Polymer Chemistry最新文献

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Photoactive Complex Enabled Photo-controlled RAFT Polymerization with CF3 Radical 光活性配合物使CF3自由基光控RAFT聚合
IF 4.6 2区 化学
Polymer Chemistry Pub Date : 2025-05-06 DOI: 10.1039/d5py00291e
Xiang Li, Yong-Liang Tu, Zhi-Xiang Wang, Xiang-Yu Chen
{"title":"Photoactive Complex Enabled Photo-controlled RAFT Polymerization with CF3 Radical","authors":"Xiang Li, Yong-Liang Tu, Zhi-Xiang Wang, Xiang-Yu Chen","doi":"10.1039/d5py00291e","DOIUrl":"https://doi.org/10.1039/d5py00291e","url":null,"abstract":"Recent advances in photo-controlled reversible addition-fragmentation chain-transfer (RAFT) polymerization have largely focused on the developments of initiators and chain-transfer agents. In this work, we report a photocatalytic platform enabling photo-controlled RAFT polymerization of acrylate-based monomers. The system employs readily accessible N-heterocyclic nitrenium as the photocatalyst, commercially available CF₃SO₂Cl as the CF₃ radical source, and a bis(trithiocarbonate) disulfide as the chain-transfer agent. This approach leverages a photoactive complex formed between the N-heterocyclic nitrenium and CF₃SO₂Cl to initiate polymerization, enabling polymerization with precise molar mass control and low dispersity.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143910516","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}
引用次数: 0
Synthesis of Butadiene-Derived Polyolefin Graft Copolymers and Their Crystallization Behaviors 丁二烯衍生聚烯烃接枝共聚物的合成及其结晶行为
IF 4.6 2区 化学
Polymer Chemistry Pub Date : 2025-05-02 DOI: 10.1039/d5py00243e
Jin Qian, Zhe Qiang
{"title":"Synthesis of Butadiene-Derived Polyolefin Graft Copolymers and Their Crystallization Behaviors","authors":"Jin Qian, Zhe Qiang","doi":"10.1039/d5py00243e","DOIUrl":"https://doi.org/10.1039/d5py00243e","url":null,"abstract":"The ability to synthesize polyolefin-based copolymers with controlled chemical composition and chain microstructure provides great opportunities for their use in compatibilizing polyolefin blends, particularly including polyethylene (PE) and polypropylene (PP), to address their waste recycling challenges. In this study, polyolefin graft copolymers comprising semicrystalline PE side chain and amorphous polyethylethylene (PEE) backbone were synthesized by grafting amine-terminated 1,4-polybutadiene (PB) onto carboxyl-grafted 1,2-PB, followed by hydrogenation. A suite of characterization tehcniques were employed to assess the degree of functionalization, polymer microstructure, and molecular weight of these graft copolymers containing different side chain lengths and graft densities. Moreover, since most commodity polyolefins are semicrystalline, understanding the crystallization behavior of these polyolefin copolymers is important. Specifically, the non-isothermal crystallization behavior of these graft copolymers was investigated using differential scanning calorimetry (DSC) and the Jeziorny-modified Avrami model. Both the graft copolymers and their homopolymer grafts exhibited heterogeneous nucleation with predominantly one-dimensional crystal growth and similar overall crystallization rates. However, PEE-g-PE10k and PEE-g-PE5k showed opposite trends in activation energy, likely due to a competition between nucleation facilitation and crystal growth restriction introduced by the graft structure. A preliminary investigation indicates that the incorporation of these graft copolymers into mixed PE:PP (50:50) blends can lead to improved mechanical performance. This study reveals the impact of graft architecture on the crystallization behavior and kinetics of polyolefin-based blend compatibilizers.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"111 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898149","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}
引用次数: 0
Large Aromatic Amide Helices via Living Polycondensation 通过活性缩聚形成的大芳酰胺螺旋
IF 4.6 2区 化学
Polymer Chemistry Pub Date : 2025-05-02 DOI: 10.1039/d5py00275c
Dinh Phuong Trinh Nguyen, Saquib Farooq, Nicoleta Meyer, Andreas F.M. Kilbinger
{"title":"Large Aromatic Amide Helices via Living Polycondensation","authors":"Dinh Phuong Trinh Nguyen, Saquib Farooq, Nicoleta Meyer, Andreas F.M. Kilbinger","doi":"10.1039/d5py00275c","DOIUrl":"https://doi.org/10.1039/d5py00275c","url":null,"abstract":"We employ a living polymerization strategy and a crescent-shaped monomer to synthesize large aromatic amide helices with cavity sizes exceeding 1 nm. These polymeric foldamer helices are stabilized by a continuous strand of three-center hydrogen bonds, ensuring structural integrity. Our method efficiently yields polymeric helices of varying lengths while also producing macrocycles as side products when targeting higher molecular weights. The isolation and characterization of a 7-mer macrocycle provided key insights into the number of repeat units required to complete a full turn of the corresponding polymeric helix. Additionally, macrocycles were obtained in greater quantities by performing the polycondensation in the absence of an initiator. This straightforward and versatile approach paves the way for the development of novel materials with potential applications in host-guest chemistry, catalysis, and molecular transport.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"70 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143898148","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}
引用次数: 0
Generation of Topologically Defined Linear and Cyclic DNA Bottle Brush Polymers via a Graft-to Approach 通过接枝到方法生成拓扑定义的线性和环状DNA瓶刷聚合物
IF 4.6 2区 化学
Polymer Chemistry Pub Date : 2025-05-01 DOI: 10.1039/d5py00082c
Nicholas Pierini, Wynter Paiva, Owen Durant, Aubrianna Dobbins, Matthew Currier, Ben Wheeler, James Vesenka, Nathan Oldenhuis
{"title":"Generation of Topologically Defined Linear and Cyclic DNA Bottle Brush Polymers via a Graft-to Approach","authors":"Nicholas Pierini, Wynter Paiva, Owen Durant, Aubrianna Dobbins, Matthew Currier, Ben Wheeler, James Vesenka, Nathan Oldenhuis","doi":"10.1039/d5py00082c","DOIUrl":"https://doi.org/10.1039/d5py00082c","url":null,"abstract":"Herein, we report a graft-to approach for synthesizing linear and circular double-stranded DNA (dsDNA) bottlebrush polymers (BBP). Using a bioreactor, plasmid DNA (pDNA) serves as an inexpensive and abundant source of circular, biodegradable, and unimolecular polymers. pDNA is easily converted to the linear isoform through enzymatic restriction, providing access to polymeric backbones with distinct topological states. DNA is grafted with polyethylene glycol monomethyl ether chloroethylamines (mPEGCEA) to yield DNA BBPs. Importantly this PEGylation occurs rapidly under ambient conditions in aqueous buffer. By varying the molecular weight of mPEGCEA (Mw = 750, 2000, 5000 Da) and the concentration relative to µmol of nucleotides, different brush arm densities and lengths were achieved with both linear and macrocyclic DNA backbones. Analysis of the DNA BBPs was achieved through agarose gel electrophoresis, which showed graft densities of up to 68.7% and 74.8% for linear and ring DNA respectively. The grafting process does not alter base pairing or circularity as determined using atomic force microscopy. Shear rheology was used to compare the mechanical response of 1% wt / wt solutions of the ring and linear DNA BBPs to their un-alkylated forms. Linear DNA BBPs exhibited a lower shear modulus versus linear DNA, which is expected due to the increased persistence length and decreased ability to interpenetrate associated with the attachment of polymer arms. However, the circular DNA BBPs exhibited a universally higher shear modulus versus the alkylated sample suggesting an increase in interchain interaction via addition of polymer arms. Finally, the increased steric encumbrance of the DNA BBPs slows enzymatic degradation, potentially providing a general method to increase stability of DNA constructs towards nuclease.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"72 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893791","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}
引用次数: 0
Effective photoinitiating systems using citric acid-derived chromophores as photosensitizers for 3D bio-printing applications 有效的光引发系统使用柠檬酸衍生的发色团作为3D生物打印应用的光敏剂
IF 4.6 2区 化学
Polymer Chemistry Pub Date : 2025-05-01 DOI: 10.1039/d4py01409j
Katarzyna Starzak, Alicja Wysocka, Łukasz Waluda, Patryk Szymaszek, Wiktor Kasprzyk, Joanna Ortyl
{"title":"Effective photoinitiating systems using citric acid-derived chromophores as photosensitizers for 3D bio-printing applications","authors":"Katarzyna Starzak, Alicja Wysocka, Łukasz Waluda, Patryk Szymaszek, Wiktor Kasprzyk, Joanna Ortyl","doi":"10.1039/d4py01409j","DOIUrl":"https://doi.org/10.1039/d4py01409j","url":null,"abstract":"The growing interest in the use of naturally derived compounds, associated with the increasing focus on green chemistry principles in various fields of chemical technology, is also evident in the development of light-cured resins for 3D printing. Therefore, in this work, four fluorophores formed alongside carbon dots as one of the products of the reaction between citric acid and specific β-amines were comprehensively studied. These studies facilitated the detailed optical characterization of the compounds, which in turn led to a better understanding of the electron transfer mechanisms accompanying the initiation of photopolymerization processes. In addition, cyclic voltammetry and photostability studies enabled a preliminary assessment of the applicability of the fluorophores as photosensitizers of commercially available diphenyl iodonium salts (SpeedCure 938®). FT-IR analyses and supporting photorheology measurements made it possible to determine the kinetics of the photopolymerization process and demonstrate the influence of the water content (non-reactive agent) on its course. Finally, it was possible to develop resins for 3D printing with low viscosity for use in the stereolithography (SLA) method and high viscosity for use in the direct ink writing (DIW) method enriched with light-curing of the finished pattern.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"20 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143893697","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}
引用次数: 0
Crosslinking of polymers from monofunctional acrylates via C–H bond activation 通过C-H键激活单功能丙烯酸酯聚合物的交联
IF 4.6 2区 化学
Polymer Chemistry Pub Date : 2025-04-29 DOI: 10.1039/d5py00239g
Junkyu Kim, Seokju Lee, Youngjoo Park, Woojin Jeon, Min Sang Kwon
{"title":"Crosslinking of polymers from monofunctional acrylates via C–H bond activation","authors":"Junkyu Kim, Seokju Lee, Youngjoo Park, Woojin Jeon, Min Sang Kwon","doi":"10.1039/d5py00239g","DOIUrl":"https://doi.org/10.1039/d5py00239g","url":null,"abstract":"Cross–linked acrylic polymers are highly valued for their durability and chemical resistance, making them extensively used in various applications and industries. Typically, they are synthesized by adding crosslinkers (multifunctional monomers or oligomers) or through post-treatment processes. However, our preliminary studies indicated that even monofunctional acrylic monomers can form cross–linked structures. The formation of these cross–linked structures is thought to result from a chain transfer mechanism involving hydrogen atom transfer (HAT) between monomer substituents and radicals. Despite this, the process has not been thoroughly analyzed, and few studies have applied this concept to the design of polymer networks. To clarify this phenomenon, we conducted a series of screening experiments using ten widely–used monomers and three different photoinitiation systems, discovering that 2–hydroxyethyl acrylate (HEA), 4–hydroxybutyl acrylate (HBA), and 2–[2–(2–methoxyethoxy)ethoxy]ethyl acrylate (MEEEA) exhibited superior crosslinking capabilities. Furthermore, quantum chemical calculations were employed to elucidate why these specific monomers excel in forming cross–linked networks. Assuming the propagating acryl radical acts as the hydrogen acceptor for HAT, it was found that the reactions occurring in the substituents of MEEEA and under hydrogen bonding conditions in HEA and HBA are thermodynamically stable. Consequently, the cross–linked structures formed by monofunctional acrylates were determined to be due to radicals generated at the substituents of the monomers. This enhanced understanding offers a new paradigm in the synthesis of cross–linked polymers, expanding their potential across diverse applications.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"8 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143884960","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}
引用次数: 0
A Versatile Synthetic Strategy for Non-Symmetric Isoindigo Polymers via Modular Sidechain Engineering 基于模侧链工程的非对称等靛蓝聚合物多用途合成策略
IF 4.6 2区 化学
Polymer Chemistry Pub Date : 2025-04-29 DOI: 10.1039/d5py00289c
Rachael J. Warner, P. Blake St. Onge, Alyssa Shaw, Tiago Carneiro Gomes, Xiaodan Gu, Simon Rondeau-Gagné
{"title":"A Versatile Synthetic Strategy for Non-Symmetric Isoindigo Polymers via Modular Sidechain Engineering","authors":"Rachael J. Warner, P. Blake St. Onge, Alyssa Shaw, Tiago Carneiro Gomes, Xiaodan Gu, Simon Rondeau-Gagné","doi":"10.1039/d5py00289c","DOIUrl":"https://doi.org/10.1039/d5py00289c","url":null,"abstract":"Sidechain engineering is a powerful strategy for tailoring the intrinsic properties of semiconducting polymers, enabling precise modulation of structure-property relationships critical for organic electronic applications. Breaking symmetry via sidechain engineering—by incorporating two non-identical sidechains onto the conjugated backbone—is an emerging approach to control molecular stacking and polymer chain interactions. However, the fundamental impact of sidechain induced non-symmetry remains underexplored, limiting the full tunability and optimization of this design in soft organic electronics. In this work, we investigate the structure-property relationships of isoindigo-thienothiophene-based semiconducting polymers, employing a novel “lego-like” synthetic strategy for non-symmetric condensation of alkylated precursors. This method significantly enhances specificity, customizability, and reproducibility, facilitating the development of fully tunable systems. Using this approach, we synthesized a series of non-symmetric polymers with linear and branched aliphatic sidechains to evaluate their impact on polymer packing motifs and performance in organic field-effect transistors (OFETs). Multimodal characterization revealed that these non-symmetric polymers exhibit electronic properties comparable to their symmetric counterparts while demonstrating reduced crystallinity and low Young’s moduli, as shown by atomic force microscopy. Furthermore, increasing the carbon spacer length from 1 to 4 carbons in the branched chain moiety improved charge transport, achieving average hole mobilities of up to 0.12 cm²/Vs and 0.10 cm²/Vs for P[(iITT)(C1C10C12)(C12)] and P[(iITT)(C4C10C12)(C12)], respectively. Overall, this work establishes a straightforward and highly tunable approach for designing a library of non-symmetric isoindigo derivatives through sidechain engineering, providing precise control over nanoscale polymer structures in thin films and unlocks new pathways for enhancing the performance of organic electronic materials.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"18 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143884958","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}
引用次数: 0
Developing environmentally friendly fishing nets by integrating halogenated marine terpene with hydrogel polymers 将卤代海洋萜烯与水凝胶聚合物相结合,开发环保型渔网
IF 4.6 2区 化学
Polymer Chemistry Pub Date : 2025-04-28 DOI: 10.1039/d5py00263j
Daiki Osada, Yohei Kotsuchibashi, Kazumi Nimura, Yukimasa Yamagishi, Takashi Kamada
{"title":"Developing environmentally friendly fishing nets by integrating halogenated marine terpene with hydrogel polymers","authors":"Daiki Osada, Yohei Kotsuchibashi, Kazumi Nimura, Yukimasa Yamagishi, Takashi Kamada","doi":"10.1039/d5py00263j","DOIUrl":"https://doi.org/10.1039/d5py00263j","url":null,"abstract":"Barnacles (<em>Amphibalanus amphitrite</em>) and blue mussels (<em>Mytilus galloprovincialis</em>) cause significant damage to ship hulls and fishing nets. To address these issues, organotin compounds such as tributyltin oxide have historically been used as antifouling agents. However, the use of organotin compounds has been globally restricted since 2008 owing to their environmental impact. Currently, copper-based compounds are being used as alternatives; however, concerns regarding their ecological effects remain unaddressed. While antifouling measures for ship hulls are well-established, effective solutions for fishing nets are still limited. To address this gap, we aimed to develop environmentally friendly fishing nets using halogenated marine terpene and hydrogel polymers. The marine red alga genus <em>Laurencia</em> is known to be a rich source of halogenated secondary metabolites with various bioactivities. Among these, laurinterol, a compound abundantly found in <em>Laurencia okamurae</em>, exhibits remarkable antifouling effects on sessile organisms. Additionally, polyvinyl alcohol (PVA)/poly methacrylic acid (poly(MAAc)) displays antifouling activity. Based on this, we attempted to create novel fishing nets with antifouling properties by combining the natural terpenoid laurinterol with PVA/poly(MAAc). The antifouling assay revealed that PVA/poly(MAAc) loading laurinterol suppressed byssal thread formation by 93%. This study presents data on the development of these environmentally friendly fishing nets, including detailed results of durability tests conducted in a large flowing water tank.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"17 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143880677","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}
引用次数: 0
Basic Concepts and Tools of Artificial Intelligence in Polymer Science 高分子科学中人工智能的基本概念和工具
IF 4.6 2区 化学
Polymer Chemistry Pub Date : 2025-04-28 DOI: 10.1039/d5py00148j
Khalid Ferji
{"title":"Basic Concepts and Tools of Artificial Intelligence in Polymer Science","authors":"Khalid Ferji","doi":"10.1039/d5py00148j","DOIUrl":"https://doi.org/10.1039/d5py00148j","url":null,"abstract":"In recent years, artificial intelligence (AI) has emerged as a transformative force across scientific disciplines, offering new ways to analyze data, predict material properties, and optimize processes. Yet, its integration into polymer science remains a challenge, as the field has traditionally relied on empirical methods and intuition-driven discovery. The complexity of polymer systems, combined with technical barriers and a lack of interdisciplinary training, has slowed AI adoption, leaving many researchers uncertain about where to begin. This perspective serves as an entry point for polymer scientists, introducing AI’s real-world applications, accessible tools, and key challenges. Rather than an exhaustive review for specialists, it aims to lower entry barriers and spark interdisciplinary dialogue, bridging the gap between conventional polymer research and data-driven innovation. As AI reshapes material discovery, those who embrace this transformation today will define the future of polymer science.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"17 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143880680","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}
引用次数: 0
Advanced Mechanical Properties of Amphiphilic Polymer Conetworks through Hierarchical Reinforcement with Peptides and Cellulose Nanocrystals 通过多肽和纤维素纳米晶体分层增强两亲性聚合物网络的先进力学性能
IF 4.6 2区 化学
Polymer Chemistry Pub Date : 2025-04-25 DOI: 10.1039/d4py01283f
Sara T. R. Velasquez, Daseul Jang, Jessica Ariel Thomas, Patrick Grysan, LaShanda Korley, Nico Bruns
{"title":"Advanced Mechanical Properties of Amphiphilic Polymer Conetworks through Hierarchical Reinforcement with Peptides and Cellulose Nanocrystals","authors":"Sara T. R. Velasquez, Daseul Jang, Jessica Ariel Thomas, Patrick Grysan, LaShanda Korley, Nico Bruns","doi":"10.1039/d4py01283f","DOIUrl":"https://doi.org/10.1039/d4py01283f","url":null,"abstract":"Amphiphilic polymer conetworks (APCNs) have been explored for various applications, including soft contact lenses, biomaterials, and membranes. They combine important properties of hydrogels and elastomers, including elasticity, transparency, and the capability to swell in water. Moreover, they also swell in organic solvents. However, their mechanical properties could be improved. We developed a two-level, bio-inspired, hierarchical reinforcement of APCNs using cellulose nanocrystals (CNCs) to reinforce peptide-reinforced APCNs formed from hydrophobic poly-β-benzyl-L-aspartate-block-polydimethylsiloxane-block-poly-β-benzyl-L-aspartate (PBLA-b-PDMS-b-PBLA) triblock copolymer crosslinkers and hydrophilic poly(2-hydroxy ethyl acrylate) (PHEA) chain segments. Bio-inspired peptide-polymer hybrids combine the structural hierarchy often found in natural materials with synthetic macromolecules, such as block copolymers with soft and hard segments, to enhance their mechanical properties. On the other hand, CNCs provide an additional means to dissipate mechanical energy in polymeric materials, thereby enhancing reinforcement. The key to homogeneously incorporating CNCs into the APCNs is the combination of hydrophobic CNCs (HCNCs) with peptide-blocks in the APCNs, exploiting the hydrogen bonding capability of the peptides to disperse the HCNCs. The effect of HCNCs on the ability of APCNs to swell in water and organic solvents, as well as on their thermal and mechanical properties, was characterized. Additionally, the nanostructure of the materials was analyzed via small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). The swellability of the HCNC-containing APCNs was independent of the HCNC concentration, and all samples were highly transparent. The ideal HCNC concentration, in terms of maximal stress, strain, toughness, and reinforcement, was found to be between 6 and 15 wt%. An increase in Young´s modulus of up to 500% and toughness of up to 200% was achieved. The hierarchical reinforcement also greatly strengthened the APCNs when swollen in water or n-hexane. Thus, HCNCs and peptide segments can be used to reinforce APCNs and to tailor their properties.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"129 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143872934","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}
引用次数: 0
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