Johan Liotier , Leila Issoufou Alfari , Benoit Mahler , Thomas Niehaus , Christophe Dujardin , Simon Guelen , Vincent Schanen , Véronique Dufaud , Jean Raynaud , Vincent Monteil
The upcycling of polyethersulfone (), a high-performance polymer based on an aromatic-rich aryl-ether-based backbone, can advantageously yield both the starting comonomer bisphenol S () and valuable OLED derivatives, providing a complete atom valorization strategy for waste. Deprotonated selected amines have proved particularly efficient at depolymerizing 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, promoting an innovative upcycling strategy that transforms polymer into valuable chemicals, a highly relevant approach for mitigating the ever-growing plastic waste accumulation.
{"title":"Upcycling polyethersulfones to luminescent materials by aminolysis†","authors":"Johan Liotier , Leila Issoufou Alfari , Benoit Mahler , Thomas Niehaus , Christophe Dujardin , Simon Guelen , Vincent Schanen , Véronique Dufaud , Jean Raynaud , Vincent Monteil","doi":"10.1039/d4py01250j","DOIUrl":"10.1039/d4py01250j","url":null,"abstract":"<div><div>The upcycling of polyethersulfone (), a high-performance polymer based on an aromatic-rich aryl-ether-based backbone, can advantageously yield both the starting comonomer bisphenol S () and valuable OLED derivatives, providing a complete atom valorization strategy for waste. Deprotonated selected amines have proved particularly efficient at depolymerizing 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, promoting an innovative upcycling strategy that transforms polymer into valuable chemicals, a highly relevant approach for mitigating the ever-growing plastic waste accumulation.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 10","pages":"Pages 1139-1145"},"PeriodicalIF":4.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01250j?page=search","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":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Cage silsesquioxane (POSS, polyhedral oligomeric silsesquioxane) is a crucial building block in the development of organic–inorganic hybrid polymers. However, polymers incorporating POSS units in their side chains often exhibit poor film-forming properties because of the high crystallinity of POSS. In this study, polymethylene densely grafted with POSS units was synthesized. This POSS-polymethylene structure produced a homogeneous, transparent cast film, in contrast to the turbid film formed by POSS-polyacrylate. The significant difference in the film quality was attributed to the inhibition of POSS crystallization, facilitated by the dense tethering of POSS on the polymethylene backbone.
{"title":"Polymethylene with cage silsesquioxane: densely grafted structure prevents side-chain crystallization†","authors":"Yu Tomioka , Tomoki Yasui , Kensuke Naka , Hiroaki Imoto","doi":"10.1039/d4py01222d","DOIUrl":"10.1039/d4py01222d","url":null,"abstract":"<div><div>Cage silsesquioxane (POSS, polyhedral oligomeric silsesquioxane) is a crucial building block in the development of organic–inorganic hybrid polymers. However, polymers incorporating POSS units in their side chains often exhibit poor film-forming properties because of the high crystallinity of POSS. In this study, polymethylene densely grafted with POSS units was synthesized. This POSS-polymethylene structure produced a homogeneous, transparent cast film, in contrast to the turbid film formed by POSS-polyacrylate. The significant difference in the film quality was attributed to the inhibition of POSS crystallization, facilitated by the dense tethering of POSS on the polymethylene backbone.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 10","pages":"Pages 1155-1161"},"PeriodicalIF":4.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01222d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055503","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Marianela Trujillo-Lemon , Benjamin D. Fairbanks , Andrew N. Sias , Robert R. McLeod , Christopher N. Bowman
Copolymerization and conjugate addition of disulfides generally and dithiolanes particularly have been reported for various applications. Here, a new framework for preparing high refractive index polymeric materials through the photoinitiated addition of methyl ester of lipoic acid (LipOMe) or methyl 4-methyl-1,2-dithiolane-4-carboxylate (Me-AspOMe) with various alkynes is explored, and an infrared spectroscopy methodology was developed for understanding the dithiolane homopolymerization kinetics. The effects of the 1,2-dithiolane and alkyne chemical structures on reaction rates, polymer structures, and optical properties of the synthesized polymers were examined. Characterization of the photopolymerization products showed significant dependence on the specific structure of the 1,2-dithiolane and alkyne reactants. The ability of the 1,2-dithiolane/alkyne reaction to introduce a large amount of sulfide linkages resulted in differences in the polymer refractive index relative to that of the unreacted materials, reaching values up to 0.07. Furthermore, the application of these 1,2-dithiolane-alkyne systems into two-stage photopolymeric holography materials in a two-dimensional, high-refractive index structure was demonstrated.
{"title":"1,2-Dithiolane/yne photopolymerizations to generate high refractive index polymers†","authors":"Marianela Trujillo-Lemon , Benjamin D. Fairbanks , Andrew N. Sias , Robert R. McLeod , Christopher N. Bowman","doi":"10.1039/d4py01337a","DOIUrl":"10.1039/d4py01337a","url":null,"abstract":"<div><div>Copolymerization and conjugate addition of disulfides generally and dithiolanes particularly have been reported for various applications. Here, a new framework for preparing high refractive index polymeric materials through the photoinitiated addition of methyl ester of lipoic acid (LipOMe) or methyl 4-methyl-1,2-dithiolane-4-carboxylate (Me-AspOMe) with various alkynes is explored, and an infrared spectroscopy methodology was developed for understanding the dithiolane homopolymerization kinetics. The effects of the 1,2-dithiolane and alkyne chemical structures on reaction rates, polymer structures, and optical properties of the synthesized polymers were examined. Characterization of the photopolymerization products showed significant dependence on the specific structure of the 1,2-dithiolane and alkyne reactants. The ability of the 1,2-dithiolane/alkyne reaction to introduce a large amount of sulfide linkages resulted in differences in the polymer refractive index relative to that of the unreacted materials, reaching values up to 0.07. Furthermore, the application of these 1,2-dithiolane-alkyne systems into two-stage photopolymeric holography materials in a two-dimensional, high-refractive index structure was demonstrated.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 10","pages":"Pages 1176-1187"},"PeriodicalIF":4.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01337a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143077212","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Yuan Lu , Gang Ji , Shuyang Yu , Xiaoshan Ning , Xiu-Li Sun , Yanshan Gao , Xiaoyan Wang , Yong Tang
Ethylene coordination copolymerization with vinyl polar monomers, particularly short chain alkenols, offers an attractive method for controlled synthesis of important hydroxy-functionalized polyethylenes under mild conditions. However, reports on short-chain alkenol copolymerization are limited due to issues like chelating coordination and β-O elimination. Here, we report the synthesis and characterization of binuclear Ni complexes for ethylene copolymerization with various alkenol monomers such as allyl-OH, 3-buten-1-ol, 4-penten-1-ol and 9-decen-1-ol. These complexes, upon activation with Et2AlCl, achieved notable activity (as high as 592 kg (mol cat h atm)−1) in ethylene/3-buten-1-ol copolymerization, producing copolymers with 1.7 mol% comonomer incorporation and a high molecular weight (Mn = 64.2 kg mol−1). The activity and comonomer content were influenced by Et2AlCl loading, reaction temperature, and alkenol monomer length, with longer alkenols such as 9-decen-1-ol yielding higher activity, comonomer incorporation and molecular weight. Activities up to 169 kg (mol cat h atm)−1 were also achieved in ethylene/allyl-OH copolymerization with reduced molecular weight (Mn = 17.2 kg mol−1). Microstructural analysis revealed predominant in-chain and chain-end polar monomer incorporation in all cases. Notably, ethylene/allyl-OH copolymers exhibited unique olefinic end groups and microstructures assignable to Friedel–Crafts reactions, which is likely due to an alternative chain termination pathway associated with the short chain length between the O atom and the active Ni center. For comparison, ethylene/allyl-OAc copolymers showed exclusively olefinic groups, indicating a β-OAc elimination mechanism. This process resulted in lower activity and molecular weight, suggesting catalyst poisoning from rapid chain termination.
{"title":"Binuclear Ni catalyzed ethylene copolymerization with short chain alkenol monomers†","authors":"Yuan Lu , Gang Ji , Shuyang Yu , Xiaoshan Ning , Xiu-Li Sun , Yanshan Gao , Xiaoyan Wang , Yong Tang","doi":"10.1039/d4py01480d","DOIUrl":"10.1039/d4py01480d","url":null,"abstract":"<div><div>Ethylene coordination copolymerization with vinyl polar monomers, particularly short chain alkenols, offers an attractive method for controlled synthesis of important hydroxy-functionalized polyethylenes under mild conditions. However, reports on short-chain alkenol copolymerization are limited due to issues like chelating coordination and β-O elimination. Here, we report the synthesis and characterization of binuclear Ni complexes for ethylene copolymerization with various alkenol monomers such as allyl-OH, 3-buten-1-ol, 4-penten-1-ol and 9-decen-1-ol. These complexes, upon activation with Et<sub>2</sub>AlCl, achieved notable activity (as high as 592 kg (mol cat h atm)<sup>−1</sup>) in ethylene/3-buten-1-ol copolymerization, producing copolymers with 1.7 mol% comonomer incorporation and a high molecular weight (<em>M</em><sub>n</sub> = 64.2 kg mol<sup>−1</sup>). The activity and comonomer content were influenced by Et<sub>2</sub>AlCl loading, reaction temperature, and alkenol monomer length, with longer alkenols such as 9-decen-1-ol yielding higher activity, comonomer incorporation and molecular weight. Activities up to 169 kg (mol cat h atm)<sup>−1</sup> were also achieved in ethylene/allyl-OH copolymerization with reduced molecular weight (<em>M</em><sub>n</sub> = 17.2 kg mol<sup>−1</sup>). Microstructural analysis revealed predominant in-chain and chain-end polar monomer incorporation in all cases. Notably, ethylene/allyl-OH copolymers exhibited unique olefinic end groups and microstructures assignable to Friedel–Crafts reactions, which is likely due to an alternative chain termination pathway associated with the short chain length between the O atom and the active Ni center. For comparison, ethylene/allyl-OAc copolymers showed exclusively olefinic groups, indicating a β-OAc elimination mechanism. This process resulted in lower activity and molecular weight, suggesting catalyst poisoning from rapid chain termination.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 10","pages":"Pages 1146-1154"},"PeriodicalIF":4.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143071983","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}
Tanzida Zubair , Raul S. Ramos , Ashley Morales , Robert M. Pankow
Conjugated polymers (CPs) are foundational materials in established and emerging organic electronic technologies, including organic photovoltaics, lithium-ion batteries, electrochromic displays and smart-windows, and thin-film transistors. Although CPs can be prepared via sustainable syntheses relative to their inorganic counterparts, current polymerization methods often invoke the use of toxic, hazardous solvents, such as toluene, chlorobenzene, or dimethylformamide, and high-temperatures (T > 100 °C) to afford polymer products in desirable yields and molecular weights (Mn). Here, we report the solvent-free synthesis of poly(3,4-propylenedioxythiophene) (PProDOT) analogues using mechanochemical oxidative polymerization without the application of external heating. PProDOT-OC6, which is functionalized with n-hexyloxy sidechains, is synthesized in 46% yield with a Mn of 16.9 kg mol−1 in 1 h using only a milling jar and ball, FeCl3 oxidant, and NaCl as an additive. The structural fidelity of mechanochemically synthesized PProDOT-OC6 is confirmed via1H-NMR relative to PProDOT-OC6 synthesized using solvent based oxidative polymerization, in addition to the optical absorption and electrochemical properties. The optimal mechanochemical polymerization conditions are then applied to PProDOT analogues with extended, n-decyloxy (PProDOT-OC10) or oligo(ethylene glycol) sidechains (PProDOT-OEG3) to demonstrate the tolerance of these solvent-free polymerization conditions towards structurally diverse sidechains. These findings offer a new platform and approach for further developing sustainable CP polymerization methods.
{"title":"Synthesis of poly(3,4-propylenedioxythiophene) (PProDOT) analogues via mechanochemical oxidative polymerization†","authors":"Tanzida Zubair , Raul S. Ramos , Ashley Morales , Robert M. Pankow","doi":"10.1039/d4py01253d","DOIUrl":"10.1039/d4py01253d","url":null,"abstract":"<div><div>Conjugated polymers (CPs) are foundational materials in established and emerging organic electronic technologies, including organic photovoltaics, lithium-ion batteries, electrochromic displays and smart-windows, and thin-film transistors. Although CPs can be prepared <em>via</em> sustainable syntheses relative to their inorganic counterparts, current polymerization methods often invoke the use of toxic, hazardous solvents, such as toluene, chlorobenzene, or dimethylformamide, and high-temperatures (<em>T</em> > 100 °C) to afford polymer products in desirable yields and molecular weights (<em>M</em><sub>n</sub>). Here, we report the solvent-free synthesis of poly(3,4-propylenedioxythiophene) (PProDOT) analogues using mechanochemical oxidative polymerization without the application of external heating. PProDOT-OC6, which is functionalized with <em>n</em>-hexyloxy sidechains, is synthesized in 46% yield with a <em>M</em><sub>n</sub> of 16.9 kg mol<sup>−1</sup> in 1 h using only a milling jar and ball, FeCl<sub>3</sub> oxidant, and NaCl as an additive. The structural fidelity of mechanochemically synthesized PProDOT-OC6 is confirmed <em>via</em><sup>1</sup>H-NMR relative to PProDOT-OC6 synthesized using solvent based oxidative polymerization, in addition to the optical absorption and electrochemical properties. The optimal mechanochemical polymerization conditions are then applied to PProDOT analogues with extended, <em>n</em>-decyloxy (PProDOT-OC10) or oligo(ethylene glycol) sidechains (PProDOT-OEG<sub>3</sub>) to demonstrate the tolerance of these solvent-free polymerization conditions towards structurally diverse sidechains. These findings offer a new platform and approach for further developing sustainable CP polymerization methods.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 10","pages":"Pages 1188-1196"},"PeriodicalIF":4.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050490","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}
Manyu Chen , Guangze Hu , Zuping Xiong , Haoyuan Hu , Jing Zhi Sun , Haoke Zhang , Ben Zhong Tang
Room-temperature organic magnetic materials have long been a sought-after but challenging topic. Besides the reported organic-based magnets including pure organic radicals, charge-transfer salts, and coordination polymers, we report a novel and alternative approach to fabricating purely organic/polymeric magnets based on the crystal of a 4-substituted 1,6-diyne (M) and its polymer (P). Both the white M crystal and the black P powder samples exhibit room-temperature magnetism. The saturation magnetization of P is about 0.25 emu g−1 and its Curie temperature is higher than 400 K. After repeated recrystallization of M and precipitation of P to thoroughly remove the metal-catalyst residues, the room-temperature magnetism of M and P is tentatively assigned to the stable radicals in the solid samples. The results demonstrated in this work suggest an unprecedented strategy to obtain room-temperature organic magnets.
{"title":"Room-temperature magnetism in the crystal of a 1,6-heptadiyne derivative and its processable polymer†","authors":"Manyu Chen , Guangze Hu , Zuping Xiong , Haoyuan Hu , Jing Zhi Sun , Haoke Zhang , Ben Zhong Tang","doi":"10.1039/d4py01459f","DOIUrl":"10.1039/d4py01459f","url":null,"abstract":"<div><div>Room-temperature organic magnetic materials have long been a sought-after but challenging topic. Besides the reported organic-based magnets including pure organic radicals, charge-transfer salts, and coordination polymers, we report a novel and alternative approach to fabricating purely organic/polymeric magnets based on the crystal of a 4-substituted 1,6-diyne (M) and its polymer (P). Both the white M crystal and the black P powder samples exhibit room-temperature magnetism. The saturation magnetization of P is about 0.25 emu g<sup>−1</sup> and its Curie temperature is higher than 400 K. After repeated recrystallization of M and precipitation of P to thoroughly remove the metal-catalyst residues, the room-temperature magnetism of M and P is tentatively assigned to the stable radicals in the solid samples. The results demonstrated in this work suggest an unprecedented strategy to obtain room-temperature organic magnets.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 10","pages":"Pages 1120-1125"},"PeriodicalIF":4.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418042","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}
Jiali Wang , Yunpeng Luo , Weixun Duan , Daquan Wang , Lingjie Meng
A novel microenvironment-responsive drug co-delivery system leverages acylalkynyl–hydroxyl click polymerization to incorporate diverse drug molecules with hydroxyl groups. This innovative polyprodrug approach enables precise drug grafting and selective tumor microenvironment degradation, facilitating targeted combination therapy. By successfully synthesizing dual-drug polyprodrugs with demonstrated tumor cell-killing potential and minimal normal cell damage, the method provides a promising platform for personalized, synergistic therapeutic strategies.
{"title":"A click-reaction for precise combination drug delivery: a general pH-responsive degradable backboned polyprodrug strategy†","authors":"Jiali Wang , Yunpeng Luo , Weixun Duan , Daquan Wang , Lingjie Meng","doi":"10.1039/d4py01390e","DOIUrl":"10.1039/d4py01390e","url":null,"abstract":"<div><div>A novel microenvironment-responsive drug co-delivery system leverages acylalkynyl–hydroxyl click polymerization to incorporate diverse drug molecules with hydroxyl groups. This innovative polyprodrug approach enables precise drug grafting and selective tumor microenvironment degradation, facilitating targeted combination therapy. By successfully synthesizing dual-drug polyprodrugs with demonstrated tumor cell-killing potential and minimal normal cell damage, the method provides a promising platform for personalized, synergistic therapeutic strategies.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 10","pages":"Pages 1126-1130"},"PeriodicalIF":4.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435124","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}
Samuel Mckeating , Corinna Smith , Oliver Penrhyn-Lowe , Sean Flynn , Stephen Wright , Pierre Chambon , Andrew Dwyer , Steve Rannard
Transfer-dominated Branching Radical Telomerisation (TBRT) allows the free radical homopolymerisation of multi-vinyl monomers whilst avoiding gelation. When using dimethacrylates, high molecular weight branched polyesters are formed with complete reaction of all vinyl functional groups. Here, we present the first report of TBRT using diacrylates and compare their homopolymerisation with that of analogous dimethacrylates. To establish very high molecular weight polyesters, diacrylate TBRT reactions required elevated temperatures. The reasons for this are investigated, including the use of model linear telomerisations of analogous mono-vinyl methacrylate and acrylate monomers.
{"title":"Novel hyperbranched polymers from transfer-dominated branching radical telomerisation (TBRT) of diacrylate taxogens†","authors":"Samuel Mckeating , Corinna Smith , Oliver Penrhyn-Lowe , Sean Flynn , Stephen Wright , Pierre Chambon , Andrew Dwyer , Steve Rannard","doi":"10.1039/d5py00062a","DOIUrl":"10.1039/d5py00062a","url":null,"abstract":"<div><div>Transfer-dominated Branching Radical Telomerisation (TBRT) allows the free radical homopolymerisation of multi-vinyl monomers whilst avoiding gelation. When using dimethacrylates, high molecular weight branched polyesters are formed with complete reaction of all vinyl functional groups. Here, we present the first report of TBRT using diacrylates and compare their homopolymerisation with that of analogous dimethacrylates. To establish very high molecular weight polyesters, diacrylate TBRT reactions required elevated temperatures. The reasons for this are investigated, including the use of model linear telomerisations of analogous mono-vinyl methacrylate and acrylate monomers.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 10","pages":"Pages 1131-1138"},"PeriodicalIF":4.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d5py00062a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143462449","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Julien Rosselgong , Ali Dhaini , Manon Rochedy , Lourdes Mónica Bravo-Anaya , Jean-François Carpentier , Sophie M. Guillaume
Self-assembled poly(β-hydroxyalkanoate) (PHA)-based block copolymers are attractive materials for biomedical applications due to the biocompatibility and (bio)degradability of the PHA segment. Herein, we report the synthesis and formation of self-assemblies based on PHAs: namely, poly(3-hydroxybutyrate) (PHB) was prepared by ring-opening polymerization (ROP) of racemic β-butyrolactone (rac-β-BL) using a discrete yttrium-based catalyst in the presence of a hydroxy-terminated trithiocarbonate (TTC-OH) as initiator. The resulting TTC end-capped PHB prepolymer next promoted the controlled reversible addition–fragmentation chain-transfer (RAFT) polymerization of 2-hydroxy ethyl methacrylate (HEMA). When performed in THF, in which the initial solvophilic PHB-TTC segment and HEMA monomer are both fully soluble, this second step resulted in a polymerization-induced self-assembly (PISA) leading to the formation of nanoparticles, as the solvophobic PHEMA precipitated in the dispersed medium. The effective extension of the PHB block by a PHEMA segment, as evidenced by SEC and NMR analyses, highlighted the efficiency of the PHB-TTC macro-RAFT agent. This ROP/RAFT/PISA strategy revealed successful at various polyester (DP = 45–90) and polymethacrylate (DP = 200–500) block lengths. The size, polydispersity index (PDI) and morphology of the resulting self-assembled PHBx-b-PHEMAy particles were assessed by dynamic light scattering (DLS) measurements, transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). Depending on both segments chain-lengths, DLS enabled identifying particles in suspension having hydrodynamic diameters (DH) varying from 56 to 194 nm, with narrow polydispersity index, i.e. PDI < 0.140. SAXS measurements and TEM observations revealed vesicles morphology for specific PHBx-b-PHEMAy samples presenting apparent diameters ranging from 134 to 316 nm. These morphologies support the successful copolymerization through a PISA process, first reported herein for the elaboration of PHA-based objects that may be valuable nano-vehicles of active ingredients for biomedical applications.
{"title":"Poly(β-hydroxyalkanoate)/polymethacrylate self-assembled architectures by ring-opening polymerization (ROP)/reversible addition–fragmentation chain-transfer (RAFT) polymerization and polymerization-induced self-assembly (PISA)†","authors":"Julien Rosselgong , Ali Dhaini , Manon Rochedy , Lourdes Mónica Bravo-Anaya , Jean-François Carpentier , Sophie M. Guillaume","doi":"10.1039/d4py01447b","DOIUrl":"10.1039/d4py01447b","url":null,"abstract":"<div><div>Self-assembled poly(β-hydroxyalkanoate) (PHA)-based block copolymers are attractive materials for biomedical applications due to the biocompatibility and (bio)degradability of the PHA segment. Herein, we report the synthesis and formation of self-assemblies based on PHAs: namely, poly(3-hydroxybutyrate) (PHB) was prepared by ring-opening polymerization (ROP) of racemic β-butyrolactone (<em>rac</em>-β-BL) using a discrete yttrium-based catalyst in the presence of a hydroxy-terminated trithiocarbonate (TTC-OH) as initiator. The resulting TTC end-capped PHB prepolymer next promoted the controlled reversible addition–fragmentation chain-transfer (RAFT) polymerization of 2-hydroxy ethyl methacrylate (HEMA). When performed in THF, in which the initial solvophilic PHB-TTC segment and HEMA monomer are both fully soluble, this second step resulted in a polymerization-induced self-assembly (PISA) leading to the formation of nanoparticles, as the solvophobic PHEMA precipitated in the dispersed medium. The effective extension of the PHB block by a PHEMA segment, as evidenced by SEC and NMR analyses, highlighted the efficiency of the PHB-TTC macro-RAFT agent. This ROP/RAFT/PISA strategy revealed successful at various polyester (DP = 45–90) and polymethacrylate (DP = 200–500) block lengths. The size, polydispersity index (PDI) and morphology of the resulting self-assembled PHB<sub><em>x</em></sub>-<em>b</em>-PHEMA<sub><em>y</em></sub> particles were assessed by dynamic light scattering (DLS) measurements, transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). Depending on both segments chain-lengths, DLS enabled identifying particles in suspension having hydrodynamic diameters (<em>D</em><sub>H</sub>) varying from 56 to 194 nm, with narrow polydispersity index, <em>i.e.</em> PDI < 0.140. SAXS measurements and TEM observations revealed vesicles morphology for specific PHB<sub><em>x</em></sub>-<em>b</em>-PHEMA<sub><em>y</em></sub> samples presenting apparent diameters ranging from 134 to 316 nm. These morphologies support the successful copolymerization through a PISA process, first reported herein for the elaboration of PHA-based objects that may be valuable nano-vehicles of active ingredients for biomedical applications.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 10","pages":"Pages 1162-1175"},"PeriodicalIF":4.1,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01447b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044629","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abdullah Adewale Adeoba, Xiangyu Shen, Fuzhen Bi, Jianan Niu, Mingxin Sun, Shuguang Wen and Xichang Bao
Correction for ‘Simple oxime functionalized fluorene polymers for organic solar cells’ by Abdullah Adewale Adeoba et al., Polym. Chem., 2024, 15, 4474–4481.
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