BiomacromoleculesPub Date : 2025-10-03DOI: 10.1021/acs.biomac.5c01335
Yanhong Song, Yueze Hong, Jun Deng, Haoyu Zou, Jianyu Xin, Fanjun Zhang, Qing Jiang, Yunbing Wang
{"title":"Foldable and Hydration-Rigidified Acrylate Polymer for a Highly Stable and UV-Filtering Phakic Intraocular Lens.","authors":"Yanhong Song, Yueze Hong, Jun Deng, Haoyu Zou, Jianyu Xin, Fanjun Zhang, Qing Jiang, Yunbing Wang","doi":"10.1021/acs.biomac.5c01335","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c01335","url":null,"abstract":"<p><p>Phakic intraocular lenses (pIOLs) are widely used for myopia correction, but face challenges such as unfolding, displacement, glistenings, and bioadhesion. To address these issues, various transparent BPH polymers were synthesized by integrating hydrophilic poly(ethylene glycol) methyl ether methacrylate (PEGMMA) with hydrophobic benzyl methacrylate (BzMA) and 2-hydroxy-4-(methacryloyloxy)benzophenone (HMBP). The prepared BPH materials exhibit high transparency, a tunable refractive index, and UV-filtering properties. With the integration of PEGMMA, the polymers exhibit a decreasing glass transition temperature (<i>T</i><sub>g</sub>) and modulus and an interesting hydration-induced rigidification due to microphase separation triggered by water uptake of hydrophilic PEG chain segments. This characteristic simultaneously endows the BPH pIOLs with the foldability essential for small-incision implantation and the rigidity required for enhanced stability after implantation. PEGMMA introduction also reduces glistenings and enhances hydrophilicity, improving resistance to protein, cell, and bacterial adhesion. In vitro cytotoxicity and in vivo subcutaneous implantation confirm their biosafety. The UV-filtering BPH platform resolves the foldability-stability trade-off and suppresses glistenings and bioadhesion, representing a promising option for pIOLs.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145211153","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 : 2025-10-02DOI: 10.1021/acs.biomac.5c01512
Guoming Yuan, , , Hui Yang, , , Zhijun Liu, , , Haoting Zheng, , , Yanhan Tao, , , Bo Yang, , , Kun Wu*, , and , Jun Shi,
{"title":"Cattail-Biomimetic Biobased Organosilicon Composite with Excellent Low Dielectric, Anticorrosion, And Greatly Improved Thermal and Mechanical Properties","authors":"Guoming Yuan, , , Hui Yang, , , Zhijun Liu, , , Haoting Zheng, , , Yanhan Tao, , , Bo Yang, , , Kun Wu*, , and , Jun Shi, ","doi":"10.1021/acs.biomac.5c01512","DOIUrl":"10.1021/acs.biomac.5c01512","url":null,"abstract":"<p >The rapid development and multiapplication scenarios (such as marine communication) of communication technology demand higher-performance interlayer dielectric materials. A poly(benzoxazine)-modified organosilicon composite (P(M-Fa-Si)) was prepared from renewable magnolol. The binding energy of a single poly(benzoxazine) and a single organosilicon link was calculated by DFT to be −3.99 eV, indicating good compatibility. Surprisingly, P(M-Fa-Si) with a cattail-biomimetic micronanostructure had a water contact angle of 127.1° (vs 103.2° for P(EM-Si)). Given its unique surface morphology and high cross-linking density (4.79 × 10<sup>4</sup> mol/m<sup>3</sup>), P(M-Fa-Si) achieved 99.84% copper protection, 2.21 × 10<sup>07</sup> Ω·cm<sup>2</sup> impedance after a 20-day corrosion, showing excellent anticorrosion. The <i>D</i><sub>k</sub> and <i>D</i><sub>f</sub> of P(M-Fa-Si) were 2.68 and 0.00754 (10 MHz), respectively, with excellent low dielectric properties. Its <i>T</i><sub>d,5%</sub> (323.12 °C) and <i>T</i><sub>g</sub> (129.52 °C) exceeded P(EM-Si) (236.82 °C, 73.89 °C), and its tensile/flexural/impact strengths were over 5× higher. This biobased composite expanded sustainable polymer use in electronics and guided high-performance material design.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 10","pages":"7152–7164"},"PeriodicalIF":5.4,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145204930","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 : 2025-10-01DOI: 10.1021/acs.biomac.5c01205
Pierre-Louis Brassart, , , Matthias Da Conceicao, , , Alina Vashchuk, , , Jelena Stanisavljevic, , , Mathieu Morel*, , and , Christophe Tribet*,
{"title":"Fast Microdialysis Buffer Exchange to Study Poly(glutamate)/Lysozyme Coacervates in Concentrated Conditions","authors":"Pierre-Louis Brassart, , , Matthias Da Conceicao, , , Alina Vashchuk, , , Jelena Stanisavljevic, , , Mathieu Morel*, , and , Christophe Tribet*, ","doi":"10.1021/acs.biomac.5c01205","DOIUrl":"10.1021/acs.biomac.5c01205","url":null,"abstract":"<p >Complex coacervation between oppositely charged proteins and polyelectrolytes has broad relevance, from membraneless organelles to biomedical applications. Unlike well-characterized synthetic polyelectrolytes, protein coacervates pose experimental challenges due to limited quantities, constraints of mild handling, fine-tuning of pH, and ionic strength affecting contributions of charge patches or non-Coulombic binding. To alleviate these constraints, we propose to use a microdialysis chip allowing in situ control of microvolumes. We studied model lysozyme/polyglutamate coacervates. Rapid equilibration with phosphate buffers of varying concentrations showed that (i) fine control of the ionic strength was essential due to the release of counterions affecting the phase diagram above 80 g/L lysozyme, (ii) phase separation was reversible, (iii) chirality of the polyglutamate affects coacervation, and (iv) coacervates can be annealed into homogeneous films allowing FRAP measurements across fluid-like to solid-like transition as betrayed by a marked decrease of polyglutamate diffusivity below a threshold of 60 mM phosphate.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 10","pages":"6906–6916"},"PeriodicalIF":5.4,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145197393","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":"Direct Protein–Polymer Conjugation via Tyrosine-Terminated Radical Polymerization","authors":"Kebing Yi, , , Xinyue Zhou, , , Yaran Zhang, , , Yanchao Liu, , , Feng Gong, , , Yimiao He, , , Yu Feng, , , Chuanxin Du, , , Hui Gong, , , Zhijian Li, , , Longqing Niu, , , Hui Xu, , , Fubing Wang, , , Fuxiang Zhou, , , Xinghu Ji*, , and , Zhike He*, ","doi":"10.1021/acs.biomac.5c00729","DOIUrl":"10.1021/acs.biomac.5c00729","url":null,"abstract":"<p >Protein–polymer conjugates (PPCs) combine the unique bioactivities of the proteins with the tunable properties of the polymers, but their synthesis typically requires premodification of components. Herein, we report the occurrence of radical polymerization termination by phenol derivatives as a prevalent side reaction, allowing direct covalent conjugation of polymer chains to solvent-accessible tyrosine residues in native proteins. This reaction, we termed grafting via tyrosine-terminated radical polymerization (TyrTer-grafting). TyrTer-grafting exhibits applicability to diverse monomers and proteins, achieves improved conjugation efficiency under proximity-driven enzymatic catalysis, and preserves protein function more effectively than the traditional activated ester-mediated method. In addition, TyrTer-grafting enables both direct cell-surface polymerization to control cellular aggregation and anchor-free expansion microscopy (ExM) to generate high-quality images with super-resolved details. This work provides a new perspective for fabricating functional macromolecules and presents a significant discovery for radical chemistry and bioconjugation chemistry.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 10","pages":"6563–6573"},"PeriodicalIF":5.4,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145204994","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":"Microstructure and Performance Evolution of Poly(l-Lactic Acid) during Physical Aging: Effect of Molecular Weight","authors":"Zhi-xuan Zhang, , , Chao-qun Wu, , , Yi-fan Zha, , , De-xiang Sun*, , , Xiao-dong Qi, , , Jing-hui Yang, , and , Yong Wang*, ","doi":"10.1021/acs.biomac.5c01668","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c01668","url":null,"abstract":"<p >With the growing public awareness of environmental protection, poly(<span>l</span>-lactic acid) (PLLA) has started to establish a presence across various industries. However, the inevitable physical aging of PLLA products leads to substantial alterations in both microstructural evolution and macroscopic properties. Therefore, it is essential to conduct an in-depth discussion of the underlying mechanism associated with physical aging. As an intrinsic parameter of PLLA, the mechanism by which molecular weight influences physical aging remains to be clarified. In this article, the regulatory mechanism of molecular weight over the physical aging timeline in PLLA is elucidated according to the cohesional entanglement theory. The ″growth process″ of cohesional entanglements within the high-molecular-weight sample system is inhibited, leading to a decrease in the effective number of such structures, which is manifested as a delay in physical aging behavior. Moreover, the effect of molecular weight on the physical aging exhibits a nonlinear increase, and a ″saturation effect″ is observed. This work provides a theoretical basis for elucidating the regulatory mechanism of molecular weight on the physical aging behavior of PLLA.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 10","pages":"7190–7203"},"PeriodicalIF":5.4,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145262146","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":"Sodium Alginate Silk Fibroin Hydrogel Loaded with Neural Stem Cells for Treatment of Cerebral Palsy","authors":"Simiao Yu, , , Chenyu Liu*, , , Zhangrong Lou, , and , Weihong Qiao*, ","doi":"10.1021/acs.biomac.5c01300","DOIUrl":"10.1021/acs.biomac.5c01300","url":null,"abstract":"<p >The application of stem cell therapy for neural tissue regeneration is often limited by low cell survival after transplantation. To overcome this, we developed an injectable hydrogel via dual cross-linking: Schiff base formation between oxidized alginate and silk fibroin (SF) and host–guest interactions between β-cyclodextrin (β-CD) and adamantane. The resulting hydrogel exhibits high water content, injectability, electrical conductivity, suitable degradation, and excellent biocompatibility. Neural stem cells (NSCs) encapsulated within the hydrogel showed high viability, proliferation, and neuronal differentiation capacity <i>in vitro</i>. In a rat model of cerebral palsy (CP), NSC-laden hydrogel transplanted via intracranial injection promoted significant structural repair and functional recovery, as confirmed by behavioral tests, histology, and proteomics. indicating its potential therapeutic effect on the repair of cerebral tissue in CP. This indicates that the hydrogel has broad application prospects in the field of brain nerve tissue repair.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 10","pages":"6984–7001"},"PeriodicalIF":5.4,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145197434","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":"Targeted Nanoactuator-Integrated Multicomponent Supramolecular Assemblies for Augmented Chemo/Chemodynamic Combination Therapies","authors":"Shuai Chen, , , Ning Han, , , Yuheng Ren, , , Hongxia Wang, , , Jianmei Yang, , , Junnan He, , , Mingming Chen, , , Fei Zhu, , , Jinxin Yang, , , Yan Zhao*, , and , Jin Zhang*, ","doi":"10.1021/acs.biomac.5c01597","DOIUrl":"10.1021/acs.biomac.5c01597","url":null,"abstract":"<p >Lung cancer remains the leading cause of cancer mortality, highlighting the need for innovative therapies. Aloe-emodin (AE), a natural anthraquinone from Aloe vera, faces clinical challenges due to tumor heterogeneity and immunosuppressive microenvironments. To address this, we combine chemodynamic therapy (CDT) with a novel supramolecular assembly (MIL-101(Fe)-Fc@AE@FACD), designed by functionalizing iron-based metal–organic frameworks (MIL-101(Fe)) with folic acid-conjugated cyclodextrin (FACD) for tumor targeting. This assembly enables dual therapeutic mechanisms: CDT-induced reactive oxygen species (ROS) generation and pH-triggered AE release. In vitro, it shows enhanced cytotoxicity against A549 cells, reducing cell viability to <15%. In vivo, it significantly inhibits tumor growth with minimal hepatorenal toxicity. This hybrid supramolecular platform enhances the antitumor efficacy of AE against lung cancer.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 10","pages":"7165–7176"},"PeriodicalIF":5.4,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145204967","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":"Chitosan-Based Microneedle Patch with Multi-Anchoring and Integrated Hemostatic Mechanisms for Highly Efficient Bleeding Control in Dynamic, Wet Intestinal Conditions","authors":"Chuchu Tang, , , Xianda Liu, , , Shuxiang Zhang, , , Shengjun Cheng, , , Wenjie Wang, , , Xiran Zhou, , , Junhan Tang, , , Ran Wei, , , Weifeng Zhao*, , and , Changsheng Zhao, ","doi":"10.1021/acs.biomac.5c00979","DOIUrl":"10.1021/acs.biomac.5c00979","url":null,"abstract":"<p >Severe intestinal bleeding poses life-threatening risks, including hemorrhagic shock, organ damage, infection, and death. Current hemostatic materials struggle to adhere to wet, dynamic intestinal tissues, hindering effective hemostasis. Inspired by the hookworm’s rigid mouthpart and flexible body, which enable robust anchoring in the intestine, we developed a hydrogel microneedle patch (40K@P/G MNs) integrating multianchoring and hemostatic mechanisms. The patch leverages microneedle topology and gallic acid-grafted chitosan for enhanced mucosal adhesion, coupled with an extensible backing layer of optimized elasticity, achieving robust tissue adhesion (86.17 ± 26.19 mm Hg) in porcine intestinal models. The patch enhances clotting through a synergistic mechanism involving both chitosan and kaolin, which collectively promote platelet adhesion and activate the coagulation cascade, yielding a low blood coagulation index (4.92 ± 0.68%). It demonstrated excellent hemostatic performance in a rat liver hemorrhage model, achieving hemostasis within 35 s and preventing rebleeding. Its backing layer matches the intestine’s mechanical stress, providing elasticity to withstand peristaltic forces. This multianchoring microneedle patch offers a carbohydrate-based solution for rapid, localized hemostasis in challenging intestinal environments.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 10","pages":"6716–6730"},"PeriodicalIF":5.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145190411","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 : 2025-09-30DOI: 10.1021/acs.biomac.5c00190
Mojtaba Nasirinezhad*, , , Mahboube Mohamadi*, , , Saba Abbasi Sedaghat, , , Sara Etminanrezaeieh, , and , Katayoun Behnejhad Takleh,
{"title":"A Comprehensive Review of Sources, Structure, Characteristics, Extraction, and Applications of Pectin in Drug Delivery","authors":"Mojtaba Nasirinezhad*, , , Mahboube Mohamadi*, , , Saba Abbasi Sedaghat, , , Sara Etminanrezaeieh, , and , Katayoun Behnejhad Takleh, ","doi":"10.1021/acs.biomac.5c00190","DOIUrl":"10.1021/acs.biomac.5c00190","url":null,"abstract":"<p >Pectin, a naturally derived biopolymer, has gained significant attention in pharmaceutical and biomedical applications due to its biocompatibility, low toxicity, biodegradability, tunable physicochemical characteristics, cost-effectiveness, and abundant availability. The functional versatility and bioactivity of pectin are governed by its structural features, particularly its degree of esterification and the presence of reactive functional groups, such as hydroxyl and carboxyl moieties. To further optimize its performance and expand its biomedical applications, various strategies, including chemical modifications (e.g., cross-linking) and the development of pectin-based blend/hybrid/composite materials, have been explored. This review provides a comprehensive overview of pectin, beginning with its sources, structural attributes, physicochemical properties, and extraction methodologies. Subsequently, we examine the applications of pectin-based biomaterials in diverse drug delivery platforms such as nasal, oral, ocular, cancer-targeted, and gene delivery systems. Furthermore, the synthesis, functional properties, and performance of pectin-containing hybrid and composite materials are critically discussed. By consolidating current knowledge on pectin extraction, modification techniques, and advanced applications, this review aims to elucidate the pivotal role of pectin in the development of next-generation drug delivery systems and biomedical innovations.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 10","pages":"6357–6380"},"PeriodicalIF":5.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145190414","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":"Polyacrylic Acid-Based Chlorella Loading Hydrogel Featuring Antibacterial and Microenvironment Remodeling Properties for Expedited Wound Healing","authors":"Siyuan Yuan, , , Yongjie Zhang, , , Xiaomei Dai*, , , Yuqin Zou, , , Menglin Huang, , , Xue Yang, , , Hongqi Chen, , and , Feng Gao*, ","doi":"10.1021/acs.biomac.5c01694","DOIUrl":"10.1021/acs.biomac.5c01694","url":null,"abstract":"<p >Polyacrylic acid (PAA)-based hydrogels have been widely used in commercial wound dressings. However, they may trigger a series of adverse reactions within biological organisms due to PAA’s nonbiodegradable nature and the difficulty of metabolism in physiological environments. To overcome this issue, a degradable PAA derivative (PLC) containing acrylic acid, α-lipoic acid (LA), and 2-(<i>N</i>-3-sulfopropyl-<i>N</i>,<i>N</i>-dimethylammonium)ethyl methacrylate was synthesized by reversible addition–fragmentation chain-transfer (RAFT) polymerization. Then, a multifunctional PLC-based hydrogel (CAPLCT@<i>Chlorella</i>) was developed through a facile mixture of PLC, tannic acid (TA), <span>l</span>-arginine-coupled chitosan (CA), and <i>Chlorella</i>. <i>Chlorella</i> in the hydrogel could constantly generate oxygen (O<sub>2</sub>) through photosynthesis, relieving hypoxia. CA in the hydrogel endows CAPLCT@<i>Chlorella</i> the release of nitric oxide (NO), which could promote angiogenesis. The hydrogel not only exhibits excellent antibacterial and antibiofilm activities but can also relieve oxidative stress and modulate the inflammatory microenvironment. CAPLCT@<i>Chlorella</i> offers a promising therapeutic option for bacteria-infected wound healing.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":"26 10","pages":"7204–7216"},"PeriodicalIF":5.4,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145197429","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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