Pub Date : 2025-12-11DOI: 10.1016/j.progpolymsci.2025.102065
Yuhang Huang , Eugenia Kumacheva
Hydrogels with multiple characteristic pore dimensions (HMPs) have emerged as a powerful class of soft materials inspired by biological systems. By incorporating distinct average pore sizes into a single network, simultaneous control over competing hydrogel transport properties can be achieved, including throughput and selectivity, both of which are important in drug delivery, tissue engineering, catalysis, sensing, and water remediation hydrogel applications. This review highlights recent advances in the design, synthesis, characterization, and applications of HMPs. It highlights the fundamental principles of transport in these hydrogels, including the role of spatial arrangement of regions with different pore dimensions in probe mobility and fluid flow. Experimental and theoretical characterization of distinct pore dimensions in HMPs is followed by the discussion of the contribution of multiple pore dimensions to HMP functionality. The review provides the summary of the strategies for fabricating HMPs and their applications. An outlook highlights key challenges and future opportunities in this field to advance HMPs as the new generation of hydrogel-based materials for diverse applications.
{"title":"Hydrogels with multiple characteristic pore dimensions: From transport properties to multifunctional materials","authors":"Yuhang Huang , Eugenia Kumacheva","doi":"10.1016/j.progpolymsci.2025.102065","DOIUrl":"10.1016/j.progpolymsci.2025.102065","url":null,"abstract":"<div><div>Hydrogels with multiple characteristic pore dimensions (HMPs) have emerged as a powerful class of soft materials inspired by biological systems. By incorporating distinct average pore sizes into a single network, simultaneous control over competing hydrogel transport properties can be achieved, including throughput and selectivity, both of which are important in drug delivery, tissue engineering, catalysis, sensing, and water remediation hydrogel applications. This review highlights recent advances in the design, synthesis, characterization, and applications of HMPs. It highlights the fundamental principles of transport in these hydrogels, including the role of spatial arrangement of regions with different pore dimensions in probe mobility and fluid flow. Experimental and theoretical characterization of distinct pore dimensions in HMPs is followed by the discussion of the contribution of multiple pore dimensions to HMP functionality. The review provides the summary of the strategies for fabricating HMPs and their applications. An outlook highlights key challenges and future opportunities in this field to advance HMPs as the new generation of hydrogel-based materials for diverse applications.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"173 ","pages":"Article 102065"},"PeriodicalIF":26.1,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718441","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-10DOI: 10.1016/j.progpolymsci.2025.102064
Rohan Shorey , Elnaz Esmizadeh , Tizazu H. Mekonnen
Many bioplastics offer potential advantages over petroleum-based plastics, such as renewability, improved sustainability, and, in some cases, biodegradability or lower toxicity. However, in most cases, their limited mechanical performance, processing stability, or higher production costs hinder widespread adoption. Blending is a key strategy to overcome these limitations; however, the inherent immiscibility of most biopolymers leads to challenges like coarse morphology and poor interfacial adhesion. This review aims to provide an in-depth analysis of bioplastic blends by examining the fundamental principles (thermodynamic interactions, process kinematics, and morphology development) that control their behavior. It critically evaluates a broad spectrum of compatibilization strategies that span non-reactive and reactive methods and those utilizing nanofillers, aimed at stabilizing blend microstructures and enhancing material performance. A novel aspect of this work is its integration of these material science concepts with important end-of-life considerations, including biodegradability and recyclability challenges. Furthermore, it highlights the transformative role of artificial intelligence (AI) and machine learning (ML) as novel instruments for accelerating the design and optimization of next-generation bioplastic formulations. Overall, this review concludes that unlocking the full potential of bioplastics for high-performance industrial applications necessitates a holistic approach that integrates tailored blending strategies with advanced computational design, thus paving the way for the realization of a circular bioeconomy.
{"title":"Progress in bioplastics blends, compatibilization, modifications, and AI-driven innovations for material applications","authors":"Rohan Shorey , Elnaz Esmizadeh , Tizazu H. Mekonnen","doi":"10.1016/j.progpolymsci.2025.102064","DOIUrl":"10.1016/j.progpolymsci.2025.102064","url":null,"abstract":"<div><div>Many bioplastics offer potential advantages over petroleum-based plastics, such as renewability, improved sustainability, and, in some cases, biodegradability or lower toxicity. However, in most cases, their limited mechanical performance, processing stability, or higher production costs hinder widespread adoption. Blending is a key strategy to overcome these limitations; however, the inherent immiscibility of most biopolymers leads to challenges like coarse morphology and poor interfacial adhesion. This review aims to provide an in-depth analysis of bioplastic blends by examining the fundamental principles (thermodynamic interactions, process kinematics, and morphology development) that control their behavior. It critically evaluates a broad spectrum of compatibilization strategies that span non-reactive and reactive methods and those utilizing nanofillers, aimed at stabilizing blend microstructures and enhancing material performance. A novel aspect of this work is its integration of these material science concepts with important end-of-life considerations, including biodegradability and recyclability challenges. Furthermore, it highlights the transformative role of artificial intelligence (AI) and machine learning (ML) as novel instruments for accelerating the design and optimization of next-generation bioplastic formulations. Overall, this review concludes that unlocking the full potential of bioplastics for high-performance industrial applications necessitates a holistic approach that integrates tailored blending strategies with advanced computational design, thus paving the way for the realization of a circular bioeconomy.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"173 ","pages":"Article 102064"},"PeriodicalIF":26.1,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145728907","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-15DOI: 10.1016/j.progpolymsci.2025.102057
Jeffrey E. Thompson , John B. Matson , Kevin J. Edgar
Polysaccharide graft (co)polymers represent a fascinating, complex, and diverse class of materials. By combining the sustainable, biodegradable, and abundant nature of polysaccharides with the physicochemical tunability of synthetic polymers, polysaccharide graft (co)polymers are appealing candidates for high-performance sustainable materials. Careful synthetic design of polysaccharide graft (co)polymers, while challenging, is necessary to fully understand their structure, which is required to elucidate structure-property relationships. With explorations including stimuli responsive nanoparticles, renewable thermoplastic elastomers, and smart drug delivery systems, polysaccharide graft (co)polymers show great promise in a variety of applications. In this review, we discuss the synthetic tools available in producing well-defined polysaccharide graft (co)polymers, as well as their applications and structure-property relationships, highlighting the value of these materials to those striving for a sustainable future.
{"title":"Well-defined polysaccharide graft (Co)polymers: Synthesis, applications, and structure-property relationships","authors":"Jeffrey E. Thompson , John B. Matson , Kevin J. Edgar","doi":"10.1016/j.progpolymsci.2025.102057","DOIUrl":"10.1016/j.progpolymsci.2025.102057","url":null,"abstract":"<div><div>Polysaccharide graft (co)polymers represent a fascinating, complex, and diverse class of materials. By combining the sustainable, biodegradable, and abundant nature of polysaccharides with the physicochemical tunability of synthetic polymers, polysaccharide graft (co)polymers are appealing candidates for high-performance sustainable materials. Careful synthetic design of polysaccharide graft (co)polymers, while challenging, is necessary to fully understand their structure, which is required to elucidate structure-property relationships. With explorations including stimuli responsive nanoparticles, renewable thermoplastic elastomers, and smart drug delivery systems, polysaccharide graft (co)polymers show great promise in a variety of applications. In this review, we discuss the synthetic tools available in producing well-defined polysaccharide graft (co)polymers, as well as their applications and structure-property relationships, highlighting the value of these materials to those striving for a sustainable future.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"172 ","pages":"Article 102057"},"PeriodicalIF":26.1,"publicationDate":"2025-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145516128","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-14DOI: 10.1016/j.progpolymsci.2025.102054
Govardhana Babu Bodedla , Miao Zhang , Wai-Yeung Wong
Conjugated polymers, such as conjugated porous polymers, covalent organic frameworks, covalent triazine frameworks, and linear conjugated polymers comprising thiazolo[5,4-d]thiazole (TzTz) moieties, have been demonstrated as a promising new class of materials for various applications. These include photocatalytic water splitting, hydrogen peroxide production, carbon dioxide reduction, degradation of pollutants, photocatalytic organic transformations, organic light-emitting diodes, organic field-effect transistors, organic solar cells, Zn-air batteries, electrochromic devices, photocatalytic enzyme activity, carbon dioxide uptake, and nonlinear optical applications. Remarkably, the introduction of rigid, planar, and electron-withdrawing TzTz building blocks in polymeric architectures enhances their light-harvesting ability, the separation and mobility of charge carriers, favorable energy level alignments, and surface properties due to the extension of π-conjugated structures, strong intermolecular π-π stacking, and high oxidative stability. Considering the intriguing applications of TzTz-based conjugated polymers in the above-mentioned areas, this review comprehensively discusses how the structure-activity relationship can advance these applications. To our knowledge, no review has yet summarized the structure-optoelectronic, morphological, and thermal property relationships and applications of TzTz-based conjugated polymers. Hence, this review will be helpful in designing more efficient TzTz-based conjugated polymers for various future applications.
{"title":"Advancements in the molecular design of thiazolo[5,4‑d]thiazole-based conjugated polymers and their emerging applications","authors":"Govardhana Babu Bodedla , Miao Zhang , Wai-Yeung Wong","doi":"10.1016/j.progpolymsci.2025.102054","DOIUrl":"10.1016/j.progpolymsci.2025.102054","url":null,"abstract":"<div><div>Conjugated polymers, such as conjugated porous polymers, covalent organic frameworks, covalent triazine frameworks, and linear conjugated polymers comprising thiazolo[5,4-d]thiazole (TzTz) moieties, have been demonstrated as a promising new class of materials for various applications. These include photocatalytic water splitting, hydrogen peroxide production, carbon dioxide reduction, degradation of pollutants, photocatalytic organic transformations, organic light-emitting diodes, organic field-effect transistors, organic solar cells, Zn-air batteries, electrochromic devices, photocatalytic enzyme activity, carbon dioxide uptake, and nonlinear optical applications. Remarkably, the introduction of rigid, planar, and electron-withdrawing TzTz building blocks in polymeric architectures enhances their light-harvesting ability, the separation and mobility of charge carriers, favorable energy level alignments, and surface properties due to the extension of π-conjugated structures, strong intermolecular π-π stacking, and high oxidative stability. Considering the intriguing applications of TzTz-based conjugated polymers in the above-mentioned areas, this review comprehensively discusses how the structure-activity relationship can advance these applications. To our knowledge, no review has yet summarized the structure-optoelectronic, morphological, and thermal property relationships and applications of TzTz-based conjugated polymers. Hence, this review will be helpful in designing more efficient TzTz-based conjugated polymers for various future applications.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"172 ","pages":"Article 102054"},"PeriodicalIF":26.1,"publicationDate":"2025-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145516130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-13DOI: 10.1016/j.progpolymsci.2025.102053
Daniel A. Heinze , Arit Das , Christopher B. Williams , Claire McIlroy , Amy M. Peterson , Michael J. Bortner
Semicrystalline polymers pose unique advantages and challenges in translating from small-format extrusion-based additive manufacturing (EB-AM) to large-format EB-AM due to their complex crystallization behavior and the spatio-temporal thermo-mechanical property variations they exhibit during printing and solidification. In this work, we aim to synthesize the current state-of-the-art regarding semicrystalline polymers in EB-AM, with a focus on how polymer physics control process-structure-property relationships at disparate length- and time scales. The impact of crystallization kinetics, polymer chain mobility, and entanglement density on the evolution of printed microstructure and extent of interlayer diffusion is explored, thereby tying the link among molecular scale phenomena, mesoscale morphology development, and macroscopic printed part properties. The widely different thermal and shear histories encountered during small- and large-format EB-AM can have a profound effect on the chain stretch and orientation, crystallization behavior, rheological response, and residual stress state during printing. Strategies to mitigate the exacerbated volumetric shrinkage and warpage issues for semicrystalline polymers in EB-AM through material design and processing modifications are highlighted. Such approaches are critical to not only ensure dimensionally accurate parts but also minimize anisotropy and poor interlayer adhesion. Routes to monitor spherulitic growth and melt-viscosity variations during EB-AM, such as in-situ scattering techniques and infrared thermography, provide insights needed to achieve consistent and reliable processing. Finally, we identify the fundamental research gaps that currently plague semicrystalline polymers in EB-AM and highlight the importance of developing predictive multiscale modeling frameworks coupled with formulation of next-generation material systems and process monitoring capabilities to enable widespread adoption of the technique.
{"title":"Realizing semicrystalline polymer physics across disparate processing scales: From desktop extrusion to large-format additive manufacturing","authors":"Daniel A. Heinze , Arit Das , Christopher B. Williams , Claire McIlroy , Amy M. Peterson , Michael J. Bortner","doi":"10.1016/j.progpolymsci.2025.102053","DOIUrl":"10.1016/j.progpolymsci.2025.102053","url":null,"abstract":"<div><div>Semicrystalline polymers pose unique advantages and challenges in translating from small-format extrusion-based additive manufacturing (EB-AM) to large-format EB-AM due to their complex crystallization behavior and the spatio-temporal thermo-mechanical property variations they exhibit during printing and solidification. In this work, we aim to synthesize the current state-of-the-art regarding semicrystalline polymers in EB-AM, with a focus on how polymer physics control process-structure-property relationships at disparate length- and time scales. The impact of crystallization kinetics, polymer chain mobility, and entanglement density on the evolution of printed microstructure and extent of interlayer diffusion is explored, thereby tying the link among molecular scale phenomena, mesoscale morphology development, and macroscopic printed part properties. The widely different thermal and shear histories encountered during small- and large-format EB-AM can have a profound effect on the chain stretch and orientation, crystallization behavior, rheological response, and residual stress state during printing. Strategies to mitigate the exacerbated volumetric shrinkage and warpage issues for semicrystalline polymers in EB-AM through material design and processing modifications are highlighted. Such approaches are critical to not only ensure dimensionally accurate parts but also minimize anisotropy and poor interlayer adhesion. Routes to monitor spherulitic growth and melt-viscosity variations during EB-AM, such as <em>in-situ</em> scattering techniques and infrared thermography, provide insights needed to achieve consistent and reliable processing. Finally, we identify the fundamental research gaps that currently plague semicrystalline polymers in EB-AM and highlight the importance of developing predictive multiscale modeling frameworks coupled with formulation of next-generation material systems and process monitoring capabilities to enable widespread adoption of the technique.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"172 ","pages":"Article 102053"},"PeriodicalIF":26.1,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145508915","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-13DOI: 10.1016/j.progpolymsci.2025.102055
Premkumar Kothavade , Abdullah Kafi , Kadhiravan Shanmuganathan , Stuart Bateman
High performance polymers (HPPs), particularly polyimides (PIs), including both thermosetting and thermoplastic types, exhibit remarkable properties such as exceptional mechanical properties, outstanding thermal stability, and inherent flame retardancy. PIs are lightweight and potentially economical alternatives to metal based materials used in demanding applications, such as aerospace, transportation, and defense. However, processing PIs into the desired complex shapes is a significant challenge owing to their high melting temperature, high melt flow viscosity, and very narrow processing temperature window. Additive manufacturing (AM) techniques present an important avenue for processing such materials and emerged as a revolutionary approach to overcome these limitations, offering unprecedented design flexibility, reduced material waste, and the capability for rapid prototyping and production. Despite these advantages, AM of PIs has received considerably less attention, primarily due to significant processing challenges including material printability, thermal management complexities, and dimensional accuracy challenges that have hindered further advancements in this field. This comprehensive review explores the evolution and current status of polyimides additive manufacturing, providing insights into their chemistry, structural modifications, and detailed structure-property relationships. Various AM techniques including vat photopolymerization, material extrusion, direct ink writing, material jetting along with hybrid and emerging approaches are critically discussed, highlighting recent innovations, key challenges, and strategic solutions to enhance processing capabilities. Furthermore, the review identifies prospective research directions, emphasizing the potential for multifunctional and stimuli-responsive polyimides that could revolutionize next-generation applications. Overall, this review aims to stimulate further advancements in polyimide based additive manufacturing, fostering its broader industrial adoption and facilitating significant developments in high performance polymer technology.
{"title":"High performance polyimides for additive manufacturing: A critical review","authors":"Premkumar Kothavade , Abdullah Kafi , Kadhiravan Shanmuganathan , Stuart Bateman","doi":"10.1016/j.progpolymsci.2025.102055","DOIUrl":"10.1016/j.progpolymsci.2025.102055","url":null,"abstract":"<div><div>High performance polymers (HPPs), particularly polyimides (PIs), including both thermosetting and thermoplastic types, exhibit remarkable properties such as exceptional mechanical properties, outstanding thermal stability, and inherent flame retardancy. PIs are lightweight and potentially economical alternatives to metal based materials used in demanding applications, such as aerospace, transportation, and defense. However, processing PIs into the desired complex shapes is a significant challenge owing to their high melting temperature, high melt flow viscosity, and very narrow processing temperature window. Additive manufacturing (AM) techniques present an important avenue for processing such materials and emerged as a revolutionary approach to overcome these limitations, offering unprecedented design flexibility, reduced material waste, and the capability for rapid prototyping and production. Despite these advantages, AM of PIs has received considerably less attention, primarily due to significant processing challenges including material printability, thermal management complexities, and dimensional accuracy challenges that have hindered further advancements in this field. This comprehensive review explores the evolution and current status of polyimides additive manufacturing, providing insights into their chemistry, structural modifications, and detailed structure-property relationships. Various AM techniques including vat photopolymerization, material extrusion, direct ink writing, material jetting along with hybrid and emerging approaches are critically discussed, highlighting recent innovations, key challenges, and strategic solutions to enhance processing capabilities. Furthermore, the review identifies prospective research directions, emphasizing the potential for multifunctional and stimuli-responsive polyimides that could revolutionize next-generation applications. Overall, this review aims to stimulate further advancements in polyimide based additive manufacturing, fostering its broader industrial adoption and facilitating significant developments in high performance polymer technology.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"172 ","pages":"Article 102055"},"PeriodicalIF":26.1,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145499301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-13DOI: 10.1016/j.progpolymsci.2025.102056
Run-Tan Gao , Bing-Hui Duan , Yang Zong , Na Liu , Zong-Quan Wu
The exquisite helix in biological macromolecules is indispensable to realize the living functions. With the aims to mimic natural helices and also to develop chiral materials, controlled synthesis of helical polymers has been a long-term of hot research topic. In the context of reported helical polymers, helical polyisocyanide is constituted of carbon-carbon single bands and bears substituent on each backbone atom and has exhibited significant potentials in chiral recognition, asymmetric catalysis, enantiomer separation, circularly polarized luminescence, and so on. Thus, controlled synthesis of helical polyisocyanide has attracted considerable research interest. This review delves into the controlled polymerization of isocyanides to synthesize helical polyisocyanides. We first summarized the advancements in catalysts and living polymerization strategies that have enabled the precise synthesis of polyisocyanides with controlled handedness, desired molar mass, and low polydispersity. We then discussed the synthesis of block copolymers containing polyisocyanides segments and topological polyisocyanides, including star-shaped polymers, bottlebrush polymers, and cross linked polyisocyanides. The intriguing properties related to these topological structures and helical chirality were also discussed in details. The supramolecular block copolymers, miktoarm star polymers, and bottlebrush polymers containing helical polyisocyanide blocks connected via supramolecular interactions were also summarized and discussed. In addition to the controlled synthesis of helical polyisocyanides, we reviewed the applications of polyisocyanides in chiral recognition, asymmetric catalysis, self-assembly, and drug delivery, by emphasizing the helical chirality in enantioselective processes and smart materials. Lastly, we summarized the remaining challenges and future perspectives in this field, including the requirements for more efficient catalysts and polymerization methods for optically active helical polyisocyanides, and the potential applications of helical polyisocyanides in emerging areas such as sustainable materials, energy, and environmental remediation. This review underscores the significant progress in the field of helical polyisocyanides and their potential to impact a wide range of scientific and technological fields.
{"title":"Controlled isocyanide polymerization: Towards helical polymers with chiral functions","authors":"Run-Tan Gao , Bing-Hui Duan , Yang Zong , Na Liu , Zong-Quan Wu","doi":"10.1016/j.progpolymsci.2025.102056","DOIUrl":"10.1016/j.progpolymsci.2025.102056","url":null,"abstract":"<div><div>The exquisite helix in biological macromolecules is indispensable to realize the living functions. With the aims to mimic natural helices and also to develop chiral materials, controlled synthesis of helical polymers has been a long-term of hot research topic. In the context of reported helical polymers, helical polyisocyanide is constituted of carbon-carbon single bands and bears substituent on each backbone atom and has exhibited significant potentials in chiral recognition, asymmetric catalysis, enantiomer separation, circularly polarized luminescence, and so on. Thus, controlled synthesis of helical polyisocyanide has attracted considerable research interest. This review delves into the controlled polymerization of isocyanides to synthesize helical polyisocyanides. We first summarized the advancements in catalysts and living polymerization strategies that have enabled the precise synthesis of polyisocyanides with controlled handedness, desired molar mass, and low polydispersity. We then discussed the synthesis of block copolymers containing polyisocyanides segments and topological polyisocyanides, including star-shaped polymers, bottlebrush polymers, and cross linked polyisocyanides. The intriguing properties related to these topological structures and helical chirality were also discussed in details. The supramolecular block copolymers, miktoarm star polymers, and bottlebrush polymers containing helical polyisocyanide blocks connected via supramolecular interactions were also summarized and discussed. In addition to the controlled synthesis of helical polyisocyanides, we reviewed the applications of polyisocyanides in chiral recognition, asymmetric catalysis, self-assembly, and drug delivery, by emphasizing the helical chirality in enantioselective processes and smart materials. Lastly, we summarized the remaining challenges and future perspectives in this field, including the requirements for more efficient catalysts and polymerization methods for optically active helical polyisocyanides, and the potential applications of helical polyisocyanides in emerging areas such as sustainable materials, energy, and environmental remediation. This review underscores the significant progress in the field of helical polyisocyanides and their potential to impact a wide range of scientific and technological fields.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"172 ","pages":"Article 102056"},"PeriodicalIF":26.1,"publicationDate":"2025-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145508913","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-01DOI: 10.1016/j.progpolymsci.2025.102042
Takuya Katashima
Transient polymer networks, formed by polymer chains linked through reversible bonds, exhibit time-dependent viscoelasticity, that bridges solid-like elasticity and liquid-like flow. These materials have attracted increasing attention due to their potential for self-healing, toughness, and recyclability. Classical models, such as the Green–Tobolsky and Tanaka–Edwards theories, primarily describe stress relaxation by bond dissociation kinetics, assuming homogeneous equilibrium structures and small deformations. However, real-world applications often involve large, dynamic strains, where nonlinear viscoelasticity, finite extensibility, and spatial flow heterogeneity dominate. Conventional systems frequently suffer from structural and dynamic heterogeneities, complicating efforts to connect molecular dynamics with bulk mechanical behavior. To address these challenges, recent studies have developed a model transient network—Tetra-PEG slime—constructed from tetrafunctional polyethylene glycol (PEG) precursors connected via dynamic covalent bonds between phenylboronic acid and diol groups. This system allows for precise control over network connectivity, bond lifetime, and strand architecture, while minimizing unwanted heterogeneities. Leveraging this model, researchers have applied a multimodal approach, combining surface plasmon resonance (SPR), macroscopic rheology, two-dimensional rheo-optics, and particle-tracking microrheology to investigate relaxation behavior across linear and nonlinear regimes. These efforts have uncovered clear correlations between molecular kinetics and viscoelastic relaxation, time–strain separability under large deformations, damping mechanisms tied to strand pullout, and emergent spatial heterogeneity near the percolation threshold. This review summarizes these findings and explores their implications for the rational design of transient networks with programmable mechanical properties, while offering perspectives on future integrations with theory and simulation.
{"title":"Precise analysis of rheological properties of transient network using model materials","authors":"Takuya Katashima","doi":"10.1016/j.progpolymsci.2025.102042","DOIUrl":"10.1016/j.progpolymsci.2025.102042","url":null,"abstract":"<div><div>Transient polymer networks, formed by polymer chains linked through reversible bonds, exhibit time-dependent viscoelasticity, that bridges solid-like elasticity and liquid-like flow. These materials have attracted increasing attention due to their potential for self-healing, toughness, and recyclability. Classical models, such as the Green–Tobolsky and Tanaka–Edwards theories, primarily describe stress relaxation by bond dissociation kinetics, assuming homogeneous equilibrium structures and small deformations. However, real-world applications often involve large, dynamic strains, where nonlinear viscoelasticity, finite extensibility, and spatial flow heterogeneity dominate. Conventional systems frequently suffer from structural and dynamic heterogeneities, complicating efforts to connect molecular dynamics with bulk mechanical behavior. To address these challenges, recent studies have developed a model transient network—Tetra-PEG slime—constructed from tetrafunctional polyethylene glycol (PEG) precursors connected via dynamic covalent bonds between phenylboronic acid and diol groups. This system allows for precise control over network connectivity, bond lifetime, and strand architecture, while minimizing unwanted heterogeneities. Leveraging this model, researchers have applied a multimodal approach, combining surface plasmon resonance (SPR), macroscopic rheology, two-dimensional rheo-optics, and particle-tracking microrheology to investigate relaxation behavior across linear and nonlinear regimes. These efforts have uncovered clear correlations between molecular kinetics and viscoelastic relaxation, time–strain separability under large deformations, damping mechanisms tied to strand pullout, and emergent spatial heterogeneity near the percolation threshold. This review summarizes these findings and explores their implications for the rational design of transient networks with programmable mechanical properties, while offering perspectives on future integrations with theory and simulation.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"171 ","pages":"Article 102042"},"PeriodicalIF":26.1,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145424122","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-29DOI: 10.1016/j.progpolymsci.2025.102041
Zhiqiang Cao, Yunfei Wang, Xiaodan Gu
Neutron scattering techniques are powerful tools for characterizing the structure and dynamics of materials. They are particularly well-suited for studying polymer systems, which are typically rich in hydrogen. By combining neutron scattering with deuterium labeling, researchers can unravel complex structural features and dynamic behaviors within these systems. This review highlights recent advances in neutron scattering methods for probing the hierarchical structures and dynamics of polymeric materials, with a focus on developments over the past decade. We begin by discussing elastic techniques—such as small-angle neutron scattering (SANS)—used to examine polymer organization in both solution and solid states. Subsequently, we address the application of neutron reflectometry (NR) and grazing-incidence neutron scattering (GINS) techniques to the study of polymer thin-film structures. Next, we explore inelastic and quasi-elastic techniques, including inelastic neutron scattering (INS), quasi-elastic neutron scattering (QENS), and neutron spin echo (NSE), which provide insight into polymer dynamics across a broad range of time and length scales. Finally, we consider future directions for neutron scattering in soft matter research, emphasizing emerging methodologies and next-generation neutron sources that promise to further advance our understanding of these complex systems.
{"title":"Recent advancements in neutron scattering techniques for quantifying the structure and dynamics of polymers","authors":"Zhiqiang Cao, Yunfei Wang, Xiaodan Gu","doi":"10.1016/j.progpolymsci.2025.102041","DOIUrl":"10.1016/j.progpolymsci.2025.102041","url":null,"abstract":"<div><div>Neutron scattering techniques are powerful tools for characterizing the structure and dynamics of materials. They are particularly well-suited for studying polymer systems, which are typically rich in hydrogen. By combining neutron scattering with deuterium labeling, researchers can unravel complex structural features and dynamic behaviors within these systems. This review highlights recent advances in neutron scattering methods for probing the hierarchical structures and dynamics of polymeric materials, with a focus on developments over the past decade. We begin by discussing elastic techniques—such as small-angle neutron scattering (SANS)—used to examine polymer organization in both solution and solid states. Subsequently, we address the application of neutron reflectometry (NR) and grazing-incidence neutron scattering (GINS) techniques to the study of polymer thin-film structures. Next, we explore inelastic and quasi-elastic techniques, including inelastic neutron scattering (INS), quasi-elastic neutron scattering (QENS), and neutron spin echo (NSE), which provide insight into polymer dynamics across a broad range of time and length scales. Finally, we consider future directions for neutron scattering in soft matter research, emphasizing emerging methodologies and next-generation neutron sources that promise to further advance our understanding of these complex systems.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"171 ","pages":"Article 102041"},"PeriodicalIF":26.1,"publicationDate":"2025-10-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145384009","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Proteins are intricate biomolecules composed of amino acids that perform a wide array of essential biological functions. In recent years, considerable efforts have been made to replicate their structural and functional complexity through synthetic approaches. Among these, the ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydride (NCA) has emerged as the most effective method for synthesizing high-molecular-weight polypeptides on a larger scale. Advances in controlled polymerization techniques, alongside improvements in NCA monomer synthesis, have significantly enhanced the precision and efficiency of polypeptide production. These developments have spurred progress in peptide engineering, enabling the creation of multiblock, branched, and functionally diverse polypeptides, including those incorporating non-natural motifs. Such modifications mimic post-translational modifications found in natural proteins, underscoring the increasing relevance of synthetic polypeptides in designing next-generation functional materials. Synthetic polypeptides and their potential in biomaterial applications have emerged as a highly active research area, particularly following the advent of controlled ROP of NCA monomers. In this article, we present a comprehensive overview of recent progress in the field, primarily over the past decade, emphasizing key developments and emerging directions. Furthermore, it explores how peptide engineering facilitates the development of tailor-made polypeptides with tunable properties, culminating in a discussion on their potential in self-assembly and biomaterials applications.
{"title":"Recent advances in the molecular engineering of synthetic polypeptides: Design, synthesis, functionality, and biological applications","authors":"Prabir Maity , Arjun Singh Bisht , Ankita Kumari , Raj Kumar Roy","doi":"10.1016/j.progpolymsci.2025.102040","DOIUrl":"10.1016/j.progpolymsci.2025.102040","url":null,"abstract":"<div><div>Proteins are intricate biomolecules composed of amino acids that perform a wide array of essential biological functions. In recent years, considerable efforts have been made to replicate their structural and functional complexity through synthetic approaches. Among these, the ring-opening polymerization (ROP) of α-amino acid N-carboxyanhydride (NCA) has emerged as the most effective method for synthesizing high-molecular-weight polypeptides on a larger scale. Advances in controlled polymerization techniques, alongside improvements in NCA monomer synthesis, have significantly enhanced the precision and efficiency of polypeptide production. These developments have spurred progress in peptide engineering, enabling the creation of multiblock, branched, and functionally diverse polypeptides, including those incorporating non-natural motifs. Such modifications mimic post-translational modifications found in natural proteins, underscoring the increasing relevance of synthetic polypeptides in designing next-generation functional materials. Synthetic polypeptides and their potential in biomaterial applications have emerged as a highly active research area, particularly following the advent of controlled ROP of NCA monomers. In this article, we present a comprehensive overview of recent progress in the field, primarily over the past decade, emphasizing key developments and emerging directions. Furthermore, it explores how peptide engineering facilitates the development of tailor-made polypeptides with tunable properties, culminating in a discussion on their potential in self-assembly and biomaterials applications.</div></div>","PeriodicalId":413,"journal":{"name":"Progress in Polymer Science","volume":"171 ","pages":"Article 102040"},"PeriodicalIF":26.1,"publicationDate":"2025-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145314808","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}