Jie Liu, Pengcheng Miao, Xuefei Leng, Yidi Li, Wei Wang, Yang Li
Polyhydroxyurethanes (PHUs) are considered a sustainable and safer alternative to traditional toxic isocyanate-based polyurethanes (PUs). There are two important characteristics of PHUs, which are their mechanical and self-healing properties. However, these two features are contradictory properties difficult to optimize simultaneously. In this work, a strong and rapid self-healing bio-based PHU network was prepared based on carbonated daidzein (DZ-BCC) and amines. The self-healing properties are tailored by using aminopropyl-terminated polydimethylsiloxane (H2N-PDMS-NH2) as a soft segment, increasing the chain mobility. The high crosslinking density of networks and the benzopyran ring structure in daidzein give the resulting PHUs a strength of up to 28.3 MPa. Despite their excellent mechanical properties, these materials show rapid self-healing capability, chemical recyclability, and remarkable reprocessing efficiency. Notably, 94% of the original tensile strength can be recovered after self-healing for 30 min at 150 °C. In addition, the prepared materials have the potential to be used as adhesives in wood and glass bonding, achieving lap shear strengths of up to 6.4 MPa and 3.4 MPa, respectively. Moreover, bonded glasses with PHUs exhibit excellent high-temperature resistance, maintaining stability up to 150 °C. This study presents bio-based PHUs derived from daidzein with good mechanical and dynamic performance simultaneously, and broadens their applications in high temperature-resistant adhesives.
{"title":"High strength and rapid self-healing daidzein-based polyhydroxyurethanes for high temperature-resistant adhesives","authors":"Jie Liu, Pengcheng Miao, Xuefei Leng, Yidi Li, Wei Wang, Yang Li","doi":"10.1039/d4py01396d","DOIUrl":"https://doi.org/10.1039/d4py01396d","url":null,"abstract":"Polyhydroxyurethanes (PHUs) are considered a sustainable and safer alternative to traditional toxic isocyanate-based polyurethanes (PUs). There are two important characteristics of PHUs, which are their mechanical and self-healing properties. However, these two features are contradictory properties difficult to optimize simultaneously. In this work, a strong and rapid self-healing bio-based PHU network was prepared based on carbonated daidzein (DZ-BCC) and amines. The self-healing properties are tailored by using aminopropyl-terminated polydimethylsiloxane (H<small><sub>2</sub></small>N-PDMS-NH<small><sub>2</sub></small>) as a soft segment, increasing the chain mobility. The high crosslinking density of networks and the benzopyran ring structure in daidzein give the resulting PHUs a strength of up to 28.3 MPa. Despite their excellent mechanical properties, these materials show rapid self-healing capability, chemical recyclability, and remarkable reprocessing efficiency. Notably, 94% of the original tensile strength can be recovered after self-healing for 30 min at 150 °C. In addition, the prepared materials have the potential to be used as adhesives in wood and glass bonding, achieving lap shear strengths of up to 6.4 MPa and 3.4 MPa, respectively. Moreover, bonded glasses with PHUs exhibit excellent high-temperature resistance, maintaining stability up to 150 °C. This study presents bio-based PHUs derived from daidzein with good mechanical and dynamic performance simultaneously, and broadens their applications in high temperature-resistant adhesives.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"91 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975278","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}
Chirality and chiral materials demonstrate ever-growing importance. Non-spherical chiral polymer particles have witnessed an increasing interest in recent years, owing to their fascinating physicochemical properties as well as wide-ranging applications. There is a trend to develop new technologies based on existing technical principles, and the design and synthesis of polymer particles will play a vital role in the further development of chiral applications. In this review, the state-of-the-art research progress of non-spherical chiral polymer particles in the past ten years is summarized. First, the preparation strategies of non-spherical chiral polymer particles are detailed from multiple perspectives, including emulsion polymerization, precipitation polymerization and suspension polymerization, as well as special processes such as spray drying, microfluidics, photolithography, and self-assembly. In addition, this review adds to the development from spherical to non-spherical particle morphology. Then, the applications of the resulting beguiling particles in chiral separation, asymmetric catalysis, drug release, and circularly polarized luminescence are illustrated. Finally, the challenges and opportunities that exist in the field are pointed out. This review aims to offer important guidance and stimulate more research attention to this rapidly developing field.
{"title":"Evolution and Recent Progress of Non-spherical Chiral Micro- and Nanoparticles: Preparation, Design, and Advanced Applications","authors":"Pengpeng Li, Jiahao Zhang, Xinlong Liu, Xin Zhang, Jinsong Ma, Guohua Sun, Lianlong Hou, Saleem Raza","doi":"10.1039/d4py01057d","DOIUrl":"https://doi.org/10.1039/d4py01057d","url":null,"abstract":"Chirality and chiral materials demonstrate ever-growing importance. Non-spherical chiral polymer particles have witnessed an increasing interest in recent years, owing to their fascinating physicochemical properties as well as wide-ranging applications. There is a trend to develop new technologies based on existing technical principles, and the design and synthesis of polymer particles will play a vital role in the further development of chiral applications. In this review, the state-of-the-art research progress of non-spherical chiral polymer particles in the past ten years is summarized. First, the preparation strategies of non-spherical chiral polymer particles are detailed from multiple perspectives, including emulsion polymerization, precipitation polymerization and suspension polymerization, as well as special processes such as spray drying, microfluidics, photolithography, and self-assembly. In addition, this review adds to the development from spherical to non-spherical particle morphology. Then, the applications of the resulting beguiling particles in chiral separation, asymmetric catalysis, drug release, and circularly polarized luminescence are illustrated. Finally, the challenges and opportunities that exist in the field are pointed out. This review aims to offer important guidance and stimulate more research attention to this rapidly developing field.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"21 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975279","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 Yang, Xiaoting Ji, Xinlong Sha, Jincheng Ding, Lin Cheng, Guangfeng Li
With the increasing global attention on energy and environmental issues, there is a growing push towards the eco-friendly transformation of adhesive materials. However, designing and developing eco-friendly adhesive materials with ultra-strong adhesion has always been a significant challenge in the field of adhesion. Herein, we present an eco-friendly adhesive (CBA) derived from bio-based thioctic acid (TA) that combines synergistic covalent and dynamic covalent polymeric segments, demonstrating strong adhesive strength and closed-loop recyclability. Specifically, leveraging the synergistic effects of dynamic covalent and covalent chain segments within the polymer network, the adhesive CBA exhibits ultra-strong adhesive strength (16.1 MPa), exceptional antifreeze performance (11.6 MPa at −196 °C), high reusability with 12.1 MPa retained after ten cycles, and resistance to common organic solvents. Importantly, the main chains of disulfide bonds formed through solid-phase thermal-induced ring-opening polymerization of TA, combined with robust reversible amide bonds to crosslink into a network, enables closed-loop recyclability. This approach of using bio-based materials with synergistic dynamic covalent and covalent bonds effectively balances adhesive strength with environmental sustainability, offering an excellent solution for designing and developing new adhesive materials.
{"title":"An Eco-Friendly Adhesive with Ultra-Strong Adhesive Performance","authors":"Zhenyu Yang, Xiaoting Ji, Xinlong Sha, Jincheng Ding, Lin Cheng, Guangfeng Li","doi":"10.1039/d4py01398k","DOIUrl":"https://doi.org/10.1039/d4py01398k","url":null,"abstract":"With the increasing global attention on energy and environmental issues, there is a growing push towards the eco-friendly transformation of adhesive materials. However, designing and developing eco-friendly adhesive materials with ultra-strong adhesion has always been a significant challenge in the field of adhesion. Herein, we present an eco-friendly adhesive (CBA) derived from bio-based thioctic acid (TA) that combines synergistic covalent and dynamic covalent polymeric segments, demonstrating strong adhesive strength and closed-loop recyclability. Specifically, leveraging the synergistic effects of dynamic covalent and covalent chain segments within the polymer network, the adhesive CBA exhibits ultra-strong adhesive strength (16.1 MPa), exceptional antifreeze performance (11.6 MPa at −196 °C), high reusability with 12.1 MPa retained after ten cycles, and resistance to common organic solvents. Importantly, the main chains of disulfide bonds formed through solid-phase thermal-induced ring-opening polymerization of TA, combined with robust reversible amide bonds to crosslink into a network, enables closed-loop recyclability. This approach of using bio-based materials with synergistic dynamic covalent and covalent bonds effectively balances adhesive strength with environmental sustainability, offering an excellent solution for designing and developing new adhesive materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"36 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975281","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}
Christoph Schmidleitner, Matthias Udo Kriehuber, Roman Korotkov, Sandra Schlögl, Elisabeth Rossegger
Frontal polymerization is a curing method that is known for its high conversion, short reaction times and low energy consumption. However, the resulting materials are typical thermosets, allowing no reprocessing, reshaping nor recycling. Herein, a new approach is pursued, which combines the energy efficiency of frontal polymerization with the unique post-processability of covalent adaptable networks. Thus, selected thiol-acrylate resins, bearing a sufficiently high number of ester linkages and free hydroxyl groups, were investigated, using phosphate esters as transesterification catalysts. The amount of phosphate ester and thiol was varied and its influence on material properties and frontal polymerization kinetics were analyzed. The reaction kinetics were studied with FTIR and photo-DSC measurements, showing a trend towards lower reactivity and higher conversions with an increased thiol content. The obtained networks exhibited tunable bond exchange rates by varying either the amount of thiol or of the catalyst. DMA measurements reveal a higher network homogeneity with increasing thiol content. Moreover, reprocessing, recycling as well as reshaping of the material was successfully demonstrated. Concludingly, these findings could significantly lower energy consumption and increase circularity in future thermoset production.
{"title":"Frontal Polymerization of Thiol-Acrylate Covalent Adaptable Networks","authors":"Christoph Schmidleitner, Matthias Udo Kriehuber, Roman Korotkov, Sandra Schlögl, Elisabeth Rossegger","doi":"10.1039/d4py01106f","DOIUrl":"https://doi.org/10.1039/d4py01106f","url":null,"abstract":"Frontal polymerization is a curing method that is known for its high conversion, short reaction times and low energy consumption. However, the resulting materials are typical thermosets, allowing no reprocessing, reshaping nor recycling. Herein, a new approach is pursued, which combines the energy efficiency of frontal polymerization with the unique post-processability of covalent adaptable networks. Thus, selected thiol-acrylate resins, bearing a sufficiently high number of ester linkages and free hydroxyl groups, were investigated, using phosphate esters as transesterification catalysts. The amount of phosphate ester and thiol was varied and its influence on material properties and frontal polymerization kinetics were analyzed. The reaction kinetics were studied with FTIR and photo-DSC measurements, showing a trend towards lower reactivity and higher conversions with an increased thiol content. The obtained networks exhibited tunable bond exchange rates by varying either the amount of thiol or of the catalyst. DMA measurements reveal a higher network homogeneity with increasing thiol content. Moreover, reprocessing, recycling as well as reshaping of the material was successfully demonstrated. Concludingly, these findings could significantly lower energy consumption and increase circularity in future thermoset production.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"41 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975280","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}
Johan Liotier, Leila Issoufou Alfari, Benoit Mahler, Thomas A Niehaus, C. Dujardin, Simon Guelen, Vincent Schanen, Véronique Dufaud, Jean Raynaud, Vincent Monteil
Upcycling of polyethersulfone (PES), a high-performance polymer based on an aromatic-rich aryl-ether-based backbone, can advantageously yield both starting Bisphenol S (BPS) comonomer and valuable OLED derivatives, providing complete atom valorization strategy for PES waste. Deprotonated selected amines proved particularly efficient at depolymerizing PES at moderate temperatures (~ 120 °C). The recycled monomer yields validate the back-to-monomer chemical recycling method for industrial compliance. The OLED derivatives afforded by the same simple process can easily be isolated and promote an innovative upcycling strategy using polymer-to-valuable chemicals, a very relevant approach to help mitigate the ever-growing plastic waste accumulation.
{"title":"Polyethersulfones upcycling to luminescent materials by aminolysis","authors":"Johan Liotier, Leila Issoufou Alfari, Benoit Mahler, Thomas A Niehaus, C. Dujardin, Simon Guelen, Vincent Schanen, Véronique Dufaud, Jean Raynaud, Vincent Monteil","doi":"10.1039/d4py01250j","DOIUrl":"https://doi.org/10.1039/d4py01250j","url":null,"abstract":"Upcycling of polyethersulfone (PES), a high-performance polymer based on an aromatic-rich aryl-ether-based backbone, can advantageously yield both starting Bisphenol S (BPS) comonomer and valuable OLED derivatives, providing complete atom valorization strategy for PES waste. Deprotonated selected amines proved particularly efficient at depolymerizing PES at moderate temperatures (~ 120 °C). The recycled monomer yields validate the back-to-monomer chemical recycling method for industrial compliance. The OLED derivatives afforded by the same simple process can easily be isolated and promote an innovative upcycling strategy using polymer-to-valuable chemicals, a very relevant approach to help mitigate the ever-growing plastic waste accumulation.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"24 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142939511","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}
Zhongxuan Chen, Xuanhua Guo, Guangqiang Xu, Huibin Zou, Qinggang Wang
The chiral (BisSalen)Al complexes have been confirmed as powerful catalysts for perfect asymmetric kinetic resolution polymerization (AKRP) of racemic phenethylglycolide (Pegl). However, the control mechanism in the AKRP mediated by (BisSalen)Al complexes is not sufficient. Herein, the polymerization of diastereomeric (rac and meso-) Pegl mixtures mediated by (BisSalen)Al complex SS-1 was investigated for the first time. The origin of AKRP in Pegl was determined to be enantiomorphic site control (ESC) through NMR-HPLC analysis, kinetic study and stereosequence analysis.
{"title":"The control mechanism of (BisSalen)Al mediated asymmetric kinetic resolution polymerization of phenethylglycolide","authors":"Zhongxuan Chen, Xuanhua Guo, Guangqiang Xu, Huibin Zou, Qinggang Wang","doi":"10.1039/d4py01439a","DOIUrl":"https://doi.org/10.1039/d4py01439a","url":null,"abstract":"The chiral (BisSalen)Al complexes have been confirmed as powerful catalysts for perfect asymmetric kinetic resolution polymerization (AKRP) of racemic phenethylglycolide (Pegl). However, the control mechanism in the AKRP mediated by (BisSalen)Al complexes is not sufficient. Herein, the polymerization of diastereomeric (<em>rac</em> and <em>meso</em>-) Pegl mixtures mediated by (BisSalen)Al complex <em>SS</em>-1 was investigated for the first time. The origin of AKRP in Pegl was determined to be enantiomorphic site control (ESC) through NMR-HPLC analysis, kinetic study and stereosequence analysis.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"13 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142939514","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}
Philipp Martschin, Timo Prölß, Andreas Hutzler, Simon Thiele, Jochen Kerres
The membrane is the heart of an electrochemical cell. Nowadays, PFSA-based materials, e.g., Nafion®, are state-of-the-art in large-scale energy applications. However, PFSAs are relatively expensive and give rise to concerns regarding toxic intermediates in the production process. Moreover, their recyclability and their biodegradability are questionable. Thus, there is a strong need to develop alternative materials with comparable or better properties. This study presents a new class of phosphonated hydrocarbon polymers based on commercially available polysulfone Udel (PSU) synthesized by a lithiation reaction. The modified PSUs were subsequently phosphonated by a Michaelis-Arbuzov reaction. All synthesized polymers/ionomers were further characterized by NMR, DSC, TGA, GPC, TEM, and titration. Moreover, the first blend membranes could be produced out of the new class of PSU derivatives. In summary, four different polymers were synthesized, of which three were successfully phosphonated. Starting from the phosphonated species, three different acid-acid blend membranes were manufactured with sufficient ionic conductivity. These novel phosphonic acid group-containing materials are promising candidates for membranes or ionomers in electrochemical applications, like (HT)-PEMFCs, (HT)-PEMWEs, or redox flow batteries.
{"title":"Preparation of a new class of phosphonated hydrocarbon polymers based on polysulfone","authors":"Philipp Martschin, Timo Prölß, Andreas Hutzler, Simon Thiele, Jochen Kerres","doi":"10.1039/d4py01289e","DOIUrl":"https://doi.org/10.1039/d4py01289e","url":null,"abstract":"The membrane is the heart of an electrochemical cell. Nowadays, PFSA-based materials, e.g., Nafion®, are state-of-the-art in large-scale energy applications. However, PFSAs are relatively expensive and give rise to concerns regarding toxic intermediates in the production process. Moreover, their recyclability and their biodegradability are questionable. Thus, there is a strong need to develop alternative materials with comparable or better properties. This study presents a new class of phosphonated hydrocarbon polymers based on commercially available polysulfone Udel (PSU) synthesized by a lithiation reaction. The modified PSUs were subsequently phosphonated by a Michaelis-Arbuzov reaction. All synthesized polymers/ionomers were further characterized by NMR, DSC, TGA, GPC, TEM, and titration. Moreover, the first blend membranes could be produced out of the new class of PSU derivatives. In summary, four different polymers were synthesized, of which three were successfully phosphonated. Starting from the phosphonated species, three different acid-acid blend membranes were manufactured with sufficient ionic conductivity. These novel phosphonic acid group-containing materials are promising candidates for membranes or ionomers in electrochemical applications, like (HT)-PEMFCs, (HT)-PEMWEs, or redox flow batteries.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"44 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937166","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}
Ibrahim Raji, Torin Wilcox, Christopher Scott Hartley, Dominik Konkolewicz
Light- and carbodiimide-responsive hydrogels were synthesized. An “AND” gate was developed using ortho-nitrobenzyl (ONB) protected carboxylic acids in the polymer backbone. Crosslinking was only realized in the presence of both UV stimulus to photocleave the ONB group and carbodiimide fuels to induce anhydride bonds. In the presence of water, the anhydride bonds eventually hydrolyze to carboxylic acids and the system returns to the solution state. The mechanical properties of the out-of-equilibrium hydrogels were investigated using oscillatory rheology to examine the effects of deprotection efficiency, carbodiimide concentration and chain architecture on the hydrogels’ moduli and decrosslinking time. Higher moduli and longer decrosslinking times were found with increased carbodiimide concentration and deprotection efficiency. These discoveries unveil new possibilities for photoresponsive chemically fueled soft materials.
{"title":"Photoresponsive Polymers for Carbodiimide-Fueled Transient Hydrogels","authors":"Ibrahim Raji, Torin Wilcox, Christopher Scott Hartley, Dominik Konkolewicz","doi":"10.1039/d4py01244e","DOIUrl":"https://doi.org/10.1039/d4py01244e","url":null,"abstract":"Light- and carbodiimide-responsive hydrogels were synthesized. An “AND” gate was developed using ortho-nitrobenzyl (ONB) protected carboxylic acids in the polymer backbone. Crosslinking was only realized in the presence of both UV stimulus to photocleave the ONB group and carbodiimide fuels to induce anhydride bonds. In the presence of water, the anhydride bonds eventually hydrolyze to carboxylic acids and the system returns to the solution state. The mechanical properties of the out-of-equilibrium hydrogels were investigated using oscillatory rheology to examine the effects of deprotection efficiency, carbodiimide concentration and chain architecture on the hydrogels’ moduli and decrosslinking time. Higher moduli and longer decrosslinking times were found with increased carbodiimide concentration and deprotection efficiency. These discoveries unveil new possibilities for photoresponsive chemically fueled soft materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"19 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142939510","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}
Solvent is often indispensable for polymerization reactions, especially to circumvent the negative effects of high viscosity. Cationic ring-opening polymerization (CROP) of 2-oxazolines has been studied for decades for the bio-related characteristics and applications of the products. The commonly used solvent, acetonitrile (AN), raises sustainability concerns for its volatility and toxicity. We report here that bio-sourced, high-boiling-point, high-polarity, and nontoxic (γ-alkyl) γ-butyrolactones are valid green solvents for the CROP of 2-ethyl-2-oxazoline. Polymerization efficiency and control are found the same as in AN. Livingness of the CROP is confirmed by block copolymerization with 2-phenyl-2-oxazoline. A series of organo-initiators, including phosphorus-based acids and carboxylic acids, are employed to gain insights into the structure-activity relationship. Particularly, it is the first time to disclose the initiating activity of 2,6-dihydroxybenzoic acid. This work provides a solution for enhancing the environmental friendliness of synthesis of biomimetic poly(2-oxazoline).
{"title":"Cationic Ring-Opening Polymerization of 2-Oxazolines in γ-Butyrolactones using Various Initiators","authors":"Tingwei Chen, Chenke Zhao, Tao Lai, Junpeng Zhao","doi":"10.1039/d4py01422g","DOIUrl":"https://doi.org/10.1039/d4py01422g","url":null,"abstract":"Solvent is often indispensable for polymerization reactions, especially to circumvent the negative effects of high viscosity. Cationic ring-opening polymerization (CROP) of 2-oxazolines has been studied for decades for the bio-related characteristics and applications of the products. The commonly used solvent, acetonitrile (AN), raises sustainability concerns for its volatility and toxicity. We report here that bio-sourced, high-boiling-point, high-polarity, and nontoxic (γ-alkyl) γ-butyrolactones are valid green solvents for the CROP of 2-ethyl-2-oxazoline. Polymerization efficiency and control are found the same as in AN. Livingness of the CROP is confirmed by block copolymerization with 2-phenyl-2-oxazoline. A series of organo-initiators, including phosphorus-based acids and carboxylic acids, are employed to gain insights into the structure-activity relationship. Particularly, it is the first time to disclose the initiating activity of 2,6-dihydroxybenzoic acid. This work provides a solution for enhancing the environmental friendliness of synthesis of biomimetic poly(2-oxazoline).","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"12 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936130","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}
Hydrogels can be used in a wide range of applications from personal care products to drug delivery vehicles. Particularly for drug delivery, it is desirable to control the release of the loaded cargo and as well as the hydrogel degradation time. Self-immolative hydrogels have been recently investigated to enable the stimulus-mediated breakdown of the hydrogel, which can also modulate to some extent the release of loaded drugs. However, when the drug was loaded into the hydrogel using non-covalent interactions, the background release rate of the drug in the absence of the stimulus was relatively rapid. Thus, we report here a new hydrogel system based on an acetal end-capped self-immolative polyglyoxylamide backbone with photo-responsive linkers as pendent groups to enable the covalent conjugation of amine-functionalized drugs. Using phenylalanine methyl ester as a model drug, we showed that hydrogels were successfully prepared with 96% equilibrium water content and a compressive modulus of 5.5 kPa. Light irradiation stimulated the rapid and traceless release of the model drug, while no detectable release was observed without irradiation. Furthermore, the PGAm backbone depolymerized selectively at mildly acidic pH. This system therefore provides a new hydrogel platform enabling a high level of control over both hydrogel breakdown and drug release.
{"title":"Polyglyoxylamide hydrogels for the traceless stimulus-mediated release of covalently-immobilized drugs","authors":"Jue Gong, Burak Tavsanli, Elizabeth R. Gillies","doi":"10.1039/d4py01214c","DOIUrl":"https://doi.org/10.1039/d4py01214c","url":null,"abstract":"Hydrogels can be used in a wide range of applications from personal care products to drug delivery vehicles. Particularly for drug delivery, it is desirable to control the release of the loaded cargo and as well as the hydrogel degradation time. Self-immolative hydrogels have been recently investigated to enable the stimulus-mediated breakdown of the hydrogel, which can also modulate to some extent the release of loaded drugs. However, when the drug was loaded into the hydrogel using non-covalent interactions, the background release rate of the drug in the absence of the stimulus was relatively rapid. Thus, we report here a new hydrogel system based on an acetal end-capped self-immolative polyglyoxylamide backbone with photo-responsive linkers as pendent groups to enable the covalent conjugation of amine-functionalized drugs. Using phenylalanine methyl ester as a model drug, we showed that hydrogels were successfully prepared with 96% equilibrium water content and a compressive modulus of 5.5 kPa. Light irradiation stimulated the rapid and traceless release of the model drug, while no detectable release was observed without irradiation. Furthermore, the PGAm backbone depolymerized selectively at mildly acidic pH. This system therefore provides a new hydrogel platform enabling a high level of control over both hydrogel breakdown and drug release.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"15 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142935402","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：