Polymer Chemistry最新文献

{"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}

{"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}

{"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}

{"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}

{"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}

{"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}

{"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}

{"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}

{"title":"Synthesis Strategy and Application of Multifunctional Antifreeze Hydrogels","authors":"Hongyu Jiang, Haotian Yang, Siyue Qiu, Jialiang Nie, Meizhu Qin, Zihan Wang, Xinfeng Yang, Shaohua Zhang, Gang Liu, Wenlong Xu","doi":"10.1039/d5py00346f","DOIUrl":"https://doi.org/10.1039/d5py00346f","url":null,"abstract":"Hydrogels, renowned for their exceptional mechanical properties, superior swelling capacity, excellent biocompatibility, and notable ionic conductivity, have demonstrated significant potential across diverse fields, including biomedicine, food industry, and flexible electronics. However, conventional hydrogels face a significant limitation in cold environments: the internal water within these materials tends to freeze at low temperatures. This freezing process not only compromises the structural integrity of the hydrogels but also drastically reduces their performance, severely limiting their utility in cold environments. As a result, the development of antifreeze hydrogels has become a critical area of research. These advanced hydrogels are designed to effectively inhibit the formation and growth of ice crystals, enabling them to maintain optimal performance even under low-temperature conditions. This article provides a comprehensive and in-depth review of the current research progress on antifreeze hydrogels, meticulously analyzing their antifreeze mechanisms and synthesis strategies. Furthermore, we systematically discuss the unique properties of antifreeze hydrogels and their specific applications across various fields. Finally, we present insights into the current challenges and future directions for the development of antifreeze hydrogels.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"109 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866148","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}

{"title":"Impact of imine bonds on the electronic properties of degradable carotenoid-based conjugated polymers","authors":"Azalea Uva, Yaejin Kim, Sofia Michailovich, Sung Yuan Hsu, David C. Bain, Shine Han Huang, Andrew J Musser, Helen Tran","doi":"10.1039/d5py00235d","DOIUrl":"https://doi.org/10.1039/d5py00235d","url":null,"abstract":"Carotenoids are ideal building blocks for degradable π-conjugated polymers due to their intrinsic single-molecule conductance and well-documented degradation pathways. Previously, we reported a carotenoid-based polymer, p(CP-hexyl), which incorporated a cleavable imine linker enabling degradation via acid hydrolysis or sunlight; however, there was limited insight into its electronic properties. In this current study, we compare the optoelectronic and photophysical properties of p(CP-hexyl) with a structural analog, caro-PPV, which replaces the imine bonds with vinylene groups, to improve charge transport while maintaining degradability. Ultraviolet-visible (UV-Vis) spectroscopy, density functional theory (DFT), and transient absorption (TA) spectroscopy provided a comprehensive understanding of these polymers’ optoelectronic properties. Further, chemical doping and oxidative degradation were evaluated using FeCl3 and trifluoroacetic acid (TFA), unveiling differences in radical formation and degradation mechanisms for both carotenoid-based polymers. Lastly, charge carrier mobility measurements in organic field-effect transistors (OFETs) unveiled caro-PPV’s superior semiconductor performance, with mobilities 10<small>³</small> -10<small>⁴</small> times greater than p(CP-hexyl). These findings highlight the potential of carotenoid monomers in the design of π-conjugated polymers for degradable electronics.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"2 1 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866146","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}