fidelity of polymers and grafting-to efficiency is illustrated through grafting-to assays for various GNPs.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Multidisciplinary
Xin Luo, Zesheng An
Summary: Polymerization-induced self-assembly (PISA) is an effective method for preparing block copolymer (BCP) particles with various morphologies, but the preparation of BCPs with inverse bicontinuous phase structure via PISA is rarely reported. In this study, particles with inverse bicontinuous phases were successfully prepared using PISA in ethanol/water. The bicontinuous structure of the BCP particles was characterized by transmission electron microscopy, and the effects of solvent composition and the degree of polymerization of the core-forming block were investigated.
CHINESE JOURNAL OF CHEMISTRY
(2021)
Review
Chemistry, Multidisciplinary
Ruoyu Li, Weina Kong, Zesheng An
Summary: This Minireview discusses the key roles enzymes play in reversible deactivation radical polymerization (Enz-RDRP) and highlights their applications in surface brush fabrication, sensing, polymerization-induced self-assembly, and high-throughput synthesis. The authors also reflect on the challenges and future directions of this emerging area.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Editorial Material
Polymer Science
Yiyong Mai, Zesheng An, Shiyong Liu
MACROMOLECULAR RAPID COMMUNICATIONS
(2022)
Article
Geochemistry & Geophysics
Xiao Wang, Jixiong Zhang, Meng Li, Feng Gao, Abbas Taheri, Binbin Huo, Ling Jin
Summary: The cemented foam backfill using hydrogen dioxide as a foaming agent is proposed to mitigate the issues of bleeding and shrinkage in coal mines. The formulation with lower cement, fly ash, and solid concentration shows improved volume increment and prolonged expanding duration.
Article
Chemistry, Multidisciplinary
Ruoyu Li, Shudi Zhang, Quanshun Li, Greg G. Qiao, Zesheng An
Summary: This study presents a novel enzymatic cascade catalysis for high-throughput synthesis of ultrahigh molecular weight polymers. The enzymatic cascade, consisting of formate oxidase and horseradish peroxidase, enables reversible addition-fragmentation chain transfer synthesis of polymers at extremely low volumes. This method offers a green and efficient approach for the synthesis of well-defined polymers without waste accumulation.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Polymer Science
Ruoyu Li, Weina Kong, Zesheng An
Summary: Reversible deactivation radical polymerization (RDRP) is a powerful method for synthesizing well-defined polymers, and the involvement of biocatalysts has enhanced its sustainability. In this Perspective, the green conditions, oxygen tolerance, versatile function, and access to difficult polymers in bioRDRP are highlighted. The future of bioRDRP may benefit from expanding the biocatalyst library, improving bacterial redox potential, enhancing biocatalyst robustness, and conducting mechanistic studies.
Article
Chemistry, Multidisciplinary
Qingchi Ma, Greg G. Qiao, Zesheng An
Summary: Visible-light controlled photoiniferter reversible addition-fragmentation chain transfer (RAFT) polymerization enables the synthesis of polymers with high molecular weights, controlled sequence, and tunable dispersities, offering great potential for the synthesis of advanced materials.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Fei Lv, Zesheng An, Peiyi Wu
Summary: Polymerization-induced cooperative assembly (PICA) is reported to efficiently access inverse bicontinuous mesophases within particles consisting of amphiphilic block copolymers (BCPs) and solvophobic copolymers. Through systematic variation of core-forming block/solvophobic copolymer at different CTA molar ratios, PICA promotes the formation of inverse bicontinuous mesophases more effectively compared with PISA. The synthesized BCPs/solvophobic copolymers by PICA have low dispersity and the particle morphology was investigated by TEM, SEM, and SAXS.
Review
Polymer Science
Zixin An, Shilong Zhu, Zesheng An
Summary: Photocatalytic reversible deactivation radical polymerization (RDRP) allows spatial-temporal regulation of radical polymerization using sustainable solar light, with heterogeneous photocatalysts offering additional advantages such as facile preparation, tunable photoelectronic properties, and potential for catalyst recyclization.
Article
Polymer Science
Jianyu Liu, Huazhang Guo, Qingjie Gao, Hongbin Li, Zesheng An, Wenke Zhang
Summary: This study directly observed the temperature- and solvent-dependent transition of water-soluble thermoresponsive polymer PNIPAM under external force using single-molecule magnetic tweezers and atomic force microscopy. The research found that upon heating or salt concentration change, the PNIPAM first forms nuclei each consisting of -31 repeat units, rather than random sizes, before undergoing subsequent transitions involving a merger of adjacent beads.
