BiomacromoleculesPub Date : 2025-10-11DOI: 10.1021/acs.biomac.5c01523
Yan Yan, Jinlong Chen, Qun-Liang Zhang, Youhua Tao
{"title":"Quaternized Nylon-6 Polymers via Ring-Opening Polymerization of Cyclic Lysine Derivatives: A Versatile Antibacterial Platform.","authors":"Yan Yan, Jinlong Chen, Qun-Liang Zhang, Youhua Tao","doi":"10.1021/acs.biomac.5c01523","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c01523","url":null,"abstract":"<p><p>Nylon-6, while commercially essential, has proven challenging to endow with persistent antibacterial properties due to the lack of efficient and facile synthetic approaches. Poly(ε-lysine) derivatives have attracted considerable research attention due to their structural backbone similarity to that of nylon-6. Capitalizing on this structural similarity, herein, we achieved hydrophobicity-tunable quaternized nylon-6 polymers through rational design of side-chain structures in lysine-derived cyclic monomers and controlled quaternization reactions. By precisely controlling the quaternization process, amphiphilic quaternized nylon-6 polymers with adjustable hydrophobicity and cationic charge density were successfully prepared, enabling systematic evaluation of their broad-spectrum antimicrobial properties. Notably, enhanced hydrophobicity was found to significantly improve antibacterial efficacy against both <i>Escherichia coli</i> and its biofilms, with the amphiphilic polymers demonstrating superior antimicrobial performance. Furthermore, these amphiphilic quaternized nylon-6 polymers exhibited a thermoresponsive behavior. This work proposes a new design strategy for antimicrobial nylon-6 polymers, enabling the simultaneous enhancement of antibacterial functionality and the incorporation of temperature-responsive properties.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145273134","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}
BiomacromoleculesPub Date : 2025-10-10DOI: 10.1021/acs.biomac.5c00955
Shahar Tevet, Michal Brodsky, Roey J Amir
{"title":"Unimer Exchange as a Tool for Programming Enzymatic Degradation through Micellar Dynamics.","authors":"Shahar Tevet, Michal Brodsky, Roey J Amir","doi":"10.1021/acs.biomac.5c00955","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00955","url":null,"abstract":"<p><p>A key challenge in designing enzyme-responsive micellar nanocarriers lies in balancing their stability and enzymatic degradation. While it has been widely assumed that the micelle-unimer exchange governs enzyme accessibility to the hydrophobic blocks, this relationship had not been directly demonstrated. Here, to uncover this long-assumed mechanistic link, we synthesized a set of triblock amphiphiles that convert by an in situ transition to diblock amphiphiles via reductive cleavage of a central disulfide bond. In parallel, hydrophobicity was independently tuned by modifying the aliphatic end-groups. Enzymatic degradation studies and Förster resonance energy transfer (FRET)-based exchange assays showed two consistent trends across all systems: increasing hydrophobicity led to slower micelle-unimer exchange and reduced enzymatic degradation rates, while transition to diblock consistently enhanced both. These results provide direct evidence that exchange kinetics govern enzymatic degradation and lay the mechanistic foundation for overcoming the stability-degradability barrier for enzyme-responsive micelles by applying architectural transitions as a molecular programming tool.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145273114","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}
BiomacromoleculesPub Date : 2025-10-10DOI: 10.1021/acs.biomac.5c01280
Sophie Laroque, James Harris, Santhosh Kalash Rajendrakumar, Vadim Vasilyev, Jaspreet Grewal, Robert Dallmann, Katherine E S Locock, Sébastien Perrier
{"title":"Cationic Antimicrobial Copolymers Reveal Immunomodulatory Properties in Lipopolysaccharide Stimulated Macrophages <i>in Vitro</i>.","authors":"Sophie Laroque, James Harris, Santhosh Kalash Rajendrakumar, Vadim Vasilyev, Jaspreet Grewal, Robert Dallmann, Katherine E S Locock, Sébastien Perrier","doi":"10.1021/acs.biomac.5c01280","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c01280","url":null,"abstract":"<p><p>Antimicrobial polymers, which have emerged as a promising alternative to antibiotics in the fight against antimicrobial resistance, are based on the design of cationic host defense peptides (CHDPs). Being part of the mammalian innate immune system, CHDPs possess both antimicrobial and immunoregulatory effects to manage bacterial infections. However, the immunomodulatory effects of antimicrobial polymers remain largely unexplored. Within this work, a library of 15 copolymers was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and their abilities to modulate pro-inflammatory pathways in lipopolysaccharide (LPS)-activated murine and human macrophages were investigated. We found that two diblock copolymers with cationic units copolymerized with either apolar or hydrophilic comonomers appeared to have anti-inflammatory activity through suppression of the activation of the nuclear factor kappa-light-chain enhancer of the activated B cell (NF-κB) signaling pathway, scavenging of reactive oxygen species, and reduced production of the pro-inflammatory cytokine interleukin-6 (IL-6). Furthermore, the cationic-apolar copolymer exhibits significant antimicrobial activity against <i>P. aeruginosa</i>. Thus, this promising copolymer holds potential as a dual-action therapeutic, effectively combating bacterial infections while curbing prolonged inflammation and thereby preventing sepsis at the site of infection.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145273103","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}
BiomacromoleculesPub Date : 2025-10-10DOI: 10.1021/acs.biomac.5c01378
Binhu Zou, Huizhi Qin, Lijun Ye, Yuanyuan Liang, Yongjin Li
{"title":"Recyclable Polysaccharide-Based Supramolecular Ionogel Electrolytes for Flexible Supercapacitors.","authors":"Binhu Zou, Huizhi Qin, Lijun Ye, Yuanyuan Liang, Yongjin Li","doi":"10.1021/acs.biomac.5c01378","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c01378","url":null,"abstract":"<p><p>Growing concerns over the environmental impact of fossil fuels have spurred the development of green and renewable materials for advanced electrochemical energy storage (EES) devices. Herein, a supramolecular ionogel polymer electrolyte based on glycol chitosan (GC) and imidazolium-based ionic liquids (IL) was developed. The as-fabricated optimized GC<sub>0.1</sub>-DMSO<sub>1</sub>/IL<sub>1</sub> supramolecular ionogel electrolytes exhibited an impressive conductivity of 4.4 mS cm<sup>-1</sup> at 25 °C, enabling a supercapacitor with a stable voltage window of 2.5 V. The supercapacitor exhibited a specific capacitance of 40.0 F g<sup>-1</sup> at a current density of 1 A g<sup>-1</sup> and achieved a maximum energy density of 22.2 Wh kg<sup>-1</sup> at a power density of 770 W kg<sup>-1</sup>. After over 700 charge-discharge cycles at 1 Ag<sup>-1</sup>, a capacitance retention of 94.7% was obtained. Moreover, the noncovalent bonded GC<sub>0.1</sub>-DMSO<sub>1</sub>/IL<sub>1</sub> could be easily recycled in water without generating any environmental hazards. This strategy offers new insights into the potential of polysaccharide-based supramolecular ionogel electrolytes for flexible and sustainable EES applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145273191","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}
BiomacromoleculesPub Date : 2025-10-09DOI: 10.1021/acs.biomac.5c01715
Yasuyuki Maki, Koichi Matsuo, Masahiko Annaka
{"title":"Effect of Sucrose and Sucralose on the Gelation of Gelatin.","authors":"Yasuyuki Maki, Koichi Matsuo, Masahiko Annaka","doi":"10.1021/acs.biomac.5c01715","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c01715","url":null,"abstract":"<p><p>It is well-known that sugars such as sucrose increase the gelling temperature and mechanical properties of gelatin. In this study, the effects of sucrose and sucralose, a sucrose derivative obtained by the chlorination of sucrose, on the gelation behavior of gelatin were investigated. The gelation of gelatin, monitored by rheological properties and helix formation, was enhanced by the addition of sucrose but inhibited by the addition of sucralose. For both sucrose and sucralose, the gelation kinetics were governed by the undercooling from the gelling temperature. To gain insights into the mechanisms by which sucrose and sucralose stabilize and destabilize gelatin gels, respectively, the preferential solvation of a collagen model peptide in aqueous solutions of sucrose or sucralose was measured using small-angle X-ray scattering. The observed preferential solvation behavior of the peptide was consistent with the results of the effect of these sugars on the gelation behavior of gelatin.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145248921","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":"Antiangiogenic <i>Antheraea pernyi</i> Silk Fibroin Nanocarrier As an Advanced Dual-Gene Delivery Platform for Lung Tumor Suppression.","authors":"Jing Qu, Xueping Liu, Jiru Jia, Wei Ma, Qi Xiao, Mingzhong Li","doi":"10.1021/acs.biomac.5c01484","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c01484","url":null,"abstract":"<p><p>The cationic <i>Antheraea pernyi</i> silk fibroin (CASF)-bridged endostatin peptide 2 (ES2) electrostatically coated the inhibitor of growth 4 (ING4)/interleukin-24 (IL-24) dual-gene coexpression plasmid DNA (pDNA) to construct a CASF-ES2/pDNA nanocarrier, which significantly enhanced gene expression and induced apoptosis by strengthening cell adhesion and endocytosis. The continuously released ES2 contributed to its specific action on HUVECs, including inducing apoptosis and hindering migration, invasion, and tube formation, as well as inhibiting angiogenesis in the chorioallantoic membrane. In the treatment of mice with A549 xenograft tumors, CASF-ES2/pDNA arrested the growth cycle of tumor cells and activated the Bcl-2/Bax/C Caspase-3 apoptotic pathway, promoting cell apoptosis and tissue collapse. Additionally, the released ES2 prevented the formation of tumor neovasculature, cut off the nutrient channels for tumor growth, and synergistically inhibited the development and metastasis of xenograft tumors. This safe and antiangiogenic gene vector shows great promise for application in long-term antitumor and antimetastatic therapy.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145256906","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}
BiomacromoleculesPub Date : 2025-10-09DOI: 10.1021/acs.biomac.5c01471
Tao Zhang, Vincent S D Voet, Rudy Folkersma, Katja Loos
{"title":"In Situ Photoresin Synthesis via Reactive Diluents for Vat Photopolymerization.","authors":"Tao Zhang, Vincent S D Voet, Rudy Folkersma, Katja Loos","doi":"10.1021/acs.biomac.5c01471","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c01471","url":null,"abstract":"<p><p>As climate change intensifies, there is a pressing demand for sustainable alternatives to fossil-derived photoresins in additive manufacturing. While biobased systems have been explored, many rely on hazardous solvents, limiting their environmental benefits. Here, we report a one-pot, purification-free strategy for synthesizing renewable, high-performance photoresins using furan-based monomers derived from lignocellulosic biomass. Furfuryl methacrylate and 4,4'-bismaleimidodiphenylmethane (BSM) were integrated into methacrylate networks via Diels-Alder (DA) chemistry, with 2-hydroxyethyl methacrylate (HEMA) enabling high conversion (93%) under optimized conditions. Mechanical testing revealed that UV postcuring enhanced tensile strength, whereas excessive UV or solvent exposure caused oligomer leaching. Thermal postcuring activated retro-DA reactions, improving mechanical robustness and shape memory performance. Comparative studies showed aromatic DA derivatives offered superior programmability, while aliphatic analogs provided higher renewable carbon content with stable printability. This scalable, solvent-free strategy establishes a green chemistry framework for sustainable, high-performance photoresins, advancing additive manufacturing toward circular economy objectives.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145248953","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}
BiomacromoleculesPub Date : 2025-10-09DOI: 10.1021/acs.biomac.5c00831
Fen Zheng, Shanming Zhang, Dongxuan Liu, Yitong Chen, Long Xu
{"title":"Smart Dual-Targeted NRP-1/CAIX Nanoparticles with Sequential pH/ROS Responsiveness Overcome Tumor Microenvironment Barriers for Enhanced Penetration and Antitumor Efficacy.","authors":"Fen Zheng, Shanming Zhang, Dongxuan Liu, Yitong Chen, Long Xu","doi":"10.1021/acs.biomac.5c00831","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00831","url":null,"abstract":"<p><p>Suboptimal intratumoral penetration remains a major obstacle to the clinical translation of nanomedicines, underscoring the need for innovative nanoplatforms that enable precise tumor penetration. While tumor-penetrating peptides are commonly used to improve nanomedicine accumulation and permeability in tumors, their efficacy in hypoxic regions remains limited. Herein, four pH/ROS dual-responsive polymer prodrugs, modified with or without the tumor-penetrating peptide CRGDK and the CAIX ligand, were constructed. The stability, pH/ROS responsiveness, in vitro drug release properties, and cellular uptake of the resulting micelles were evaluated. Tumor penetration was investigated using multicellular tumor spheroids (MTSs) and the PANC-1 xenograft model. Antitumor efficacy was studied in normoxic and hyperoxic cells, MTSs, and the xenograft model. Results showed that the NRP-1/CAIX dual-targeted prodrug micelles (P1) achieved deep tumor penetration in hypoxic tumor regions. A sequential targeting strategy employing both a tumor-penetrating peptide and a CAIX ligand offers a promising approach for enhancing nanomedicine infiltration into deep tumor areas.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145256940","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}
BiomacromoleculesPub Date : 2025-10-09DOI: 10.1021/acs.biomac.5c00984
Disi Qiao, Nacun Yang, Lin Shi, Longyi Chen, Jun Gu, Xinhua Peng, Chuntao Chen, Dongping Sun
{"title":"Interface modifiable bacterial cellulose hydrogel based nerve guidance conduit effectively rehabilitate sciatic nerve injured rat.","authors":"Disi Qiao, Nacun Yang, Lin Shi, Longyi Chen, Jun Gu, Xinhua Peng, Chuntao Chen, Dongping Sun","doi":"10.1021/acs.biomac.5c00984","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00984","url":null,"abstract":"<p><p>Peripheral nerve injury accounts for 2-5% of all trauma admissions worldwide and is a significant clinical challenge. In this research, a novel nerve guidance conduit biomaterial based on a tungsten oxide nanomaterial-decorated oxidized bacterial cellulose hydrogel was developed for repairing sciatic nerve injury. The bacterial cellulose was oxidized by sodium periodate, and aldehyde functional groups were introduced to enhance its reactivity and biocompatibility. At the same time, the incorporation of the tungsten oxide nanomaterial not only significantly improved its antibacterial properties but also rendered the material antioxidant. The functional recovery of the sciatic nerve in the rat transection model was assessed by the sciatic functional index, gastrocnemius histological analysis, and nerve histological analysis. This bacterial cellulose/tungsten oxide nanoparticle hybrid hydrogel biocomposite can effectively promote sciatic axon regeneration, Schwann cell activity, and nerve function recovery. This novel biocomposite provides a new therapeutic strategy for the repair of a sciatic nerve injury.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145256943","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}