Maëva Peloille, Henri Cramail, Frédérique Ham-Pichavant, Marie Reulier, Cécile Joseph, Stéphane Grelier
An alkali lignin was subjected to successive processes enabling the stabilization of oil-in-water (O/W) emulsions. Firstly, by merely using a water/acetone mixture and evaporating acetone, more than 90% of this lignin could be dispersed in pure water, with no chemical modification involved. The obtained lignin dispersion was then subjected to an ozonation reaction, without requiring any additional steps, resulting in an increase of the carboxylic acid content (+193%), through effective cleavage of phenolic structures (-93%), and a decrease in the lignin molar masses, as evidenced by 31P quantitative NMR, 2D HSQC NMR, FT-IR spectroscopy and size-exclusion chromatography. These features allowed this alkali lignin to be easily re-dispersed in water. Aqueous dispersions of lignin before and after ozonation were characterized by an acidic pH and a bimodal nano-objects composition. These nano-objects exhibited a great affinity for interfaces, especially the ozonated lignin with an ability to reduce the surface tension of water down to 48 mN/m and the interfacial tension of a water/sunflower oil system down to 8 mN/m. Both lignins were consequently involved in the preparation of O/W emulsions and were able to stabilize micro-sized oil droplets, through a Pickering mechanism, preventing oil release under both accelerated and real-time conditions (30 days). These results demonstrated that stable emulsions could be obtained from simply processed lignins for potential applications in cosmetic formulations or for the entrapment of hydrophobic compounds in the agrochemical or pharmaceutical industries.
{"title":"Alkali Lignin Stabilization of Oil-in-Water Emulsions via Simple Dispersion and Ozonation Processes","authors":"Maëva Peloille, Henri Cramail, Frédérique Ham-Pichavant, Marie Reulier, Cécile Joseph, Stéphane Grelier","doi":"10.1039/d5py00319a","DOIUrl":"https://doi.org/10.1039/d5py00319a","url":null,"abstract":"An alkali lignin was subjected to successive processes enabling the stabilization of oil-in-water (O/W) emulsions. Firstly, by merely using a water/acetone mixture and evaporating acetone, more than 90% of this lignin could be dispersed in pure water, with no chemical modification involved. The obtained lignin dispersion was then subjected to an ozonation reaction, without requiring any additional steps, resulting in an increase of the carboxylic acid content (+193%), through effective cleavage of phenolic structures (-93%), and a decrease in the lignin molar masses, as evidenced by 31P quantitative NMR, 2D HSQC NMR, FT-IR spectroscopy and size-exclusion chromatography. These features allowed this alkali lignin to be easily re-dispersed in water. Aqueous dispersions of lignin before and after ozonation were characterized by an acidic pH and a bimodal nano-objects composition. These nano-objects exhibited a great affinity for interfaces, especially the ozonated lignin with an ability to reduce the surface tension of water down to 48 mN/m and the interfacial tension of a water/sunflower oil system down to 8 mN/m. Both lignins were consequently involved in the preparation of O/W emulsions and were able to stabilize micro-sized oil droplets, through a Pickering mechanism, preventing oil release under both accelerated and real-time conditions (30 days). These results demonstrated that stable emulsions could be obtained from simply processed lignins for potential applications in cosmetic formulations or for the entrapment of hydrophobic compounds in the agrochemical or pharmaceutical industries.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"41 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857303","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}
Mohamad A. Abou-Shamat, Alan Reader, Eleanor Hilton, Niamh Haslett, Michael T Cook, Jesus Calvo-Castro, Jacqueline Leslie Stair, Najet Mahmoudi, Abhishek Rajbanshi, Marcelo Alves da Silva
Conventional thermoreversible gels exhibit a sol-gel transition upon modulation of temperature. These systems are typically comprised of block copolymers in which one block exhibits a lower critical solution temperature (LCST), triggering a solvophilic to relatively solvophobic switch to that moiety when heated. The systems, which include poly(ethylene oxide)(PEO)-b-poly(propylene oxide)(PPO)-b-PEO (“Poloxamers”) and poly(N-isopropylacrylamide) (PNIPAM)-based block copolymers, thus exhibit a single step in their rheological profile upon heating, switching from a predominantly dissipative response to an elastic one. It has been found that a mixed tertiary system of PNIPAM-PEO-PNIPAM and Poloxamer 407 displays an unconventional sol-gel-gel transition. The rheological behaviours of this system have been studied to demonstrate the rheological profiles of the sol, “Gel I” and “Gel II” phases, as well as the reversibility of the gelation. A mechanism is proposed for this process, learning from dynamic light scattering and small-angle neutron-scattering experiments in dilute and concentrated regimes, respectively.
{"title":"Two-Stepping: Sol-gel-gel transitions in mixed thermoresponsive polymer systems","authors":"Mohamad A. Abou-Shamat, Alan Reader, Eleanor Hilton, Niamh Haslett, Michael T Cook, Jesus Calvo-Castro, Jacqueline Leslie Stair, Najet Mahmoudi, Abhishek Rajbanshi, Marcelo Alves da Silva","doi":"10.1039/d4py00771a","DOIUrl":"https://doi.org/10.1039/d4py00771a","url":null,"abstract":"Conventional thermoreversible gels exhibit a sol-gel transition upon modulation of temperature. These systems are typically comprised of block copolymers in which one block exhibits a lower critical solution temperature (LCST), triggering a solvophilic to relatively solvophobic switch to that moiety when heated. The systems, which include poly(ethylene oxide)(PEO)-b-poly(propylene oxide)(PPO)-b-PEO (“Poloxamers”) and poly(N-isopropylacrylamide) (PNIPAM)-based block copolymers, thus exhibit a single step in their rheological profile upon heating, switching from a predominantly dissipative response to an elastic one. It has been found that a mixed tertiary system of PNIPAM-PEO-PNIPAM and Poloxamer 407 displays an unconventional sol-gel-gel transition. The rheological behaviours of this system have been studied to demonstrate the rheological profiles of the sol, “Gel I” and “Gel II” phases, as well as the reversibility of the gelation. A mechanism is proposed for this process, learning from dynamic light scattering and small-angle neutron-scattering experiments in dilute and concentrated regimes, respectively.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"65 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143851028","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}
Boron, aluminum, gallium, indium, and thallium are group 13 elements that can induce various electronic properties and unique functions when incorporated into main-chain conjugation through polymers. As vacant p-orbitals in these elements interact with Lewis bases, stimuli responsiveness can be induced. Additionally, the chemical and thermal stability can be enhanced by connecting with extra Lewis bases as supporting ligands. Moreover, superior optoelectronic properties, such as light absorption, emission, and carrier mobility, are often observed from group 13 element-containing π-conjugated systems. The introduction of boron into conjugated systems has been widely applied not only for improving material properties but also for providing new functionalities for conventional polymers. In contrast, there are limited examples of polymers possessing the heavier group 13 elements in their repeating units. According to recent studies, it has been shown that the chemical, physical, and material properties of π-conjugated compounds can be unexpectedly modulated by these heavier group 13 elements. In this review, we mainly explain the synthesis and fundamental photophysical properties of conjugated polymers consisting of the heavier group 13 elements in their main-chains.
{"title":"π-Conjugated polymers consisting of heavier group 13 elements","authors":"Shunichiro Ito, Kazuo Tanaka","doi":"10.1039/d5py00116a","DOIUrl":"https://doi.org/10.1039/d5py00116a","url":null,"abstract":"Boron, aluminum, gallium, indium, and thallium are group 13 elements that can induce various electronic properties and unique functions when incorporated into main-chain conjugation through polymers. As vacant p-orbitals in these elements interact with Lewis bases, stimuli responsiveness can be induced. Additionally, the chemical and thermal stability can be enhanced by connecting with extra Lewis bases as supporting ligands. Moreover, superior optoelectronic properties, such as light absorption, emission, and carrier mobility, are often observed from group 13 element-containing π-conjugated systems. The introduction of boron into conjugated systems has been widely applied not only for improving material properties but also for providing new functionalities for conventional polymers. In contrast, there are limited examples of polymers possessing the heavier group 13 elements in their repeating units. According to recent studies, it has been shown that the chemical, physical, and material properties of π-conjugated compounds can be unexpectedly modulated by these heavier group 13 elements. In this review, we mainly explain the synthesis and fundamental photophysical properties of conjugated polymers consisting of the heavier group 13 elements in their main-chains.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"6 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841917","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}
Solid polymer electrolytes (SPEs), especially those based on poly(ethylene oxide) (PEO), have garnered significant attention in the field of all-solid-state lithium batteries due to their high processability and low cost, advantages that are typically hard to achieve with their inorganic counterparts. However, the poor ionic conductivities have retarded their further applications in all-solid-state lithium batteries. Herein, we report a series of corona-shaped two-dimensional polyaramid (2DPA) derivatives that improve the overall performance of PEO-based SPE, including ionic conductivity, ion transference number, and electrochemical stability. We demonstrate that the unique corona topology, consisting of a rigid two-dimensional polyaramid core and flexible poly(ethylene glycol) (PEG) chains grafted at its periphery, effectively inhibits the crystallization of the PEO matrix through chain entanglement, thus enhancing the ionic conductivity. Furthermore, the 2D polyaramide core provides enriched Lewis acidic binding sites for counter anions, suppressing the anion motion and resulting in selective lithium ion transport. Therefore, a blend of 30% 2DPA-PEGs and PEO exhibits enhanced room temperature ionic conductivity up to 4.39 × 10-5 S cm-1 (an order of magnitude higher than the original SPE), an elevated lithium-ion transference number of 0.78, and a high oxidation voltage of 4.7 V (vs Li/Li+). Meanwhile, the assembled all-solid-state batteries exhibit improved cycle performance and higher stability. Such a heterostructural polymer design strategy showcases the promising potential of novel 2D polymer derivatives in ion transport optimization in SPEs.
{"title":"Corona-shaped two-dimensional polyaramid derivatives for poly(ethylene oxide)-based all-solid-state lithium batteries","authors":"Feifan Zheng, Liping Jiang, Xiaoli Gong, Zhengqiao Yin, Fei Wang, Yuwen Zeng","doi":"10.1039/d5py00046g","DOIUrl":"https://doi.org/10.1039/d5py00046g","url":null,"abstract":"Solid polymer electrolytes (SPEs), especially those based on poly(ethylene oxide) (PEO), have garnered significant attention in the field of all-solid-state lithium batteries due to their high processability and low cost, advantages that are typically hard to achieve with their inorganic counterparts. However, the poor ionic conductivities have retarded their further applications in all-solid-state lithium batteries. Herein, we report a series of corona-shaped two-dimensional polyaramid (2DPA) derivatives that improve the overall performance of PEO-based SPE, including ionic conductivity, ion transference number, and electrochemical stability. We demonstrate that the unique corona topology, consisting of a rigid two-dimensional polyaramid core and flexible poly(ethylene glycol) (PEG) chains grafted at its periphery, effectively inhibits the crystallization of the PEO matrix through chain entanglement, thus enhancing the ionic conductivity. Furthermore, the 2D polyaramide core provides enriched Lewis acidic binding sites for counter anions, suppressing the anion motion and resulting in selective lithium ion transport. Therefore, a blend of 30% 2DPA-PEGs and PEO exhibits enhanced room temperature ionic conductivity up to 4.39 × 10-5 S cm-1 (an order of magnitude higher than the original SPE), an elevated lithium-ion transference number of 0.78, and a high oxidation voltage of 4.7 V (vs Li/Li+). Meanwhile, the assembled all-solid-state batteries exhibit improved cycle performance and higher stability. Such a heterostructural polymer design strategy showcases the promising potential of novel 2D polymer derivatives in ion transport optimization in SPEs.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"42 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841916","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}
We report the synthesis of dual-stimuli degradable poly(vinyl ether)s with cleavable thioacetal and carbonate bonds evenly distributed in the main chains using cationic degenerative chain-transfer (DT) copolymerization of vinyl ethers with macrocyclic thioacetal carbonates (CTAC). The 22- and 26-membered cyclic thioacetal carbonates (22-CTAC and 26-CTAC) were initially synthesized by a cationic thiol-ene reaction between divinyl ether with a carbonate bond and dithiol with or without a carbonate bond under dilution conditions. These compounds were subjected to cationic copolymerization with vinyl ethers using the HCl-adduct of isobutyl vinyl ether as an initiator and ZnCl2 as a catalyst and were consumed much faster than the vinyl ethers by ring-opening reactions despite the large ring to introduce thioacetal and carbonate bonds in the main chains of the products. The in-chain thioacetal bonds subsequently served as dormant bonds for the cationic DT polymerization of vinyl ethers and enabled the synthesis of poly(vinyl ether)s with controlled total and segmental molecular weights between the thioacetal and carbonate bonds. The orthogonal degradations were successful when acid and base catalysts were used for the thioacetal and carbonate bonds, respectively; this resulted in low-molecular-weight products with controlled molecular weights. Furthermore, multiblock copolymers were synthesized by the one-time addition of the second monomer (B) to the cationic DT polymerization of the first monomer (A) and 22-CTAC and were selectively degraded into ABA and BAB triblock copolymers with acid and base catalysts, respectively.
我们报告了利用乙烯基醚与大环硫代乙醛碳酸盐（CTAC）的阳离子变性链转移（DT）共聚合合成主链中均匀分布有可裂解硫代乙醛键和碳酸键的双刺激可降解聚（乙烯基醚）的情况。22 元和 26 元环状硫代乙醛碳酸酯（22-CTAC 和 26-CTAC）最初是由具有碳酸酯键的二乙烯基醚和具有或不具有碳酸酯键的二硫醇在稀释条件下通过阳离子硫醇-烯反应合成的。这些化合物以异丁基乙烯基醚的 HCl 加合物为引发剂，ZnCl2 为催化剂，与乙烯基醚进行阳离子共聚，尽管在产物的主链中引入了大环的硫代乙醛键和碳酸键，但在开环反应中消耗的速度比乙烯基醚快得多。链内硫代乙醛键随后成为乙烯基醚阳离子 DT 聚合反应的休眠键，并能合成硫代乙醛键和碳酸键之间总分子量和分段分子量可控的聚（乙烯基醚）。当硫代乙缩醛键和碳酸键分别使用酸催化剂和碱催化剂时，正交降解成功；从而得到了分子量可控的低分子量产品。此外，在第一单体（A）和 22-CTAC 的阳离子 DT 聚合中一次性加入第二单体（B），合成了多嵌段共聚物，并在酸催化剂和碱催化剂的作用下分别选择性地降解为 ABA 和 BAB 三嵌段共聚物。
{"title":"Cyclic thioacetal carbonates for dual-stimuli degradable poly(vinyl ether)s with cleavable thioacetal and carbonate bonds evenly distributed in the main chains by cationic degenerative chain-transfer copolymerization","authors":"Mineto Uchiyama, Kaoru Matoba, Masami Kamigaito","doi":"10.1039/d5py00054h","DOIUrl":"https://doi.org/10.1039/d5py00054h","url":null,"abstract":"We report the synthesis of dual-stimuli degradable poly(vinyl ether)s with cleavable thioacetal and carbonate bonds evenly distributed in the main chains using cationic degenerative chain-transfer (DT) copolymerization of vinyl ethers with macrocyclic thioacetal carbonates (CTAC). The 22- and 26-membered cyclic thioacetal carbonates (22-CTAC and 26-CTAC) were initially synthesized by a cationic thiol-ene reaction between divinyl ether with a carbonate bond and dithiol with or without a carbonate bond under dilution conditions. These compounds were subjected to cationic copolymerization with vinyl ethers using the HCl-adduct of isobutyl vinyl ether as an initiator and ZnCl2 as a catalyst and were consumed much faster than the vinyl ethers by ring-opening reactions despite the large ring to introduce thioacetal and carbonate bonds in the main chains of the products. The in-chain thioacetal bonds subsequently served as dormant bonds for the cationic DT polymerization of vinyl ethers and enabled the synthesis of poly(vinyl ether)s with controlled total and segmental molecular weights between the thioacetal and carbonate bonds. The orthogonal degradations were successful when acid and base catalysts were used for the thioacetal and carbonate bonds, respectively; this resulted in low-molecular-weight products with controlled molecular weights. Furthermore, multiblock copolymers were synthesized by the one-time addition of the second monomer (B) to the cationic DT polymerization of the first monomer (A) and 22-CTAC and were selectively degraded into ABA and BAB triblock copolymers with acid and base catalysts, respectively.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143841683","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}
Yukikazu Takeoka, Junjia Zhang, Yian Wang, Yinglu Liu, Jeremy Odent
Ionogels are conductive soft matter with ionic liquids as conductive media, exhibiting significant potential as multifunctional materials. Over the past two decades, ionogels have been developed for applications in sensors, actuators, supercapacitors, lithium-ion batteries, adhesives, antifouling coatings, nanotriboelectric generators, thermoelectric devices, etc. To achieve recyclability that is advantageous for various applications, dissociative supramolecular interactions—e.g. electrostatic interactions, hydrogen bonds and - stacking—have garnered significant attention in the crosslinking design of ionogels. High-strength ionogels utilizing dissociative supramolecular interactions as a crosslinking mechanism have been synthesized. However, due to the inherently low bond energy and high dynamics of dissociative supramolecular crosslinking, issues such as low thermal stability and insufficient solvent resistance arise, limiting the broader applications of ionogels. To address these challenges, the network structure can be precisely designed, and reversible covalent bonds can be introduced as a crosslinking mechanism to mitigate the trade-off between material durability and dynamic behavior. Several studies provide insights into realizing this approach. For instance, hydrogels, which are also classified as soft materials, can enhance both mechanical strength and deformability by incorporating topological network structures based on organic covalent bonds. Similarly, covalent adaptable networks (CANs), a class of dynamic materials, achieve high thermal stability, solvent resistance, and recyclability by utilizing densely reversible covalent bonds. Hence, we chiefly focus on the critical roles of designing the organic polymer network structures and utilizing reversible covalent bonding to enhance key physical properties of ionogels, including mechanical strength, electrical conductivity, and processability. Last but not least, we discuss the current challenges associated with the design and application of ionogels, while also anticipating potential strategies that leverage the superior designs from materials such as hydrogels and CANs to develop innovative ionogels.
{"title":"Covalent Design of Ionogels: Bridging with Hydrogels and Covalent Adaptable Networks","authors":"Yukikazu Takeoka, Junjia Zhang, Yian Wang, Yinglu Liu, Jeremy Odent","doi":"10.1039/d5py00217f","DOIUrl":"https://doi.org/10.1039/d5py00217f","url":null,"abstract":"Ionogels are conductive soft matter with ionic liquids as conductive media, exhibiting significant potential as multifunctional materials. Over the past two decades, ionogels have been developed for applications in sensors, actuators, supercapacitors, lithium-ion batteries, adhesives, antifouling coatings, nanotriboelectric generators, thermoelectric devices, etc. To achieve recyclability that is advantageous for various applications, dissociative supramolecular interactions—e.g. electrostatic interactions, hydrogen bonds and - stacking—have garnered significant attention in the crosslinking design of ionogels. High-strength ionogels utilizing dissociative supramolecular interactions as a crosslinking mechanism have been synthesized. However, due to the inherently low bond energy and high dynamics of dissociative supramolecular crosslinking, issues such as low thermal stability and insufficient solvent resistance arise, limiting the broader applications of ionogels. To address these challenges, the network structure can be precisely designed, and reversible covalent bonds can be introduced as a crosslinking mechanism to mitigate the trade-off between material durability and dynamic behavior. Several studies provide insights into realizing this approach. For instance, hydrogels, which are also classified as soft materials, can enhance both mechanical strength and deformability by incorporating topological network structures based on organic covalent bonds. Similarly, covalent adaptable networks (CANs), a class of dynamic materials, achieve high thermal stability, solvent resistance, and recyclability by utilizing densely reversible covalent bonds. Hence, we chiefly focus on the critical roles of designing the organic polymer network structures and utilizing reversible covalent bonding to enhance key physical properties of ionogels, including mechanical strength, electrical conductivity, and processability. Last but not least, we discuss the current challenges associated with the design and application of ionogels, while also anticipating potential strategies that leverage the superior designs from materials such as hydrogels and CANs to develop innovative ionogels.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837331","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}
Magnetic polymers show great potential in biomedical, electronic devices and magnetic responsive materials. The structure and property relationship are very important in design of organic magnetic polymers. In this work, core-shell magnetic bottlebrush polymers (PS-b-QPDMA[FeCl4]) with polystyrene as core block and magnetic poly(ionic liquid)s (QPDMA[FeCl4]) as shell block is prepared by ring-opening metathesis polymerization and post-modification. The self-assembly of core-shell PS-b-QPDMA[FeCl4] is studied in core and shell selecting solvent, respectively. It self-assembles into single macromolecular core-shell nanorod in shell selecting solvent while it self-assembles into core-shell nanoparticles in core selecting solvent. The magnetic property of PS-b-QPDMA[FeCl4] are studied in different morphologies via magnetic field and temperature dependent magnetization, respectively. Compared with the paramagnetic linear block copolymer, the bottlebrush polymer without self-assembly shows ferromagnetic interaction at low temperature with the bifurcation temperature (Tb) of the zero field cooling and field cooling curves of 3.2 K. The nanoparticle self-assemblies show the similar Tb at 3.8 K, while the single macromolecular nanorod self-assemblies show a high Tb of 9.8 K, demonstrating the much stronger ferromagnetic interaction for the nanorod self-assemblies. The increasing of Tb is probably due to the confinement of glassy PS core in the nanorod self-assemblies, which decreases the Fe(III)-Fe(III) distance to enhanced the ferromagnetic interaction of FeCl4- units.
{"title":"Self-assembly of core-shell magnetic bottlebrush poly(ionic liquids): morphologies vs magnetic property","authors":"Chunman Li, Mingzhe Zhao, Zenian Gou, Tengda Zhao, Huimin Han, Kongying Zhu, Xiaoyan Yuan, Li-Xia Ren","doi":"10.1039/d5py00277j","DOIUrl":"https://doi.org/10.1039/d5py00277j","url":null,"abstract":"Magnetic polymers show great potential in biomedical, electronic devices and magnetic responsive materials. The structure and property relationship are very important in design of organic magnetic polymers. In this work, core-shell magnetic bottlebrush polymers (PS-b-QPDMA[FeCl4]) with polystyrene as core block and magnetic poly(ionic liquid)s (QPDMA[FeCl4]) as shell block is prepared by ring-opening metathesis polymerization and post-modification. The self-assembly of core-shell PS-b-QPDMA[FeCl4] is studied in core and shell selecting solvent, respectively. It self-assembles into single macromolecular core-shell nanorod in shell selecting solvent while it self-assembles into core-shell nanoparticles in core selecting solvent. The magnetic property of PS-b-QPDMA[FeCl4] are studied in different morphologies via magnetic field and temperature dependent magnetization, respectively. Compared with the paramagnetic linear block copolymer, the bottlebrush polymer without self-assembly shows ferromagnetic interaction at low temperature with the bifurcation temperature (Tb) of the zero field cooling and field cooling curves of 3.2 K. The nanoparticle self-assemblies show the similar Tb at 3.8 K, while the single macromolecular nanorod self-assemblies show a high Tb of 9.8 K, demonstrating the much stronger ferromagnetic interaction for the nanorod self-assemblies. The increasing of Tb is probably due to the confinement of glassy PS core in the nanorod self-assemblies, which decreases the Fe(III)-Fe(III) distance to enhanced the ferromagnetic interaction of FeCl4- units.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"60 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143827194","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}
Polyimide (PI) exhibits good thermal performance and high stability due to its highly rigid main chain and excellent mechanical properties, making it an ideal electrochromic material. However, its applicability is limited by poor solvent solubility, which results from the rigid backbone, and film yellowing, caused by charge-transfer complexes (CTC). Herein, a novel phenothiazine-based diamine (THZ-DA) was synthesized, where a universal joint-like structure was constructed during its formation. The introduction of the non-coplanar universal joint reduced intermolecular interactions and suppressed CTC formation, improving the solubility and enabling high transmittance of THZ-PIs in the neutral state. Moreover, the lone pair of electrons on the nitrogen atom of THZ allowed for the formation of a cationic radical (THZ+·) under electrochemical oxidation, which was stabilized by the resonance effect, enabling reversible color switching between colorless and orange–red state. Among the three systems, THZ-b, composed of THZ-DA and 3,3’,4,4’-biphenyl tetracarboxylic dianhydride, showed the best thermal stability, with a Td5% above 406 °C and Tg of 347 °C. It also exhibited good electrochemical cycling stability, with redox potentials of 1.09 and 0.88 V, as well as excellent electrochromic performance, achieving an electrochromic efficiency of 222 cm2 C–1. These results show the application potential of THZ-PI in smart windows and adaptive camouflage.
{"title":"Soluble polyimide-based colorless-to-orange–red switching electrochromic film by incorporating universal joint-like structure","authors":"Xiaoqing Sun, Chongwen Yu, Xingyao Liu, Taolve Wang, Xigao Jian, Yujie Song, Jian Xu","doi":"10.1039/d5py00149h","DOIUrl":"https://doi.org/10.1039/d5py00149h","url":null,"abstract":"Polyimide (PI) exhibits good thermal performance and high stability due to its highly rigid main chain and excellent mechanical properties, making it an ideal electrochromic material. However, its applicability is limited by poor solvent solubility, which results from the rigid backbone, and film yellowing, caused by charge-transfer complexes (CTC). Herein, a novel phenothiazine-based diamine (THZ-DA) was synthesized, where a universal joint-like structure was constructed during its formation. The introduction of the non-coplanar universal joint reduced intermolecular interactions and suppressed CTC formation, improving the solubility and enabling high transmittance of THZ-PIs in the neutral state. Moreover, the lone pair of electrons on the nitrogen atom of THZ allowed for the formation of a cationic radical (THZ+·) under electrochemical oxidation, which was stabilized by the resonance effect, enabling reversible color switching between colorless and orange–red state. Among the three systems, THZ-b, composed of THZ-DA and 3,3’,4,4’-biphenyl tetracarboxylic dianhydride, showed the best thermal stability, with a Td5% above 406 °C and Tg of 347 °C. It also exhibited good electrochemical cycling stability, with redox potentials of 1.09 and 0.88 V, as well as excellent electrochromic performance, achieving an electrochromic efficiency of 222 cm2 C–1. These results show the application potential of THZ-PI in smart windows and adaptive camouflage.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"14 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143819379","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}
Mengyu Wang, Sumin Lee, Hyunhee Lee, Byeong-Su Kim
Ring-opening polymerization (ROP) of dioxolanones (DOXs) provides access to functional polyesters with properties that are challenging to achieve via traditional polymerization of lactones. However, typical catalysts often induce epimerization in DOXs, limiting the synthesis of isotactic, crystalline polymers. This study reports a binary organocatalytic system that enables controlled ROP of chiral 2,2,5-trimethyl-1,3-dioxolan-4-ones under mild conditions, effectively minimizing epimerization by activating both the monomer and initiator via hydrogen bonding. This strategy facilitates the synthesis of highly isotactic poly(lactic acid) (PLA) with a stereoregularity parameter of 0.92. Moreover, blending enantiomeric PLA chains form a crystalline stereocomplex with a high melting temperature of 195.1 °C. These findings highlight a sustainable and scalable approach for synthesizing stereoregular polyesters, paving the way for advanced material applications.
{"title":"Highly Isotactic Polylactide by Binary Organocatalyzed Polymerization of 1,3-Dioxolan-4-Ones","authors":"Mengyu Wang, Sumin Lee, Hyunhee Lee, Byeong-Su Kim","doi":"10.1039/d5py00205b","DOIUrl":"https://doi.org/10.1039/d5py00205b","url":null,"abstract":"Ring-opening polymerization (ROP) of dioxolanones (DOXs) provides access to functional polyesters with properties that are challenging to achieve via traditional polymerization of lactones. However, typical catalysts often induce epimerization in DOXs, limiting the synthesis of isotactic, crystalline polymers. This study reports a binary organocatalytic system that enables controlled ROP of chiral 2,2,5-trimethyl-1,3-dioxolan-4-ones under mild conditions, effectively minimizing epimerization by activating both the monomer and initiator via hydrogen bonding. This strategy facilitates the synthesis of highly isotactic poly(lactic acid) (PLA) with a stereoregularity parameter of 0.92. Moreover, blending enantiomeric PLA chains form a crystalline stereocomplex with a high melting temperature of 195.1 °C. These findings highlight a sustainable and scalable approach for synthesizing stereoregular polyesters, paving the way for advanced material applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"2 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813747","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}
The design of stimuli-responsive polymers with both tunable lower critical solution temperature (LCST) and unconventional cluster luminescence represents a significant challenge in materials science. In this study, thermosensitive linear poly(ether amide)s with cluster fluorescence and LCST tunability were prepared via phosphazene base (t-BuP2)-catalyzed oxa-Michael addition polymerization of N,N'-methylene-bis(acrylamide) (MBA) with diols containing different numbers of carbon atoms. The fluorescence properties and LCST tunable behavior of the linear poly(ether amide)s were investigated by ultraviolet-visible (UV-Vis) and fluorescence spectroscopy. The fluorescence results demonstrate that the resulting linear poly(ether amide)s exhibit aggregation-induced emission (AIE) and excitation-dependent emission properties due to cluster fluorescence, which is formed by the aggregation of nonconjugated chromophores, such as amide, ether, and hydroxyl groups. It is noteworthy that the fluorescent polymers display temperature-responsive and LCST tunable characteristics, which can be attributed to the interactions between the hydrophobic carbon chains and the hydrophilic ether, amide, and hydroxyl groups present in the linear polyether amides. Moreover, linear poly(ether amide)s display distinctive LCST-dependent fluorescence characteristics, exhibiting a pronounced shift in fluorescence intensity with temperature that closely aligns with their LCST values. The intrinsic fluorescence and temperature response of linear poly(ether amide)s were exploited to demonstrate their potential as a versatile tool for security tamper-evident labels, physiological cell imaging, and traceable and controlled release of doxorubicin. This study provides an LCST-tunable strategy for linear nonconjugated fluorescent polymers, which enriches and develops the synthesis, mechanism and application studies of stimuli-responsive nonconjugated fluorescent polymers.
{"title":"Design, synthesis and applications of thermosensitive linear poly(ether amide)s with unconventional cluster luminescence and tunable LCST","authors":"Zixian Liu, Yangdan Ou, Sisi Li, Wenyan Huang, Hongjun Yang, Xiaoqiang Xue, Qimin Jiang, Bibiao Jiang","doi":"10.1039/d4py01386g","DOIUrl":"https://doi.org/10.1039/d4py01386g","url":null,"abstract":"The design of stimuli-responsive polymers with both tunable lower critical solution temperature (LCST) and unconventional cluster luminescence represents a significant challenge in materials science. In this study, thermosensitive linear poly(ether amide)s with cluster fluorescence and LCST tunability were prepared via phosphazene base (t-BuP2)-catalyzed oxa-Michael addition polymerization of N,N'-methylene-bis(acrylamide) (MBA) with diols containing different numbers of carbon atoms. The fluorescence properties and LCST tunable behavior of the linear poly(ether amide)s were investigated by ultraviolet-visible (UV-Vis) and fluorescence spectroscopy. The fluorescence results demonstrate that the resulting linear poly(ether amide)s exhibit aggregation-induced emission (AIE) and excitation-dependent emission properties due to cluster fluorescence, which is formed by the aggregation of nonconjugated chromophores, such as amide, ether, and hydroxyl groups. It is noteworthy that the fluorescent polymers display temperature-responsive and LCST tunable characteristics, which can be attributed to the interactions between the hydrophobic carbon chains and the hydrophilic ether, amide, and hydroxyl groups present in the linear polyether amides. Moreover, linear poly(ether amide)s display distinctive LCST-dependent fluorescence characteristics, exhibiting a pronounced shift in fluorescence intensity with temperature that closely aligns with their LCST values. The intrinsic fluorescence and temperature response of linear poly(ether amide)s were exploited to demonstrate their potential as a versatile tool for security tamper-evident labels, physiological cell imaging, and traceable and controlled release of doxorubicin. This study provides an LCST-tunable strategy for linear nonconjugated fluorescent polymers, which enriches and develops the synthesis, mechanism and application studies of stimuli-responsive nonconjugated fluorescent polymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"28 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813746","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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