With the goal of achieving environmentally friendly polymer synthesis strategies, enzyme-promoted polymerisation has gradually attracted people's attention. The development of hydrogel-based microfluidics provides a new carrier system for enzymatic catalysis. Here, we report a new technique for enzyme-promoted free radical polymerisation, supported on hydrogel microdots (µHDs) within a microfluidic chip. Free radical polymerisation initiated by free horseradish peroxidase (HRP) in vials confirmed the formation of poly(N-isopropyl acrylamide) (PNiPAAm), achieving high molecular weight (500,000 Da) in 5 min. For polymerisation in microfluidics, disulphide-bearing µHDs were mounted on a PDMS-on-glass chip. Utilising a disulphide-thiol exchange reaction, modified HRP was then captured “from the flow” through the chip, which was confirmed by fluorescence microscopy. Various polymerisation parameters were studied in the microfluidic chip, and the successful polymer formation was confirmed by copolymerisation with a fluorescent comonomer. The physical entanglement fixed the formed polymer on the µHDs, forming a structure similar to a semi-interpenetrating network (semi-IPN). Thus, this technique provides a new direct approach to achieving semi-IPNs within microfluidic chips, showcasing the versatility in which microfluidic systems can be utilised.
{"title":"Enzymatic Synthesis of Semi-IPNs within Hydrogel-Based Microfluidics","authors":"Chen Jiao, Dietmar Appelhans, Brigitte Voit, Nico Bruns, Jens Gaitzsch","doi":"10.1039/d4py01259c","DOIUrl":"https://doi.org/10.1039/d4py01259c","url":null,"abstract":"With the goal of achieving environmentally friendly polymer synthesis strategies, enzyme-promoted polymerisation has gradually attracted people's attention. The development of hydrogel-based microfluidics provides a new carrier system for enzymatic catalysis. Here, we report a new technique for enzyme-promoted free radical polymerisation, supported on hydrogel microdots (µHDs) within a microfluidic chip. Free radical polymerisation initiated by free horseradish peroxidase (HRP) in vials confirmed the formation of poly(N-isopropyl acrylamide) (PNiPAAm), achieving high molecular weight (500,000 Da) in 5 min. For polymerisation in microfluidics, disulphide-bearing µHDs were mounted on a PDMS-on-glass chip. Utilising a disulphide-thiol exchange reaction, modified HRP was then captured “from the flow” through the chip, which was confirmed by fluorescence microscopy. Various polymerisation parameters were studied in the microfluidic chip, and the successful polymer formation was confirmed by copolymerisation with a fluorescent comonomer. The physical entanglement fixed the formed polymer on the µHDs, forming a structure similar to a semi-interpenetrating network (semi-IPN). Thus, this technique provides a new direct approach to achieving semi-IPNs within microfluidic chips, showcasing the versatility in which microfluidic systems can be utilised.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"202 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142886681","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Taeho Lim, Seeun Hong, Soeun Kim, Soobin Kim, Kyeongsu Chung, Hyemin Park, Youngdo Jeong, Ju-Won Jeon, Jinho Chang, Sangho Cho
Redox-active polymers have garnered significant attention for their potential in organic radical batteries (ORB) due to their unique redox capabilities. However, traditional redox-active polymers often consist of non-degradable aliphatic chains, raising environmental concerns. To address this issue, we developed a polycaprolactone-based organic radical polymer, PCL-TEMPO, which leverages the biodegradable and non-toxic properties of polycaprolactone (PCL). PCL-TEMPO was synthesized by incorporating 2,2,6,6‐Tetramethylpiperidin‐1‐yl oxyl (TEMPO) as a redox-active pendant group. We further investigated its redox properties in aqueous solutions. While PCL-TEMPO exhibited redox activity, its performance as a rechargeable battery material was limited, likely due to the degradation of TEMPO during cycling. Nonetheless, cytotoxicity tests demonstrated that both PCL-TEMPO and its degradation products were non-cytotoxic, highlighting its potential as an environmentally friendly material for future applications.
{"title":"Development of redox-active polycaprolactone and its electrochemical redox behavior in aqueous media","authors":"Taeho Lim, Seeun Hong, Soeun Kim, Soobin Kim, Kyeongsu Chung, Hyemin Park, Youngdo Jeong, Ju-Won Jeon, Jinho Chang, Sangho Cho","doi":"10.1039/d4py01339e","DOIUrl":"https://doi.org/10.1039/d4py01339e","url":null,"abstract":"Redox-active polymers have garnered significant attention for their potential in organic radical batteries (ORB) due to their unique redox capabilities. However, traditional redox-active polymers often consist of non-degradable aliphatic chains, raising environmental concerns. To address this issue, we developed a polycaprolactone-based organic radical polymer, PCL-TEMPO, which leverages the biodegradable and non-toxic properties of polycaprolactone (PCL). PCL-TEMPO was synthesized by incorporating 2,2,6,6‐Tetramethylpiperidin‐1‐yl oxyl (TEMPO) as a redox-active pendant group. We further investigated its redox properties in aqueous solutions. While PCL-TEMPO exhibited redox activity, its performance as a rechargeable battery material was limited, likely due to the degradation of TEMPO during cycling. Nonetheless, cytotoxicity tests demonstrated that both PCL-TEMPO and its degradation products were non-cytotoxic, highlighting its potential as an environmentally friendly material for future applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142886682","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhenyu Wan, Nankai An, Chang Xu, Mingxin Zheng, Jinying Yuan
Polymerization-induced self-assembly (PISA) has emerged as a versatile and powerful methodology for the in situ generation of polymeric nanostructures with diverse morphologies and functionalities. Currently, dynamic covalent bonds (DCBs), known for their reversible and stimulus-responsive nature, offer a sophisticated tool for the precise modulation of polymer assemblies. The incorporation of DCBs into PISA facilitates the disaggregation, morphological transition, surface modification, controlled drug release, intra- and inter-micellar crosslinking of assemblies, thereby expanding the applications of PISA assemblies in drug delivery, targeted controlled release, molecular recognition, sensing, and modifiable micelle-crosslinked gels. The combination of PISA with DCBs offers a promising approach for designing adaptive and tunable block copolymer nano-object systems, providing new insights and opportunities in the field of polymer chemistry. This review discusses the integration of dynamic covalent bonds, including disulfide, boronate ester, imine, and [2+2] cycloaddition, within the PISA framework and provides guidelines for future research on the development of dynamically responsive and multifunctional PISA nanomaterials.
{"title":"Polymerization-induced self-assembly nanomaterials based on dynamic covalent bonds","authors":"Zhenyu Wan, Nankai An, Chang Xu, Mingxin Zheng, Jinying Yuan","doi":"10.1039/d4py01204f","DOIUrl":"https://doi.org/10.1039/d4py01204f","url":null,"abstract":"Polymerization-induced self-assembly (PISA) has emerged as a versatile and powerful methodology for the in situ generation of polymeric nanostructures with diverse morphologies and functionalities. Currently, dynamic covalent bonds (DCBs), known for their reversible and stimulus-responsive nature, offer a sophisticated tool for the precise modulation of polymer assemblies. The incorporation of DCBs into PISA facilitates the disaggregation, morphological transition, surface modification, controlled drug release, intra- and inter-micellar crosslinking of assemblies, thereby expanding the applications of PISA assemblies in drug delivery, targeted controlled release, molecular recognition, sensing, and modifiable micelle-crosslinked gels. The combination of PISA with DCBs offers a promising approach for designing adaptive and tunable block copolymer nano-object systems, providing new insights and opportunities in the field of polymer chemistry. This review discusses the integration of dynamic covalent bonds, including disulfide, boronate ester, imine, and [2+2] cycloaddition, within the PISA framework and provides guidelines for future research on the development of dynamically responsive and multifunctional PISA nanomaterials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"41 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142886680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Luis Santos Correa, Silas Leidenheimer, Michael A. R. Meier
Tricarboxylic acids are molecules of interest for the synthesis of cross-linked polymers. Herein, a recently established route to a tricarboxylic acid from high oleic sunflower oil was utilized to synthesize renewable cross-linked polymers via the Passerini three-component reaction. Ten different polymers were synthesized by variation of the diisocyanide and monoaldehyde components and subsequently characterized via infrared spectroscopy, swelling tests, thermogravimetric analysis, differential scanning calorimetry, and tensile tests. The characterization of the insoluble polymeric networks was complemented by the synthesis of model compounds to enable analysis in solution via nuclear magnetic resonance spectroscopy. Due to the fast curing of all polymers at room temperature, adhesive tests were performed to demonstrate their potential application as glues. At last, one Passerini polymer was chemically reused by transesterification with methanol and catalytic amounts of sulfuric acid to establish a proof-of-concept of the circularity of these materials. Azelaic acid dimethyl ester, an industrially relevant compound used for the synthesis of polyamides, and a difunctional α hydroxyamide were recovered in a yield of 75%. Repolymerization of the α hydroxyamide to a polyurethane was performed to demonstrate a potential second life cycle of these compounds.
{"title":"Sunflower oil-based thermosets via the Passerini three‑component reaction","authors":"Luis Santos Correa, Silas Leidenheimer, Michael A. R. Meier","doi":"10.1039/d4py01358a","DOIUrl":"https://doi.org/10.1039/d4py01358a","url":null,"abstract":"Tricarboxylic acids are molecules of interest for the synthesis of cross-linked polymers. Herein, a recently established route to a tricarboxylic acid from high oleic sunflower oil was utilized to synthesize renewable cross-linked polymers via the Passerini three-component reaction. Ten different polymers were synthesized by variation of the diisocyanide and monoaldehyde components and subsequently characterized via infrared spectroscopy, swelling tests, thermogravimetric analysis, differential scanning calorimetry, and tensile tests. The characterization of the insoluble polymeric networks was complemented by the synthesis of model compounds to enable analysis in solution via nuclear magnetic resonance spectroscopy. Due to the fast curing of all polymers at room temperature, adhesive tests were performed to demonstrate their potential application as glues. At last, one Passerini polymer was chemically reused by transesterification with methanol and catalytic amounts of sulfuric acid to establish a proof-of-concept of the circularity of these materials. Azelaic acid dimethyl ester, an industrially relevant compound used for the synthesis of polyamides, and a difunctional α hydroxyamide were recovered in a yield of 75%. Repolymerization of the α hydroxyamide to a polyurethane was performed to demonstrate a potential second life cycle of these compounds.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142886685","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Atsushi Tahara, Shogo Yashiro, Toshio Hokajo, Shinji Kudo, Yuta Yoshizaki, Tomohiro Konno, Takayuki Doi
Highly stereochemically controlled polymers were successfully synthesized from levoglucosenone (LGO), derived from cellulose. Since its discovery in the 1970s, the reactivity of LGO has been widely studied in organic chemistry, owing to its diverse functional groups that serve as linkages for polymer formation. However, most of the previous methods for synthesizing polymers from LGO lacked precise control over regio- and stereochemistry, making stereoselective polymerization from LGO a persistent challenge. Although the ketone moiety in LGO is typically reduced before polymerization, a new LGO polymer was designed, containing a C=N bond obtained by condensation with dicarboxylic dihydrazide. NMR measurements revealed that condensation occurred with high stereoselectivity to produce the E-isomer. This selectivity extended from the model compound to polymer synthesis, achieving high E / Z selectivity. The resulting polymer exhibited optical rotation (up to +89), indicating its potential as a chiral polymer. In spite of these polymers showed high tolerance toward many solvents, they were degradable in water with a simple chemical treatment. The proposed approach facilitates the development of sustainable, high-performance materials that can address both environmental and industrial needs.
{"title":"Stereoselective Polycondensation of Levoglucosenone leading to Water-Degradable Biopolymers","authors":"Atsushi Tahara, Shogo Yashiro, Toshio Hokajo, Shinji Kudo, Yuta Yoshizaki, Tomohiro Konno, Takayuki Doi","doi":"10.1039/d4py01094a","DOIUrl":"https://doi.org/10.1039/d4py01094a","url":null,"abstract":"Highly stereochemically controlled polymers were successfully synthesized from levoglucosenone (LGO), derived from cellulose. Since its discovery in the 1970s, the reactivity of LGO has been widely studied in organic chemistry, owing to its diverse functional groups that serve as linkages for polymer formation. However, most of the previous methods for synthesizing polymers from LGO lacked precise control over regio- and stereochemistry, making stereoselective polymerization from LGO a persistent challenge. Although the ketone moiety in LGO is typically reduced before polymerization, a new LGO polymer was designed, containing a C=N bond obtained by condensation with dicarboxylic dihydrazide. NMR measurements revealed that condensation occurred with high stereoselectivity to produce the <em>E</em>-isomer. This selectivity extended from the model compound to polymer synthesis, achieving high <em>E</em> / <em>Z</em> selectivity. The resulting polymer exhibited optical rotation (up to +89), indicating its potential as a chiral polymer. In spite of these polymers showed high tolerance toward many solvents, they were degradable in water with a simple chemical treatment. The proposed approach facilitates the development of sustainable, high-performance materials that can address both environmental and industrial needs.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"41 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142879780","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Developing new methods for converting inorganic sulfur into sulfur-containing polymers is crucial for advancing both sustainable development and innovative polymeric materials. In this study, we present an aziridine-based polymerization strategy to synthesize polyureas with tunable sulfur incorporation. The process begins with the reaction of aziridine with isocyanate, followed by a ring-opening reaction with an inorganic sulfur reagent. When elemental sulfur is used, oligosulfide anions form in the presence of an organobase, which then nucleophilically attack the aziridine ring, producing oligosulfide-functionalized polyureas. Alternatively, using sodium sulfide generates poly(thioether urea)s through a similar ring-opening mechanism. Model reactions confirm successful sulfur incorporation during these processes. Additionally, a cross-linked polyurea synthesized with tri-isocyanate exhibits excellent mechanical properties, with tensile stress exceeding 30 MPa, and demonstrates good reprocessability due to the dynamic nature of the oligosulfide bonds. Overall, this polymerization approach broadens the range of sulfur-containing materials and supports further advances in aziridine-based polymer chemistry.
{"title":"Aziridine-Based Organocatalytic Polymerization for Tunable Sulfur Incorporation in Polyureas","authors":"Leying Xu, Changzheng Ju, Jiazi Zheng, Qingyong Chen, Zhen Zhang","doi":"10.1039/d4py01171f","DOIUrl":"https://doi.org/10.1039/d4py01171f","url":null,"abstract":"Developing new methods for converting inorganic sulfur into sulfur-containing polymers is crucial for advancing both sustainable development and innovative polymeric materials. In this study, we present an aziridine-based polymerization strategy to synthesize polyureas with tunable sulfur incorporation. The process begins with the reaction of aziridine with isocyanate, followed by a ring-opening reaction with an inorganic sulfur reagent. When elemental sulfur is used, oligosulfide anions form in the presence of an organobase, which then nucleophilically attack the aziridine ring, producing oligosulfide-functionalized polyureas. Alternatively, using sodium sulfide generates poly(thioether urea)s through a similar ring-opening mechanism. Model reactions confirm successful sulfur incorporation during these processes. Additionally, a cross-linked polyurea synthesized with tri-isocyanate exhibits excellent mechanical properties, with tensile stress exceeding 30 MPa, and demonstrates good reprocessability due to the dynamic nature of the oligosulfide bonds. Overall, this polymerization approach broadens the range of sulfur-containing materials and supports further advances in aziridine-based polymer chemistry.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874100","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Herein, block-type and random-type vinyl-functionalized macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agents were synthesized by RAFT solution polymerization and employed to mediate aqueous photoinitiated RAFT dispersion polymerization of hydroxylpropyl methacrylate (HPMA). When using the block-type macro-RAFT agent, cross-linked block copolymer nanoparticles with various morphologies could be prepared. Control experiments demonstrate that the vinyl group in the macro-RAFT agent has little impact on the polymerization process and the morphology of block copolymer nanoparticles. Morphologies of block copolymer nanoparticles could be controlled by changing the length of the stabilizer block, the [HPMA]/[macro-RAFT] ratio, and the HPMA concentration. When using the random-type macro-RAFT agent, cross-linked block copolymer nanoparticles were still obtained. Moreover, it was found that the random distribution of vinyl group in the macro-RAFT agent facilitated the formation of higher-order morphologies. Finally, the obtained cross-linked worms and vesicles were used as seeds for seeded RAFT polymerization of tert-butyl acrylate (tBA) or glycidyl methacrylate (GlyMA), which enables the further control over the surface morphology of block copolymer nanoparticles. We expect that this study will offer new opportunities for the rational preparation of cross-linked block copolymer nanoparticles with various morphologies.
{"title":"Polymerization-induced Self-assembly mediated by Vinyl-functionalized Macromolecular Chain Transfer Agents: A Straightforward Approach for Cross-linked Block Copolymer Nanoparticles with tunable Morphologies","authors":"Honggao Huang, Liwei Luo, Li Zhang, Jianbo Tan","doi":"10.1039/d4py01048e","DOIUrl":"https://doi.org/10.1039/d4py01048e","url":null,"abstract":"Herein, block-type and random-type vinyl-functionalized macromolecular reversible addition-fragmentation chain transfer (macro-RAFT) agents were synthesized by RAFT solution polymerization and employed to mediate aqueous photoinitiated RAFT dispersion polymerization of hydroxylpropyl methacrylate (HPMA). When using the block-type macro-RAFT agent, cross-linked block copolymer nanoparticles with various morphologies could be prepared. Control experiments demonstrate that the vinyl group in the macro-RAFT agent has little impact on the polymerization process and the morphology of block copolymer nanoparticles. Morphologies of block copolymer nanoparticles could be controlled by changing the length of the stabilizer block, the [HPMA]/[macro-RAFT] ratio, and the HPMA concentration. When using the random-type macro-RAFT agent, cross-linked block copolymer nanoparticles were still obtained. Moreover, it was found that the random distribution of vinyl group in the macro-RAFT agent facilitated the formation of higher-order morphologies. Finally, the obtained cross-linked worms and vesicles were used as seeds for seeded RAFT polymerization of tert-butyl acrylate (tBA) or glycidyl methacrylate (GlyMA), which enables the further control over the surface morphology of block copolymer nanoparticles. We expect that this study will offer new opportunities for the rational preparation of cross-linked block copolymer nanoparticles with various morphologies.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"60 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874099","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A newly designed photocrosslinked hydrogel undergoes gelation under UV light irradiation and contains three types of crosslinked networks resulting from free radical polymerization, thiol-Michael addition reaction and dynamic disulfide bonds. This hybrid hydrogel exhibits an extremely fast gelling time, improved modulus and broad-spectrum antibacterial properties.
{"title":"A photocrosslinked hybrid hydrogel based on chitosan/hyaluronic acid/ZnO toward wound sealing†","authors":"Jiale Sun, Donghao Hu, Yiling Li, Jia Wei and Yanlei Yu","doi":"10.1039/D4PY01207K","DOIUrl":"10.1039/D4PY01207K","url":null,"abstract":"<p >A newly designed photocrosslinked hydrogel undergoes gelation under UV light irradiation and contains three types of crosslinked networks resulting from free radical polymerization, thiol-Michael addition reaction and dynamic disulfide bonds. This hybrid hydrogel exhibits an extremely fast gelling time, improved modulus and broad-spectrum antibacterial properties.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 3","pages":" 272-279"},"PeriodicalIF":4.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857978","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Herein, we investigated the self-assembly of amphiphilic acrylate random copolymers bearing hydrophilic poly(ethylene glycol) chains and hydrophobic dodecyl groups into micelles in water. The random copolymers formed precise yet dynamic micelles in water, dependent on degree of polymerization (DP) and composition. The copolymers shorter than a threshold DPth exclusively formed multichain micelles and the copolymers longer than the DPth self-folded into unimer micelles. The molecular weight and size of the multichain micelles were determined by the composition, and the aggregation number was controllable by the DP. Critical micelle concentration of the random copolymers was estimated to be approximately 1 × 10-3 mg/mL, and almost independent of the DP, aggregation number, monomer sequence, and backbone structures. More uniquely, owing to the flexible backbones, the acrylate random copolymer micelles induced the exchange of polymer chains even at a low temperature such as 10 °C (activation energy: Ea = ~40 kJ/mol) although corresponding methacrylate counterparts with relatively rigid backbones required at least 25 °C for polymer chain exchange.
{"title":"Precisely Controlled yet Dynamically Exchanged Micelles via the Self-Assembly of Amphiphilic Acrylate Random Copolymers in Water","authors":"Hiroyuki Kono, Makoto Ouchi, Takaya Terashima","doi":"10.1039/d4py01272k","DOIUrl":"https://doi.org/10.1039/d4py01272k","url":null,"abstract":"Herein, we investigated the self-assembly of amphiphilic acrylate random copolymers bearing hydrophilic poly(ethylene glycol) chains and hydrophobic dodecyl groups into micelles in water. The random copolymers formed precise yet dynamic micelles in water, dependent on degree of polymerization (DP) and composition. The copolymers shorter than a threshold DP<small><sub>th</sub></small> exclusively formed multichain micelles and the copolymers longer than the DP<small><sub>th</sub></small> self-folded into unimer micelles. The molecular weight and size of the multichain micelles were determined by the composition, and the aggregation number was controllable by the DP. Critical micelle concentration of the random copolymers was estimated to be approximately 1 × 10<small><sup>-3</sup></small> mg/mL, and almost independent of the DP, aggregation number, monomer sequence, and backbone structures. More uniquely, owing to the flexible backbones, the acrylate random copolymer micelles induced the exchange of polymer chains even at a low temperature such as 10 °C (activation energy: <em>E</em><small><sub>a</sub></small> = ~40 kJ/mol) although corresponding methacrylate counterparts with relatively rigid backbones required at least 25 °C for polymer chain exchange.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"4 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857977","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
J. Antonio Vazquez, Xabier Lopez de Pariza, Nathan Ballinger, Naroa Sadaba, Aileen Sun, Ayokunle Oluwafemi Olanrewaju, Haritz Sardon, Alshakim Nelson
Photo-mediated additive manufacturing from liquid resins (vat photopolymerization) is a rapidly growing field that will enable a new generation of electronic devices, sensors, and soft robotics. Radical-based polymerization remains the standard for photo-curing resins during the printing process due to its fast polymerization kinetics and the range of available photoinitiators. Comparatively, there are fewer examples of non-radical chemical reactions for vat photopolymerization, despite the potential for expanding the range of functional materials and devices. Herein, we demonstrate ionic liquid resins for vat photopolymerization that utilize photo-base generators (PBGs) to catalyze thiol-Michael additions as the network forming reaction. The ionic liquid increased the rate of curing, while also introducing ionic conductivity to the printed structures. Among the PBGs explored, 2-(2-nitrophenyl)-propyloxycarbonyl tetramethylguanidine (NPPOC-TMG) was the most effective for the vat photopolymerization process wherein 250 μm features were successfully printed. Lastly, we compared the mechanical properties of the PBG catalyzed thiol-Michael network versus the radical polymerized network. Interestingly, the thiol-Michael network had an overall improvement in ductility compared to the radical initiated resin, since step-growth methodologies afford more defined networks than chain growth. These ionic liquid resins for thiol-Michael additions expand the chemistries available for vat photopolymerization and present opportunities for fabricating devices such as sensors.
{"title":"Photobase-Catalyzed Thiol-ene Click Chemistry for Light-Based Additive Manufacturing","authors":"J. Antonio Vazquez, Xabier Lopez de Pariza, Nathan Ballinger, Naroa Sadaba, Aileen Sun, Ayokunle Oluwafemi Olanrewaju, Haritz Sardon, Alshakim Nelson","doi":"10.1039/d4py01120a","DOIUrl":"https://doi.org/10.1039/d4py01120a","url":null,"abstract":"Photo-mediated additive manufacturing from liquid resins (vat photopolymerization) is a rapidly growing field that will enable a new generation of electronic devices, sensors, and soft robotics. Radical-based polymerization remains the standard for photo-curing resins during the printing process due to its fast polymerization kinetics and the range of available photoinitiators. Comparatively, there are fewer examples of non-radical chemical reactions for vat photopolymerization, despite the potential for expanding the range of functional materials and devices. Herein, we demonstrate ionic liquid resins for vat photopolymerization that utilize photo-base generators (PBGs) to catalyze thiol-Michael additions as the network forming reaction. The ionic liquid increased the rate of curing, while also introducing ionic conductivity to the printed structures. Among the PBGs explored, 2-(2-nitrophenyl)-propyloxycarbonyl tetramethylguanidine (NPPOC-TMG) was the most effective for the vat photopolymerization process wherein 250 μm features were successfully printed. Lastly, we compared the mechanical properties of the PBG catalyzed thiol-Michael network versus the radical polymerized network. Interestingly, the thiol-Michael network had an overall improvement in ductility compared to the radical initiated resin, since step-growth methodologies afford more defined networks than chain growth. These ionic liquid resins for thiol-Michael additions expand the chemistries available for vat photopolymerization and present opportunities for fabricating devices such as sensors.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"55 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867373","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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