Matilde Porcarello, Ettore Greco, Alberto Cellai, Rafael Turra Alarcon, Elisabeth Rossegger, Marco Sangermano
In this work, we developed and characterized bio-based formulations derived from functionalized vegetable oils, aiming to create sustainable resins suitable for 3D printing with dynamic polymer network (DPNs) properties. Epoxidized castor oil (ECO), known for its inherent DPN behaviour due to the presence of hydroxyl groups enabling transesterification, was used as the primary component. However, its high viscosity at room temperature limits its printability. To address this, epoxidized soybean oil (ESO), a less viscous and equally bio-based alternative, was blended with ECO in varying weight ratios: 100% ECO, 100% ESO, ECO-ESO 70-30, and ECO-ESO 50-50. UV-curing characterizations of the prepared formulations were performed through FTIR and photo-DSC. Their thermal and mechanical properties were investigated through DMTA and tensile tests, while rheological analyses assessed their printability. DPN behaviour was evaluated via stress relaxation tests in the presence of a biobased transesterification catalyst eugenol-based phosphate ester (EUGP). Among the blends, the ECO-ESO 70-30 formulation retained a good DPN dynamics, while in the 50-50 blend this feature decreased due to the lack of hydroxyl groups in ESO. DPN systems demonstrated successful 3D printability and were proven to be thermally reprocessable. This work highlights the potential of renewable, plant-oil-based materials in advancing circular, sustainable additive manufacturing technologies.
{"title":"3D printing of biobased epoxidized formulations based on vegetable oils with dynamic polymer network properties","authors":"Matilde Porcarello, Ettore Greco, Alberto Cellai, Rafael Turra Alarcon, Elisabeth Rossegger, Marco Sangermano","doi":"10.1039/d5py01069a","DOIUrl":"https://doi.org/10.1039/d5py01069a","url":null,"abstract":"In this work, we developed and characterized bio-based formulations derived from functionalized vegetable oils, aiming to create sustainable resins suitable for 3D printing with dynamic polymer network (DPNs) properties. Epoxidized castor oil (ECO), known for its inherent DPN behaviour due to the presence of hydroxyl groups enabling transesterification, was used as the primary component. However, its high viscosity at room temperature limits its printability. To address this, epoxidized soybean oil (ESO), a less viscous and equally bio-based alternative, was blended with ECO in varying weight ratios: 100% ECO, 100% ESO, ECO-ESO 70-30, and ECO-ESO 50-50. UV-curing characterizations of the prepared formulations were performed through FTIR and photo-DSC. Their thermal and mechanical properties were investigated through DMTA and tensile tests, while rheological analyses assessed their printability. DPN behaviour was evaluated via stress relaxation tests in the presence of a biobased transesterification catalyst eugenol-based phosphate ester (EUGP). Among the blends, the ECO-ESO 70-30 formulation retained a good DPN dynamics, while in the 50-50 blend this feature decreased due to the lack of hydroxyl groups in ESO. DPN systems demonstrated successful 3D printability and were proven to be thermally reprocessable. This work highlights the potential of renewable, plant-oil-based materials in advancing circular, sustainable additive manufacturing technologies.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"67 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070479","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}
Syaiful Ahsan, Fitrilia Silvianti, Cornelis Post, Vincent Voet, Rudy Folkersma, Jeffy Joji, Louis Pitet, Subin Damodaran, Katja Loos, Dina Maniar
Annual plastic production volumes are more than 400 million tons and are anticipated to continue increasing over the next decade. The majority of plastics originate from fossil resources. Limited raw material reserves and ongoing utilization of plastics contribute to elevated CO2 emissions, ultimately contributing to climate change. Development of green polymers (i.e., biobased) is one way to reduce our environmental impact. Using renewable resources as raw materials for polymer synthesis reduces the reliance on petroleum and in some cases enables recycling and/or biodegradation. Various aliphatic biobased polyesters have been studied; however, they typically have low glass transition temperatures (Tg) and poor thermomechanical performance, which may limit their applications. In this work, we investigate the synthesis route and structure–property relationships of (co)polyesters from cyclic biobased monomers, camphoric acid and 1,4-cyclohexanedimethanol (CHDM). We observed that increasing the reaction temperature and extending the reaction time led to increased molecular weight and yield of poly(cyclohexanedimethylene camphorate) (PCHC). Conversely, substituting p-toluenesulfonic acid (p-TSA) with a titanium(IV) isopropoxide (TTIP) catalyst led to reductions in both the molecular weight and yield. Furthermore, (co)polyesters with Tg values ranging from –29 to +56 °C were successfully synthesized. DSC and WAXD analyses suggest that the polyesters derived from camphoric acid and the linear diols were amorphous, whereas those based on CHDM were semicrystalline. This work helps address existing knowledge gaps in biobased polymer development by introducing cyclic biobased monomers that expand the current library of renewable materials, thereby broadening opportunities for advanced applications such as coating and packaging materials.
{"title":"Synthesis and characterization of biobased (co)polyesters derived from cyclic monomers: camphoric acid and 1,4-cyclohexanedimethanol","authors":"Syaiful Ahsan, Fitrilia Silvianti, Cornelis Post, Vincent Voet, Rudy Folkersma, Jeffy Joji, Louis Pitet, Subin Damodaran, Katja Loos, Dina Maniar","doi":"10.1039/d5py01182e","DOIUrl":"https://doi.org/10.1039/d5py01182e","url":null,"abstract":"Annual plastic production volumes are more than 400 million tons and are anticipated to continue increasing over the next decade. The majority of plastics originate from fossil resources. Limited raw material reserves and ongoing utilization of plastics contribute to elevated CO2 emissions, ultimately contributing to climate change. Development of green polymers (i.e., biobased) is one way to reduce our environmental impact. Using renewable resources as raw materials for polymer synthesis reduces the reliance on petroleum and in some cases enables recycling and/or biodegradation. Various aliphatic biobased polyesters have been studied; however, they typically have low glass transition temperatures (Tg) and poor thermomechanical performance, which may limit their applications. In this work, we investigate the synthesis route and structure–property relationships of (co)polyesters from cyclic biobased monomers, camphoric acid and 1,4-cyclohexanedimethanol (CHDM). We observed that increasing the reaction temperature and extending the reaction time led to increased molecular weight and yield of poly(cyclohexanedimethylene camphorate) (PCHC). Conversely, substituting p-toluenesulfonic acid (p-TSA) with a titanium(IV) isopropoxide (TTIP) catalyst led to reductions in both the molecular weight and yield. Furthermore, (co)polyesters with Tg values ranging from –29 to +56 °C were successfully synthesized. DSC and WAXD analyses suggest that the polyesters derived from camphoric acid and the linear diols were amorphous, whereas those based on CHDM were semicrystalline. This work helps address existing knowledge gaps in biobased polymer development by introducing cyclic biobased monomers that expand the current library of renewable materials, thereby broadening opportunities for advanced applications such as coating and packaging materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"4 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070504","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 cycloaddition reaction of CO2 is one of the most promising pathways for CO2 utilization due to its 100% atomic utilization rate and generation of value-added carbonate products. However, it typically requires organic solvents, high temperatures, and elevated pressures. Swelling poly(ionic liquid)s (SPILs), capable of spontaneously forming porous structures under specific solvents and atmospheric conditions, are potential catalysts but face challenges in efficient catalyst-product separation. In this work, a thermosensitive SPIL catalyst, P-[VC12Im]-C12-Br, exhibiting temperature-responsive swelling behavior in the reaction substrate (epichlorohydrin), was designed and synthesized. When applied to CO2 cycloaddition under solvent-free and atmospheric conditions at 80oC, it achieved a 91.07% yield of the target product, chloromethyl oxazolidinone. Upon reaction completion, cooling to 25oC triggered spontaneous catalyst contraction and separation from the product, enabling successful high-temperature catalysis and low-temperature separation. Moreover, P-[VC12Im]-C12-Br exhibited excellent recyclability (6 cycles) and broad substrate adaptability. The catalyst undergoes hydrogen bond-induced swelling at elevated temperatures, forming porous channels. The exposed active sites (Br-) facilitate epoxide ring-opening via nucleophilic attack, while the imidazolium rings assist in CO2 capture and activation. These components synergistically catalyze the cycloaddition process. This study provides a novel strategy for efficient of CO2 conversion and also offers fundamental insights and practical guidance for developing controllable SPIL catalyst.
{"title":"Temperature-Triggered Self-Separating Swelling Poly(Ionic Liquid)s as Efficient Catalysts for CO2 Cycloaddition Reactions","authors":"Jiayi Jiayi Chen, Qing Sun, Haihong Zhao, Hao Chen","doi":"10.1039/d5py01097g","DOIUrl":"https://doi.org/10.1039/d5py01097g","url":null,"abstract":"The cycloaddition reaction of CO2 is one of the most promising pathways for CO2 utilization due to its 100% atomic utilization rate and generation of value-added carbonate products. However, it typically requires organic solvents, high temperatures, and elevated pressures. Swelling poly(ionic liquid)s (SPILs), capable of spontaneously forming porous structures under specific solvents and atmospheric conditions, are potential catalysts but face challenges in efficient catalyst-product separation. In this work, a thermosensitive SPIL catalyst, P-[VC12Im]-C12-Br, exhibiting temperature-responsive swelling behavior in the reaction substrate (epichlorohydrin), was designed and synthesized. When applied to CO2 cycloaddition under solvent-free and atmospheric conditions at 80oC, it achieved a 91.07% yield of the target product, chloromethyl oxazolidinone. Upon reaction completion, cooling to 25oC triggered spontaneous catalyst contraction and separation from the product, enabling successful high-temperature catalysis and low-temperature separation. Moreover, P-[VC12Im]-C12-Br exhibited excellent recyclability (6 cycles) and broad substrate adaptability. The catalyst undergoes hydrogen bond-induced swelling at elevated temperatures, forming porous channels. The exposed active sites (Br-) facilitate epoxide ring-opening via nucleophilic attack, while the imidazolium rings assist in CO2 capture and activation. These components synergistically catalyze the cycloaddition process. This study provides a novel strategy for efficient of CO2 conversion and also offers fundamental insights and practical guidance for developing controllable SPIL catalyst.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070480","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}
Rana Abdul Razzak, Jonathan Bath, Rachel K. O'Reilly, Andrew J Turberfield
We demonstrate a triplex-based architecture for DNA-templated synthesis. This study is motivated by progress towards the development of a synthetic ribosome - autonomous, genetically programmable, molecular machinery for synthesis. Such schemes for the creation and evolution of chemically diverse DNA-tagged chemical libraries rely on hybridization reactions of oligonucleotide adapters to control sequential, DNA-templated reactions of covalently attached building blocks. To enable parallel one-pot library synthesis it is desirable that any building block can be incorporated at any position in a product oligomer: this is incompatible with geometries commonly used for DNA-templated synthesis, which require alternate reactants to be attached to 3' and 5' termini of their adapters. Our triplex-based architecture overcomes this problem by templating reactions between building blocks attached to adapters with identical structures. It is intended to form the core of programmable molecular machinery for multistep synthesis. Here, we use single-step coupling reactions to characterize the triplex reaction template.
{"title":"A Palindromic Triplex Architecture for DNA-Templated Synthesis Designed for the Core of a Synthetic Ribosome","authors":"Rana Abdul Razzak, Jonathan Bath, Rachel K. O'Reilly, Andrew J Turberfield","doi":"10.1039/d5py01159k","DOIUrl":"https://doi.org/10.1039/d5py01159k","url":null,"abstract":"We demonstrate a triplex-based architecture for DNA-templated synthesis. This study is motivated by progress towards the development of a synthetic ribosome - autonomous, genetically programmable, molecular machinery for synthesis. Such schemes for the creation and evolution of chemically diverse DNA-tagged chemical libraries rely on hybridization reactions of oligonucleotide adapters to control sequential, DNA-templated reactions of covalently attached building blocks. To enable parallel one-pot library synthesis it is desirable that any building block can be incorporated at any position in a product oligomer: this is incompatible with geometries commonly used for DNA-templated synthesis, which require alternate reactants to be attached to 3' and 5' termini of their adapters. Our triplex-based architecture overcomes this problem by templating reactions between building blocks attached to adapters with identical structures. It is intended to form the core of programmable molecular machinery for multistep synthesis. Here, we use single-step coupling reactions to characterize the triplex reaction template.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"17 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070481","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}
Post-polymerization/functionalization approaches are promising tools for diversifying polymer synthesis. Herein, we report a combination of Cu-catalyzed azide–alkyne cycloaddition (CuAAC, Click reaction) and direct (C–H) arylation (DA) as post-polymerization strategies applied to the side chains of polystyrene. The Click reaction between azide-functionalized polystyrene (polymer 1) and an alkyne afforded a polystyrene derivative (2) bearing a 1,2,3-triazole moiety on its side chain. The triazole unit introduced via the Click reaction serves as a reactive site for subsequent C–H activation in the DA process. Post-polymerization of 2 with a bromoarene under optimized conditions enabled successful arylation, despite the generally low reactivity and selectivity associated with triazole C–H activation. Optimization was crucial to overcoming these challenges. The use of carboxylate ligands with bulky alkyl groups in the catalytic system significantly enhanced the reaction efficiency. The DA post-polymerization proceeded smoothly under a catalytic system composed of PdCl2, K2CO3, and a bulky carboxylic acid additive (isostearic acid) in N,N-dimethylformamide (DMF) at 100 °C, affording the arylated product (3) in quantitative yield without side reactions that typically lead to polymer insolubilization. To further expand this approach, we applied the Click reaction to azide-terminated polystyrene, generating a polymer with a reactive 1,2,3-triazole end group. Subsequent DA with a bromoarene led to a dual-functionalized polymer end. This Click-induced, 1,2,3-triazole-based building block strategy demonstrates potential for polycondensation and post-polymerization of functional polymers.
{"title":"Direct Arylation Post-Polymerization for Click-Generated 1,2,3-Triazole","authors":"Yuki Kitagawa, Shotaro Hayashi","doi":"10.1039/d6py00016a","DOIUrl":"https://doi.org/10.1039/d6py00016a","url":null,"abstract":"Post-polymerization/functionalization approaches are promising tools for diversifying polymer synthesis. Herein, we report a combination of Cu-catalyzed azide–alkyne cycloaddition (CuAAC, Click reaction) and direct (C–H) arylation (DA) as post-polymerization strategies applied to the side chains of polystyrene. The Click reaction between azide-functionalized polystyrene (polymer 1) and an alkyne afforded a polystyrene derivative (2) bearing a 1,2,3-triazole moiety on its side chain. The triazole unit introduced via the Click reaction serves as a reactive site for subsequent C–H activation in the DA process. Post-polymerization of 2 with a bromoarene under optimized conditions enabled successful arylation, despite the generally low reactivity and selectivity associated with triazole C–H activation. Optimization was crucial to overcoming these challenges. The use of carboxylate ligands with bulky alkyl groups in the catalytic system significantly enhanced the reaction efficiency. The DA post-polymerization proceeded smoothly under a catalytic system composed of PdCl2, K2CO3, and a bulky carboxylic acid additive (isostearic acid) in N,N-dimethylformamide (DMF) at 100 °C, affording the arylated product (3) in quantitative yield without side reactions that typically lead to polymer insolubilization. To further expand this approach, we applied the Click reaction to azide-terminated polystyrene, generating a polymer with a reactive 1,2,3-triazole end group. Subsequent DA with a bromoarene led to a dual-functionalized polymer end. This Click-induced, 1,2,3-triazole-based building block strategy demonstrates potential for polycondensation and post-polymerization of functional polymers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"53 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021837","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}
Liquid silicone rubber (SiR) exhibits significant application value in medical devices, flexible electronics, and soft robotics due to its excellent biocompatibility, tunable mechanical properties, and chemical stability. The additive manufacturing of SiR via 3D printing technology enables the customized fabrication of complex structures, particularly in multidisciplinary fields that require personalized designs, such as biomedical implants, bioinspired flexible sensors, and dynamically responsive soft robots. Despite the high precision achievable through stereolithography (SLA) or digital light processing (DLP) photocuring techniques, the low modulus of SiR remains a challenge for high-precision 3D printing. Inspired by the concept of polymer composites, blending SiR with mechanically robust polycaprolactone (PCL, a biocompatible polymer) provides an effective strategy to address these limitations, but still faces the challenge caused by the poor compatibility between SiR and PCL. In this study, a synergistic dual-compatibilization strategy was designed, amphiphilic compatibilizers (amino-functionalized carbon quantum dots, NH2-CDs) and modified polycaprolactone (PCL-DA) were introduced to enhance interfacial compatibility between the two phases. The introduced NH2-CDs, functioning as a nanoscale compatibilizer, effectively suppressed phase separation through interfacial Pickering stabilization, which resulted in a dramatic reduction of the dispersed SiR domain size from 25.94 ± 9.29 μm to 2.33 ± 0.55 μm, accompanied by the formation of a distinct interfacial layer (~860 nm). The resulting SiR/PCL-DA/NH2-CDs composite fulfills the requirements for photocurable 3D printing, achieving high precision, multi-morphological adaptability, and considerable mechanical performance. It exhibits considerable mechanical performance with a tensile strength of 440.7 kPa and an elongation at break of 367%. Additionally, the incorporation of semi-crystalline PCL and NH2-CDs endows the system with shape memory functionality (triggered at -5 °C and 60 °C) and fluorescence properties. This work presents a feasible approach for developing biocompatible, photocurable silicone elastomer-based composites via DLP 3D printing, offering broad prospects for advanced applications in smart materials and biomedical engineering.
{"title":"Digital Light Processing 3D Printable Smart Silicone-based Elastomeric Composites based on a Synergistic Dual-compatibilization Strategy","authors":"Si-Ying Lan, Fuyue Tian, Xinyue Hao, Xin-Yu Li, Jing Bai, Nanying Ning, Bing Yu, Ming Tian","doi":"10.1039/d5py01138h","DOIUrl":"https://doi.org/10.1039/d5py01138h","url":null,"abstract":"Liquid silicone rubber (SiR) exhibits significant application value in medical devices, flexible electronics, and soft robotics due to its excellent biocompatibility, tunable mechanical properties, and chemical stability. The additive manufacturing of SiR via 3D printing technology enables the customized fabrication of complex structures, particularly in multidisciplinary fields that require personalized designs, such as biomedical implants, bioinspired flexible sensors, and dynamically responsive soft robots. Despite the high precision achievable through stereolithography (SLA) or digital light processing (DLP) photocuring techniques, the low modulus of SiR remains a challenge for high-precision 3D printing. Inspired by the concept of polymer composites, blending SiR with mechanically robust polycaprolactone (PCL, a biocompatible polymer) provides an effective strategy to address these limitations, but still faces the challenge caused by the poor compatibility between SiR and PCL. In this study, a synergistic dual-compatibilization strategy was designed, amphiphilic compatibilizers (amino-functionalized carbon quantum dots, NH2-CDs) and modified polycaprolactone (PCL-DA) were introduced to enhance interfacial compatibility between the two phases. The introduced NH2-CDs, functioning as a nanoscale compatibilizer, effectively suppressed phase separation through interfacial Pickering stabilization, which resulted in a dramatic reduction of the dispersed SiR domain size from 25.94 ± 9.29 μm to 2.33 ± 0.55 μm, accompanied by the formation of a distinct interfacial layer (~860 nm). The resulting SiR/PCL-DA/NH2-CDs composite fulfills the requirements for photocurable 3D printing, achieving high precision, multi-morphological adaptability, and considerable mechanical performance. It exhibits considerable mechanical performance with a tensile strength of 440.7 kPa and an elongation at break of 367%. Additionally, the incorporation of semi-crystalline PCL and NH2-CDs endows the system with shape memory functionality (triggered at -5 °C and 60 °C) and fluorescence properties. This work presents a feasible approach for developing biocompatible, photocurable silicone elastomer-based composites via DLP 3D printing, offering broad prospects for advanced applications in smart materials and biomedical engineering.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"53 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021907","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}
Disulfide bonds have been widely explored in cancer therapeutic applications for their propensity to break in the presence of the tripeptide, Glutathione (GSH), which is overly expressed in cancerous cells due to the upregulation of the antioxidant defense pathways. Therefore, the incorporation of disulfide bonds to polymeric nanocarriers designed for anticancer drug delivery facilitates the degradation of the polymer backbone and promotes the release of the encapsulated drug under cancerous microenvironments. However, facile synthetic strategies that incorporate disulfide bonds into biodegradable and biocompatible amphiphilic polyesters for targeted delivery are limited. We have synthesized two such polyesters, P1 and P2, integrating disulfide bonds into the polyester backbone through an organocatalyzed polycondensation reaction between a dipentafluorophenyl-activated ester and functionalized diols in N, N dimethylformamide at 100 °C. Among these two, P1 is a homopolyester comprising of bis(2-hydroxyethyl) disulfide (HEDS), and P2 is a copolyester comprising an additional biotin moiety for cancer cell selectivity and a fluorescent NMI-functionalized moiety for cellular trafficking, randomly distributed in the polymer chain as pendants, along with the disulfide bonds in the backbone. The time-dependent kinetics study during the polytransesterification reaction demonstrates complete monomer conversion within 24 hours. By virtue of its amphiphilic character, P2 self-assembles into nanoaggregates in water with size of ~220 nm, and features the propensity to encapsulate the hydrophobic dye Nile Red (NR). Degradation of the nanoaggregates and subsequent NR-dye release has been illustrated in the presence of both GSH and Lipase B. The self-assembled P2 shows selective uptake towards cancerous HeLa cells compared to non-cancerous NIH 3T3 cells by biotin-receptor-mediated endocytosis, enabling its ability to selectively deliver the anticancerous drug, doxorubicin, resulting in decreased cellular viability yielding IC50 value of 19 µg/mL after 48 hours of incubation. These findings highlight the potential of this versatile methodology for designing structurally new degradable polyesters with tunable functionalities for other target-specific stimuli-responsive therapeutic applications.
{"title":"Glutathione-Responsive Degradable Amphiphilic Polyester-Based Nanocarrier for Targeted Drug Delivery","authors":"Ankita Banerjee, Subhendu Biswas, Anindita Das","doi":"10.1039/d5py01148e","DOIUrl":"https://doi.org/10.1039/d5py01148e","url":null,"abstract":"Disulfide bonds have been widely explored in cancer therapeutic applications for their propensity to break in the presence of the tripeptide, Glutathione (GSH), which is overly expressed in cancerous cells due to the upregulation of the antioxidant defense pathways. Therefore, the incorporation of disulfide bonds to polymeric nanocarriers designed for anticancer drug delivery facilitates the degradation of the polymer backbone and promotes the release of the encapsulated drug under cancerous microenvironments. However, facile synthetic strategies that incorporate disulfide bonds into biodegradable and biocompatible amphiphilic polyesters for targeted delivery are limited. We have synthesized two such polyesters, <strong>P1</strong> and <strong>P2</strong>, integrating disulfide bonds into the polyester backbone through an organocatalyzed polycondensation reaction between a dipentafluorophenyl-activated ester and functionalized diols in <em>N, N</em> dimethylformamide at 100 °C. Among these two, <strong>P1</strong> is a homopolyester comprising of bis(2-hydroxyethyl) disulfide (HEDS), and <strong>P2</strong> is a copolyester comprising an additional biotin moiety for cancer cell selectivity and a fluorescent NMI-functionalized moiety for cellular trafficking, randomly distributed in the polymer chain as pendants, along with the disulfide bonds in the backbone. The time-dependent kinetics study during the polytransesterification reaction demonstrates complete monomer conversion within 24 hours. By virtue of its amphiphilic character, <strong>P2</strong> self-assembles into nanoaggregates in water with size of ~220 nm, and features the propensity to encapsulate the hydrophobic dye Nile Red (NR). Degradation of the nanoaggregates and subsequent NR-dye release has been illustrated in the presence of both GSH and Lipase B. The self-assembled <strong>P2</strong> shows selective uptake towards cancerous HeLa cells compared to non-cancerous NIH 3T3 cells by biotin-receptor-mediated endocytosis, enabling its ability to selectively deliver the anticancerous drug, doxorubicin, resulting in decreased cellular viability yielding IC<small><sub>50</sub></small> value of 19 µg/mL after 48 hours of incubation. These findings highlight the potential of this versatile methodology for designing structurally new degradable polyesters with tunable functionalities for other target-specific stimuli-responsive therapeutic applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"71 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021845","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}
Longfei Li, Minghao Liu, Zehao Wang, Xiaowu Wang, Zhibo Li
Linear polyglycerol (linPGC)-based functionalized polyethers exhibit superior water solubility and biocompatibility compared to traditional polyethylene glycol (PEG). However, their efficient and straightforward synthesis remains a significant challenge. Herein, we report a one-component phosphonium tetraborane Lewis pair (P4B-Br) via a three-step synthesis, and demonstrate that P4B-Br enables the ring-opening polymerization (ROP) of commercially available (R)-(-)-glycidyl butyrate (RGB) at room temperature with a turnover number (TON) of 200, yielding α-Br/ω-OH and α-OH/ω-OH terminated poly(glycidyl butyrate) (PRGB). Kinetic studies reveala pseudo-zero-order dependence on the monomer concentration and first-order dependence on the catalyst concentration. An intramolecular synergistic catalysis mode is proposed.Deprotection of PRGB via alcoholysis releases pendant hydroxyl groups to form linPGC. Furthermore, RGB can be copolymerized with propylene oxide (PO), 1,2-butylene oxide (BO), allyl glycidyl ether (AGE), and tert-butyl glycidyl ether (t-BGE) to prepare linPGC-based functionalized polyethers with diverse sequence structures. This work provides a practical approach for the various linPGC derivatives.
{"title":"Synthesis of glycerol-based (co)polyethers via ring-opening polymerization of glycidyl butyrate catalyzed by one-component phosphonium tetraborane Lewis Pair †","authors":"Longfei Li, Minghao Liu, Zehao Wang, Xiaowu Wang, Zhibo Li","doi":"10.1039/d5py01129a","DOIUrl":"https://doi.org/10.1039/d5py01129a","url":null,"abstract":"Linear polyglycerol (linPGC)-based functionalized polyethers exhibit superior water solubility and biocompatibility compared to traditional polyethylene glycol (PEG). However, their efficient and straightforward synthesis remains a significant challenge. Herein, we report a one-component phosphonium tetraborane Lewis pair (P4B-Br) via a three-step synthesis, and demonstrate that P4B-Br enables the ring-opening polymerization (ROP) of commercially available (R)-(-)-glycidyl butyrate (RGB) at room temperature with a turnover number (TON) of 200, yielding α-Br/ω-OH and α-OH/ω-OH terminated poly(glycidyl butyrate) (PRGB). Kinetic studies reveala pseudo-zero-order dependence on the monomer concentration and first-order dependence on the catalyst concentration. An intramolecular synergistic catalysis mode is proposed.Deprotection of PRGB via alcoholysis releases pendant hydroxyl groups to form linPGC. Furthermore, RGB can be copolymerized with propylene oxide (PO), 1,2-butylene oxide (BO), allyl glycidyl ether (AGE), and tert-butyl glycidyl ether (t-BGE) to prepare linPGC-based functionalized polyethers with diverse sequence structures. This work provides a practical approach for the various linPGC derivatives.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"78 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146034204","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}
Wanying Wang, Pengfei Li, Yue Xu, Shiqi Wei, Xiangdie Hou, Ning Li, Zhichao Zhou, Xiaohong Li, Ziyuan Song
Polyester-polypeptide block copolymers have shown great potentials as biomaterials by combining the properties and advantages of both polymers. The preparation of the hybrid materials, however, is limited by the tedious protection/deprotection of chain-ends. Herein, we report the facile preparation of polyester-polyglutamate from bifunctional aminoalkyl alcohols, which regio-selectively initiate the polymerization of N-carboxyanhydrides (NCAs) from the amino groups with negligible interference by the hydroxyl groups. The hydroxyl-capping polypeptide marcoinitiators were then used for the preparation of diblock copolymers by skipping the conventional protection/deprotection steps. We believe that this work provides new insights in NCA stability against hydroxyl molecules, allowing for the preparation of well-defined polyester-polyglutamates in an efficient manner.
{"title":"Facile preparation of polyester-polyglutamate diblock copolymers through regio-selective polymerization of N-carboxyanhydride","authors":"Wanying Wang, Pengfei Li, Yue Xu, Shiqi Wei, Xiangdie Hou, Ning Li, Zhichao Zhou, Xiaohong Li, Ziyuan Song","doi":"10.1039/d5py01194a","DOIUrl":"https://doi.org/10.1039/d5py01194a","url":null,"abstract":"Polyester-polypeptide block copolymers have shown great potentials as biomaterials by combining the properties and advantages of both polymers. The preparation of the hybrid materials, however, is limited by the tedious protection/deprotection of chain-ends. Herein, we report the facile preparation of polyester-polyglutamate from bifunctional aminoalkyl alcohols, which regio-selectively initiate the polymerization of <em>N</em>-carboxyanhydrides (NCAs) from the amino groups with negligible interference by the hydroxyl groups. The hydroxyl-capping polypeptide marcoinitiators were then used for the preparation of diblock copolymers by skipping the conventional protection/deprotection steps. We believe that this work provides new insights in NCA stability against hydroxyl molecules, allowing for the preparation of well-defined polyester-polyglutamates in an efficient manner.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"3 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146021908","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A series of novel chiral dimeric Zn(II) complexes, comprising both (S)- and (R)-isomers, were synthesized utilizing N-Boc protected proline-derived ligand scaffolds. The reaction of diethylzinc (ZnEt₂) with equimolar amounts of pro-ligands (L1H–L4H) in anhydrous toluene afforded the corresponding Zn(II) complexes (1–4) in high yields. The solid-state structures of complexes 1 and 3 were elucidated via single-crystal X-ray diffraction, revealing a distorted tetrahedral coordination geometry around the Zn(II) center. However, spectroscopic analysis indicated the presence of monomeric Zn(II) species in solution. All synthesized complexes were evaluated for their catalytic performance in the ring-opening polymerization (ROP) of racemic lactide (rac-LA) and ring-opening copolymerization (ROCOP) of phthalic anhydride (PA) with cyclohexene oxide (CHO), as well as other epoxide–anhydride combinations. All the Zn(II) complexes demonstrated activity in the ROP of rac-LA, yielding polylactide (PLA) with stereoregularity ranging from atactic (Pr = 0.51) to slightly isotactic-enriched (Pm = 0.58), influenced by the ligand architecture and chirality. The ROP is proposed to proceed via ligand-initiated coordination–insertion mechanism. All the Zn(II) complexes (1–4) were catalytically active in the presence of a cocatalyst, with bis(triphenylphosphine)iminium chloride (PPNCl) delivering optimal performance. The ROCOP of CHO with PA yielded alternating copolyesters with moderate to high number-average molecular weights (Mn ≈ 7200 g mol⁻¹) and moderate dispersity (Đ ≈ 1.33). (R)-4 catalyzed the formation of an atactic polyester, whereas (S)-2 enabled the synthesis of a perfectly alternating poly(PA-alt-CHO) with enhanced isotacticity. Kinetic studies revealed that complex (S)-1 exhibited a fourfold higher polymerization rate compared to (R)-4. DFT energy calculations revealed a favourable mechanistic pathway wherein the dimeric zinc species dissociates into monomeric active intermediates, a crucial step in facilitating the ROCOP.
利用N-Boc保护的脯氨酸衍生配体支架合成了一系列具有(S)-和(R)-异构体的新型手性二聚体Zn（II）配合物。二乙基锌（ZnEt 2）与等摩尔量的前配体（L1H-L4H）在无水甲苯中反应得到相应的Zn（II）配合物（1-4），收率高。通过单晶x射线衍射分析了配合物1和3的固态结构，发现配合物在Zn（II）中心周围呈扭曲的四面体配位几何。然而，光谱分析表明溶液中存在单体Zn（II）。对所有合成的配合物在外消旋丙交酯（rac-LA）开环聚合（ROP）、邻苯二甲酸酐（PA）与环氧己烯氧化物（CHO）开环共聚（ROCOP）以及其他环氧-酸酐组合中的催化性能进行了评价。所有Zn（II）配合物在rac-LA的ROP中都表现出活性，生成的聚乳酸（PLA）的立体规则范围从无规（Pr = 0.51）到轻度等规富集（Pm = 0.58），受配体结构和手性的影响。ROP是通过配体引发的配位插入机制进行的。所有Zn（II）配合物（1-4）在助催化剂存在下都具有催化活性，其中双（三苯基膦）氯化亚胺（PPNCl）表现出最佳的催化活性。CHO与PA的ROCOP反应得到中高数均分子量（Mn≈7200 g mol⁻¹）和中等分散性（Đ≈1.33）的交替共聚酯。(R)-4催化形成无规聚酯，而(S)-2催化合成具有增强等规性的完全交替聚（PA-alt-CHO）。动力学研究表明，配合物(S)-1的聚合速率比(R)-4高4倍。DFT能量计算揭示了一个有利的机制途径，其中二聚体锌解离成单体活性中间体，这是促进ROCOP的关键步骤。
{"title":"Chiral Proline-derived Zn(II) Complexes as Catalysts for Ring-Opening Polymerization and Ring-Opening Copolymerization Reactions","authors":"Ranay Kumar Ray, Manoj Kumari, Kartik Chandra Mondal, Debashis Chakraborty","doi":"10.1039/d5py01089f","DOIUrl":"https://doi.org/10.1039/d5py01089f","url":null,"abstract":"A series of novel chiral dimeric Zn(II) complexes, comprising both (S)- and (R)-isomers, were synthesized utilizing N-Boc protected proline-derived ligand scaffolds. The reaction of diethylzinc (ZnEt₂) with equimolar amounts of pro-ligands (L1H–L4H) in anhydrous toluene afforded the corresponding Zn(II) complexes (1–4) in high yields. The solid-state structures of complexes 1 and 3 were elucidated via single-crystal X-ray diffraction, revealing a distorted tetrahedral coordination geometry around the Zn(II) center. However, spectroscopic analysis indicated the presence of monomeric Zn(II) species in solution. All synthesized complexes were evaluated for their catalytic performance in the ring-opening polymerization (ROP) of racemic lactide (rac-LA) and ring-opening copolymerization (ROCOP) of phthalic anhydride (PA) with cyclohexene oxide (CHO), as well as other epoxide–anhydride combinations. All the Zn(II) complexes demonstrated activity in the ROP of rac-LA, yielding polylactide (PLA) with stereoregularity ranging from atactic (Pr = 0.51) to slightly isotactic-enriched (Pm = 0.58), influenced by the ligand architecture and chirality. The ROP is proposed to proceed via ligand-initiated coordination–insertion mechanism. All the Zn(II) complexes (1–4) were catalytically active in the presence of a cocatalyst, with bis(triphenylphosphine)iminium chloride (PPNCl) delivering optimal performance. The ROCOP of CHO with PA yielded alternating copolyesters with moderate to high number-average molecular weights (Mn ≈ 7200 g mol⁻¹) and moderate dispersity (Đ ≈ 1.33). (R)-4 catalyzed the formation of an atactic polyester, whereas (S)-2 enabled the synthesis of a perfectly alternating poly(PA-alt-CHO) with enhanced isotacticity. Kinetic studies revealed that complex (S)-1 exhibited a fourfold higher polymerization rate compared to (R)-4. DFT energy calculations revealed a favourable mechanistic pathway wherein the dimeric zinc species dissociates into monomeric active intermediates, a crucial step in facilitating the ROCOP.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146001440","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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