Article
Polymer Science
Chandan Giri, Sarah E. Sisk, Louis Reisman, Irshad Kammakakam, Jason E. Bara, Kevin N. West, Brooks D. Rabideau, Paul A. Rupar
Summary: The study explores the anionic ring-opening polymerization of sulfonylaziridines in ionic liquids. In imidazolium ILs, the polymerization is not controlled due to poor solubility and solvent-transfer reactions, while in phosphonium ILs, it is controlled and living, allowing for sequential block copolymer synthesis. The slower polymerization rates in ILs compared to traditional polar solvents like DMF may be attributed to better monomer/anion organization in DMF and poorer mobilities in ILs.
Article
Chemistry, Multidisciplinary
Meng Huo, Yawen Bian, Chunyang Yu, Gangsheng Tong, Chongyin Zhang, Xinyuan Zhu
Summary: This study presents an AROP method for N-sulfonyl aziridines that can be operated in air environment using sulfanions as initiators. Open-vessel polymerization resulted in a range of polymers with high livingness and narrow molecular weight distributions, enabling further post-polymerization functionalization.
SCIENCE CHINA-CHEMISTRY
(2021)
Article
Polymer Science
Chiwon Hwang, Jong-Ho Back, Dowon Ahn, Hyun-Jong Paik, Wonjoo Lee, Youngchang Yu
Summary: UV-responsive pressure-sensitive adhesives were successfully achieved by utilizing the ring-opening reactions of N-carbonyl aziridine radicals. The post-modification of carboxylic acid-functionalized acrylic PSAs was characterized by spectroscopic analysis and their adhesion performance under UV light irradiation was evaluated, showing potential for academic research and mass-production industry applications.
Review
Polymer Science
Ryo Tanaka, Oluwaseyi Aderemi Ajala, Yuushou Nakayama, Takeshi Shiono
Summary: In coordination polymerization chemistry, cationic transition metals with vacant sites for monomer coordination are the most active species. The polymerization behavior is strongly influenced by the steric and electronic properties around the metal center. The design of neutral metal complex precursors, especially the ligand structure, plays a crucial role in the catalyst system development. Additionally, the choice of counteranions derived from the cocatalysts can significantly impact the controlled coordination polymerization.
PROGRESS IN POLYMER SCIENCE
(2023)
Article
Polymer Science
Glenn K. K. Clothier, Thiago R. . Guimaraes, Lisa T. Strover, Per B. Zetterlund, Graeme Moad
Summary: This paper describes the electrochemically initiated emulsion polymerization method with reversible addition-fragmentation chain transfer (eRAFT) for the formation of well-defined multiblock copolymers with low molar mass dispersity. Using a seeded RAFT emulsion polymerization approach at ambient temperature, the synthesis of low dispersity multiblock copolymers was successfully demonstrated. The method achieved the predicted characteristics of each generation of the multiblocks, including the desired molar mass, low molar mass dispersity, incrementing particle size, and low particle size dispersity.
Article
Multidisciplinary Sciences
Danping Tian, Ruipeng Hao, Xiaoming Zhang, Hu Shi, Yuwei Wang, Linfeng Liang, Haichao Liu, Hengquan Yang
Summary: Bioinspired multicompartment architectures are desired in synthetic biology and metabolic engineering due to their cell-like structures and ability of assembling catalytic species. This study describes a Pickering double emulsion-directed interfacial synthesis method to fabricate multicompartmental MOF microreactors, enabling tailor-made inner architectures and selective permeability. The microreactor demonstrates enhanced efficiency in chemo-enzymatic cascade reactions, showcasing its potential in complex cellular transformations.
NATURE COMMUNICATIONS
(2023)
Article
Chemistry, Multidisciplinary
Chen Chen, Nicole Janoszka, Chin Ken Wong, Christian Gramse, Ralf Weberskirch, Andre H. Groschel
Summary: Core-shell microparticles (CSMs) were successfully synthesized with an acid catalyst in the core and a base catalyst in the shell by surfactant-free emulsion polymerization (SFEP). These CSMs exhibited excellent catalytic performance in a model cascade reaction, making them promising candidates for organocatalytic applications in various solvents.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Polymer Science
Raita Goseki, Taro Koizumi, Reina Kurakake, Satoshi Uchida, Takashi Ishizone
Summary: Anionic polymerizations of 4-chlorostyrene, 4-bromostyrene, and 4-iodostyrene were successfully carried out at low temperatures using sec-butyllithium or oligo(alpha-methylstyryl)lithium as initiators. The choice of initiators and conditions allowed for control of the molecular weight distribution and molecular weights of the resulting polymers. The addition of cesium phenoxide as an additive led to the production of polymers with narrow molecular weight distributions and predictable molecular weights.
Article
Engineering, Environmental
Elnaz Zeinali, Yoshi W. Marien, Sean R. George, Michael F. Cunningham, Dagmar R. D'hooge, Paul H. M. Van Steenberge
Summary: One challenge in reversible deactivation radical polymerization in miniemulsion is finding the optimal particle size that allows for high reaction rates and control over chain length, branching, and functionality. In this study, a multi-dimensional Smith-Ewart model is combined with a method of moments model to investigate the NMP of n-butyl acrylate in miniemulsion. The model accounts for reaction and phase transfer and reveals seven kinetic regimes across a wide range of particle sizes. This work demonstrates the potential of advanced population balance models in bridging experiment and simulation for improved material design.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Physical
Shan Wang, Luca Scandurra, Rene Huebner, Ulla Gro Nielsen, Changzhu Wu
Summary: Chemoenzymatic cascades are important tools for advanced synthesis in chemistry. In this study, a simple method combining particle catalysts and enzymes in water and Pickering emulsions was successfully presented, enabling chemoenzymatic cascades. The particle catalysts acted as asymmetric catalysts for the first-step reaction and as an emulsifier to form stable Pickering emulsions. The second-step reaction of enantioselective acylation was achieved by adding Candida antarctica lipase B into the emulsions. This method has potential for generalizing to other cascade syntheses with different chemo- and biocatalysts in the future.
Review
Chemistry, Multidisciplinary
Fuqiang Chang, Carolien M. Vis, Wirawan Ciptonugroho, Pieter C. A. Bruijnincx
Summary: Pickering emulsions, stabilized by solid emulsifiers, are important in food, pharmaceutical and biomedical industries, and are increasingly used as advanced catalytic systems for green chemical transformations. Research focuses on the design of solid stabilizing particles, the range of catalytic reactions and conditions, as well as advances in reactor engineering.
Article
Nanoscience & Nanotechnology
Thomas W. Cowell, Andrew Dobria, Hee-Sun Han
Summary: This study demonstrates that double emulsion (DE) drops can address the instability issue of single emulsion (SE) drops and prevent content mixing. A simple DE drop maker is also developed, allowing for the production of single-core DEs at various flow rates and better control over shell thickness. DE drops show excellent stability during thermal cycling and maintain the monodispersity throughout the workflow. DE drops have advantages for multistep reactions due to their resistance to content mixing.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Polymer Science
Raita Goseki, Ayaka Oguri, Yuki Kurishiba, Takashi Ishizone
Summary: The selective anionic polymerization of 2,5-divinylthiophene and 2-isopropenyl-S-vinylthiophene was successfully conducted under low temperature conditions using oligo(alpha-methylstyryllithium) and excess tBuOK as initiators, resulting in polymers with predictable molecular weight and narrow molecular weight distribution. The binary initiator system effectively prevented side reactions, showing potential for controlled polymer synthesis.
Article
Polymer Science
Huishan Huang, Wenyi Luo, Linlin Zhu, Ying Wang, Zhen Zhang
Summary: An organocatalytic sequential ring-opening polymerization approach was developed for the synthesis of polysulfonamide-based copolymers, allowing for precise control of molar masses and dispersities. The method involves the use of alcohols and methoxylpolyethylene glycols as initiators, followed by tosyl isocyanate-mediated transformations and ROP reactions. Well-defined triblock and star-shaped copolymers can be successfully prepared from diol and triol initiators.
Article
Chemistry, Multidisciplinary
Yue Liao, Xia Wang, Hongdou Shen, Ziyang Tai, Qigang Wang
Summary: Cellular metabolism uses compartmentalized multienzyme efficient catalysis to realize substance metabolism, energy conversion and immune defenses. This study presents a convenient method of self-anchoring multienzymes within cell-like hydrogels using enzyme-initiated radical polymerization, resulting in higher activity, stability and recyclability compared to free enzymes.
SCIENCE CHINA-CHEMISTRY
(2022)
Correction
Chemistry, Multidisciplinary
Wenxin Wei, Francesca Mazzotta, Ingo Lieberwirth, Katharina Landfester, Calum T. J. Ferguson, Kai A. I. Zhang
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Nanoscience & Nanotechnology
Julian Heuer, Thomas Kuckhoff, Rong Li, Katharina Landfester, Calum T. J. Ferguson
Summary: The production of photocatalytic self-assembled amphiphilic polymers enables selective control over reactions based on the substrate's physical properties. By polymerizing benzothiadiazole-based photocatalysts into hydrophilic or hydrophobic compartments, we achieved stark differences in reactivity for polar substrates but similar performance for hydrophobic substrates. Additionally, the use of secondary swelling solvents led to a significant increase in conversion for a radical carbon-carbon coupling reaction.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Cyrine Ayed, Jie Yin, Katharina Landfester, Kai A. I. Zhang
Summary: Using photocatalytic oxidation to convert basic chemicals into high value compounds in environmentally benign reaction media is a current focus in catalytic research. The challenge of gaining controllability over product formation selectivity was addressed by designing covalent triazine frameworks as recyclable photocatalysts. Controlled selectivity was achieved by activating or deactivating specific photogenerated oxygen species. This study demonstrates a promising approach for achieving switchable product formation selectivity for challenging oxidation reactions in pure water.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Biochemistry & Molecular Biology
Shoupeng Cao, Tsvetomir Ivanov, Marina de Souza Melchiors, Katharina Landfester, Lucas Caire da Silva
Summary: The article discusses the importance of polymersome-based biomimetic nanoreactors (PBNs) in nanomedicine and cell mimicry. It highlights the state of the art in functional polymersomes as biomimetic nanoreactors with membrane-controlled transport.
Article
Engineering, Environmental
Stefan Peil, Hubert Gojzewski, Frederik R. Wurm
Summary: Bio-based and biodegradable cellulose acetals, with their reversible modification of cellulose, provide a versatile and sustainable alternative to non-degradable polyolefin plastics. These cellulose acetals are characterized by solubility in common organic solvents, adjustable physical properties, and the ability to undergo full degradation in compost and enzymatic processes. With the increasing urgency of climate change and plastic pollution, these cellulose derivatives offer a promising solution for a more sustainable future.
CHEMICAL ENGINEERING JOURNAL
(2023)
Correction
Chemistry, Multidisciplinary
Wenxin Wei, Francesca Mazzotta, Ingo Lieberwirth, Katharina Landfester, Calum T. J. Ferguson, Kai A. I. Zhang
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Rong Li, Julian Heuer, Thomas Kuckhoff, Katharina Landfester, Calum T. J. Ferguson
Summary: Pseudo-homogeneous polymeric photocatalysts are efficient and tunable materials with easily accessible catalytic centers. Creating highly efficient photocatalytic materials that can be separated and recovered quickly is a critical challenge. This study presents pH-responsive photocatalytic nanoparticles that are active and well-dispersed under acidic conditions but aggregate upon pH elevation, allowing easy recovery. These responsive photocatalytic polymers can be used in various transformations and can accelerate the reaction rate of anionic substrates.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Polymer Science
Timo Rheinberger, Mareike Deuker, Frederik R. Wurm
Summary: In this study, the degradation rate of polyphosphoesters (PPEs) with different side-chain structures under different pH conditions was investigated. The degradation mechanism was found to be influenced by the type and size of the side-chain and pH. By modifying the structure of the polyphosphonates or introducing additional breaking points, the half-life of the polymer could be tuned. This study highlights the versatile stability and controllability of water-soluble PPEs, making them promising for various applications, such as tissue regrowth.
EUROPEAN POLYMER JOURNAL
(2023)
Article
Pharmacology & Pharmacy
Loris Busch, Anna Maria Hanuschik, Yuri Avlasevich, Katrin Darm, Elisa F. F. Hochheiser, Christian Kohler, Evgeny A. A. Idelevich, Karsten Becker, Peter Rotsch, Katharina Landfester, Maxim E. E. Darvin, Martina C. C. Meinke, Cornelia M. M. Keck, Axel Kramer, Paula Zwicker
Summary: Hair follicles are important drug delivery targets for skin antisepsis due to their high concentration of skin microbiome. Nanoparticles can penetrate deeply into hair follicles and can be triggered to release drugs through various mechanisms. The study introduces UV-responsive nanocapsules containing hydroxyethyl starch, which demonstrated efficient release of ethanol and a strong reduction in microbial load on porcine ear skin. The findings suggest the potential for advanced skin antisepsis using UVA-responsive nanocapsules.
Article
Nanoscience & Nanotechnology
Tsvetomir Ivanov, Shoupeng Cao, Nitin Bohra, Marina de Souza Melchiors, Lucas Caire da Silva, Katharina Landfester
Summary: We have developed a fully polymeric microreactor with a coacervate-in-vesicle architecture that exhibits an adaptive response to pH. The microreactor allows for the dynamic modulation of internal subcompartments, resulting in the sequestration and localization of enzymes and reaction products driven by environmental cues.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Ran Wang, Yingjie Yu, Meiyu Gai, Ana Mateos-Maroto, Svenja Morsbach, Xiang Xia, Maomao He, Jiangli Fan, Xiaojun Peng, Katharina Landfester, Shuai Jiang, Wen Sun
Summary: Enzymatic reactions can effectively inhibit tumor growth by consuming tumor nutrients and producing cytotoxic species. Liposomal nanoreactors that perform enzymatic cascade reactions have been developed, increasing the overall efficiency of the reaction. This biomimetic approach provides a promising direction for developing catalytic nanomedicines in antitumor therapy.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Biochemistry & Molecular Biology
Jenny Schunke, Volker Mailaender, Katharina Landfester, Michael Fichter
Summary: Finding a long-term cure for tumor patients remains challenging. Immunotherapies show promise by activating the immune system against tumors and modulating the tumor microenvironment. However, current methods often fail to sufficiently activate the immune system and have limitations such as drug degradation and non-specific uptake. Encapsulating immunomodulatory molecules into nanocarriers offers a solution by protecting cargo and targeting uptake by antigen-presenting cells. This approach allows for versatile immune system stimulation and improved anti-tumor responses with reduced toxicity.
INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
(2023)
Article
Polymer Science
Maria Brio Perez, Mark A. Hempenius, Sissi de Beer, Frederik R. Wurm
Summary: Polymer brushes are widely used for versatile surface modifications but most of them are nonbiodegradable. In this study, the researchers presented a synthetic strategy for grafting degradable polymer brushes via organocatalytic surface-initiated ring-opening polymerization. The polymer brushes produced were able to hydrolyze with controlled patterns and be regrown on the same substrate after degradation. The research showed that the polyester brush coatings exhibited different levels of hydrolytic stability and degradation mechanism, making them a potential alternative to nondegradable polymer brushes.
Article
Chemistry, Multidisciplinary
Diego A. Resendiz-Lara, Suna Azhdari, Hubert Gojzewski, Andre H. Groeschel, Frederik R. Wurm
Summary: In this work, water-soluble and degradable bottlebrush polymers were synthesized via ROMP using polyphosphoesters (PPEs) as the base material. PPE-macromonomers were first synthesized via organocatalytic anionic ring-opening polymerization and then used in ROMP to produce well-defined bottlebrush polymers. The resulting polymers showed good solubility in water and were degradable, making them promising for various biomedical applications.
Article
Chemistry, Multidisciplinary
Tsvetomir Ivanov, Shoupeng Cao, Thao P. Doan-Nguyen, Heloisa Bremm Madalosso, Lucas Caire da Silva, Katharina Landfester
Summary: There is an increasing interest in multi-compartment systems that mimic the structure and function of biological cells. Droplet-based microfluidics (DBM) has emerged as a powerful technique for creating cell-like systems with multi-compartment architectures and biomimetic functionality. DBM has proven to be a reliable method for generating populations of cell-mimics with a compartment-in-compartment structure, some of which have adaptable properties that resemble the dynamic properties of natural cells. This review highlights the progress made in the construction of hierarchical cell-mimics using DBM methods.
