{"title":"Spider Silk-Inspired Flexible Biomacromolecular Composite with Electrical and Thermal Functionality from Mesoporous Bamboo.","authors":"Tianfang Zhang, Luxi He, Xiangyu Zhao, Wenrui Xie, Zhengbin He, Zhenyu Wang, Songlin Yi","doi":"10.1021/acs.biomac.5c00537","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00537","url":null,"abstract":"<p><p>Inspired by the hierarchical architecture of spider silk, this study introduces a biobased macromolecular composite that combines mechanical flexibility, thermal regulation, and electrical performance. The composite is constructed using a delignified bamboo scaffold, which acts as a naturally aligned, mesoporous framework of cellulose-based macromolecules, integrated with carboxylated multiwalled carbon nanotubes and poly (vinyl alcohol). This design yields a mechanically resilient macromolecular network with stable electrical conductivity under cyclic deformation. The composite achieves enhanced thermal conductivity and demonstrates a 7.29% increase in ice-melting efficiency. Importantly, under prolonged thermal exposure, the composite undergoes thermal degradation, forming a protective carbonaceous char layer that suppresses combustion and reduces CO<sub>2</sub> and particulate emissions by 37.2 and 84.6%, respectively. The intrinsic mesoporous structure of bamboo provides an ultralight yet robust template, maintaining mechanical integrity even under cyclic stress. Additionally, the conductive nanomaterials improve interfacial properties, making this composite a promising candidate for durable, biobased flexible electronics and thermally stable structural applications. These multifunctional characteristics highlight the potential of natural macromolecular architectures in developing sustainable, biodegradable, and high-performance polymeric systems for flexible electronics and thermally stable applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504048","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 : 2025-06-27DOI: 10.1021/acs.biomac.5c00737
Deqing Zhao, Jingpeng He, Yaling Zhao, Kaibin Ma, Yang Xu, Qinqin Xia, Xinglin Xiong, Xuan Tang, Qingyi Zhao, Rongge Wang
{"title":"Efficient and Protective Upgrading of Uncondensed Lignin Extraction with High Yield and High Purity: Mechanistic Insights into Lewis Acid Catalysis Coupled with PEG Stabilization.","authors":"Deqing Zhao, Jingpeng He, Yaling Zhao, Kaibin Ma, Yang Xu, Qinqin Xia, Xinglin Xiong, Xuan Tang, Qingyi Zhao, Rongge Wang","doi":"10.1021/acs.biomac.5c00737","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00737","url":null,"abstract":"<p><p>Maximizing the extraction and valorization of highly reactive lignin from lignocellulosic biomass is crucial for lignin-first biorefining. However, achieving high yield, superior purity, and structural preservation simultaneously is challenging. Herein, we developed a Lewis acid-catalyzed deep eutectic solvent (DES) system employing ferric chloride (FeCl<sub>3</sub>) coordinated with polyethylene glycol (PEG) to selectively extract structurally intact lignin. The engineered DES system exhibited outstanding performance, achieving a lignin yield of 32.9% with a purity of 96.2%. Structural analysis indicated that the extracted lignin retained 53.21 β-O-4 linkages per 100 aromatic units, closely approximating the native structure of cellulolytic enzyme lignin (CEL: 58.53 β-O-4/100 Ar). The identification of characteristic β'-O-4 linkages verified that PEG grafting at the C<sub>α</sub> position effectively inhibited lignin condensation. Theoretical calculations further confirmed that FeCl<sub>3</sub> enhanced the hydrogen-bonding capacity of the ternary DES with lignin, thereby aiding lignin dissociation and improving separation efficiency. This work provides valuable insights into upgrading lignin fractionation for lignin valorization.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504145","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":"Composition Engineering for Enhanced Photosensitization: A Toolbox for Biological Applications.","authors":"Mengyao Zhang, Jingbo Huang, Shunze Cheng, Yujie Bai, Pei Huang, Haili Zhang, Shunjie Liu, Hualei Wang, Yuanyuan Li","doi":"10.1021/acs.biomac.5c00659","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00659","url":null,"abstract":"<p><p>Conjugated polymers (CPs) exhibiting aggregation-induced emission (AIE) properties have found extensive applications in the biomedical sector due to their strong solid-state emission, enhanced light absorption capabilities, and effective production of reactive oxygen species (ROS). However, an explanation of the structure-function relationship was not provided. Herein, four CPs with AIE characteristics were synthesized by varying the composition and combination of donor-acceptor (D-A), among which PADAD' exhibited the highest ROS generation efficiency due to its D-A effect and aggregation-induced ROS generation ability. Furthermore, functionalized CPs were designed as a toolbox for biological applications using PADAD' as the skeleton. As a proof of concept, PADAD'-APT and PADAD'-GUA were synthesized by introducing target motifs designed to identify and photoinactivate tumor cells and bacteria, respectively. Thus, this platform holds great promise for biomedicine and provides ideas for the development of functionalized conjugated polymers.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504144","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 : 2025-06-26DOI: 10.1021/acs.biomac.5c00221
Lei Lei, Jia Liu, Yueting Shi, Yiping Wu, Wei Wu, Yuhan Hu, Haoxuan Wang, Jiaqing Wang, Xingyi Li
{"title":"A Bioadhesive Functional Peptide-Derived Supramolecular Hydrogel for the Promotion of Corneal Re-Epithelization.","authors":"Lei Lei, Jia Liu, Yueting Shi, Yiping Wu, Wei Wu, Yuhan Hu, Haoxuan Wang, Jiaqing Wang, Xingyi Li","doi":"10.1021/acs.biomac.5c00221","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00221","url":null,"abstract":"<p><p>The rapid corneal re-epithelization after injury is crucial for maintaining corneal homeostasis and barrier function. This study reports a bioadhesive functional peptide-derived supramolecular hydrogel (FBA-FFGGRGD) for promoting corneal re-epithelization. The aldehyde-modified bioactive peptide (RGD) endows the hydrogel with bioadhesive properties, enabling covalent anchoring to corneal basement membrane proteins via Schiff base reaction. Compared with its analogue (TA-FFGGRGD), FBA-FFGGRGD significantly enhances adhesion, migration, and proliferation of human corneal epithelial cells (HCECs), doubling cell numbers within 48 h and upregulating zonula occludens-1 (ZO-1) expression. <i>In vivo</i> studies show that the hydrogel exhibits excellent ocular biocompatibility, prolongs precorneal retention (∼40 min), and promotes stratified epithelium formation in a rabbit model of corneal injury. By remodeling the epithelial barrier, this bioadhesive hydrogel provides a promising strategy for corneal homeostasis preservation and ocular disorder prevention.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144493144","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 : 2025-06-26DOI: 10.1021/acs.biomac.5c00177
Olivia E Coer, Brandy L Davidson, Brycelyn M Boardman, Gretchen M Peters
{"title":"Modulating Thermal Stability and Flexibility in Chitosan Films with Neutral Polyol-Boric Acid Complexes.","authors":"Olivia E Coer, Brandy L Davidson, Brycelyn M Boardman, Gretchen M Peters","doi":"10.1021/acs.biomac.5c00177","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00177","url":null,"abstract":"<p><p>The incorporation of boron into bioplastics offers the potential for diverse applications, with the structure-property relationship between polymer chains and boron species being the key for design. Here, we report the ability to modulate the flexibility and thermal stability of chitosan materials by varying the concentrations of erythritol and the molar equivalents of boric acid. Erythritol and boric acid form neutral complexes that alter the hydrogen-bonding face of erythritol while maintaining free diol units. 1D and 2D NMR experiments indicate preferential formation of the 1,3-isomer (85%) with minor amounts of 1,2- and 2,3-isomers. Structural, thermal, mechanical, and morphological characterization was performed using ATR-FTIR, TGA and DSC, DMA, and SEM, respectively. Molecular-level interactions of the complexes and d-glucosamine, the repeat unit of chitosan, showed increased aggregation and hydrogen-bonding interactions of the free diol units with the NH of d-glucosamine, supporting the trends in flexibility observed in the polymer system.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504047","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":"Humic Acid and Cellulose Nanocrystal-Based Antifreeze Nanocomposite Hydrogel Flexible Sensor.","authors":"Chenglin Yang, Xinyue Zhang, Xinhang Yu, Wenxiang Wang, Liangjiu Bai, Hou Chen, Lixia Yang, Huawei Yang, Donglei Wei","doi":"10.1021/acs.biomac.5c00624","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00624","url":null,"abstract":"<p><p>Humic acid (HA), a natural organic compound rich in carboxyl, phenolic hydroxyl, and quinone groups, was incorporated into hydrogels to enhance mechanical strength, antifreeze performance, UV resistance, and adhesion. Cellulose nanocrystals (CNCs), extracted using phytic acid (PA), were co-introduced with HA into a polyvinyl alcohol (PVA)/β-glycerophosphate (β-GP) network. The abundant functional groups in HA provided additional cross-linking sites, forming a robust three-dimensional structure. After freeze-thaw treatment, the hydrogel exhibited a tensile strength of 4.4 MPa and UV transmittance as low as 0.0027% in the 200-400 nm range. Furthermore, β-GP modulated hydrogen bonding among water molecules, significantly improving antifreeze capability and enabling stable, sensitive detection of human motion and signal transmission at -20 °C. These results demonstrate the potential of HA-functionalized hydrogels as flexible sensors for operation in complex and low-temperature environments, broadening their applicability in wearable and bioelectronic systems.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504046","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 : 2025-06-26DOI: 10.1021/acs.biomac.5c00351
Yan Yang, Shizhuo Li, Yixuan Li, Mengyue Zhang, Shitong Li, Kun Liu, Tong Qiu, Honglian Dai
{"title":"Gradient pH Hydrogel Promotes Infected Wound Healing through pH Regulation of Microenvironment.","authors":"Yan Yang, Shizhuo Li, Yixuan Li, Mengyue Zhang, Shitong Li, Kun Liu, Tong Qiu, Honglian Dai","doi":"10.1021/acs.biomac.5c00351","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00351","url":null,"abstract":"<p><p>A healthy skin surface has an acidic environment with an average pH below 5, which helps to protect against bacterial infection. A weakly acidic environment of the dermis not only reduces bacterial infection but also affects fibroblasts' activity, vascular endothelial cell activity, and the immune response. The natural pH gradient helps to ensure the integrity of the skin and accelerates the repair process, following skin damage. In this study, GelMA-based gradient pH hydrogel was proposed for infected skin wound healing. Experiments showed that the gradient pH hydrogel had good antibacterial effects and promoted the proliferation and migration of fibroblasts and endothelial cells. The gradient pH hydrogel lowered the pH of the wound bed, reduced the bacterial load, and induced macrophage polarization to M2 and neovascularization. The gradient pH hydrogel promoted hair follicle regeneration by modulating Treg cells. Thus, this hydrogel provides a new option for the treatment of bacterially infected wounds.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144493146","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 : 2025-06-26DOI: 10.1021/acs.biomac.5c00045
Kiseok Han, Anbazhagan Sathiyaseelan, Myeong-Hyeon Wang
{"title":"<i>Wolfiporia extensa</i> Extract-Loaded Carboxymethyl Cellulose-Stabilized Cerium Oxide-Doped Hydroxyapatite Nanocomposites as Advanced Antioxidant Platform for Bone Tissue Regeneration.","authors":"Kiseok Han, Anbazhagan Sathiyaseelan, Myeong-Hyeon Wang","doi":"10.1021/acs.biomac.5c00045","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00045","url":null,"abstract":"<p><p>Excessive levels of reactive oxygen species (ROS) are known to hinder effective bone regeneration by inducing oxidative stress in osteogenic environments. In this study, we developed novel nanocomposites (NCs) composed of green-synthesized cerium oxide (CeO<sub>2</sub>), bovine-derived hydroxyapatite (HA), carboxymethylcellulose (CMC), and <i>Wolfiporia extensa</i> (WE) extract. Comprehensive physicochemical characterization confirmed the nanocomposites' uniform morphology (average size ∼201 nm) and colloidal stability (zeta potential -32.6 mV). Notably, these NCs displayed strong antioxidant activity, significantly improving the survival of MC3T3-E1 preosteoblasts exposed to H<sub>2</sub>O<sub>2</sub>-induced stress (64.9% viability at 31.2 μg/mL). Furthermore, the composites significantly enhanced calcium deposition by 72.2%, indicating promoted osteogenic differentiation, and increased cell migration by 25.5% compared to the untreated control group. Biocompatibility was corroborated through chorioallantoic membrane (CAM) assays. Collectively, the CeO<sub>2</sub>/HA/CMC/WE NCs present a promising approach to mitigating oxidative stress and facilitating bone repair in ROS-compromised conditions.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144504143","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 : 2025-06-26DOI: 10.1021/acs.biomac.5c00425
Shiqiang Zhang, Jingjing Xia, Jiyu Chen, Lei Chen, Jingjiang Qiu, Zhongwei Guo, Ronghan Wei, Wei Sun
{"title":"Ultra-Elastic, Transparent, and Conductive Gelatin/Alginate-Based Bioadhesive Hydrogel for Enhanced Human-Machine Interactive Applications.","authors":"Shiqiang Zhang, Jingjing Xia, Jiyu Chen, Lei Chen, Jingjiang Qiu, Zhongwei Guo, Ronghan Wei, Wei Sun","doi":"10.1021/acs.biomac.5c00425","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00425","url":null,"abstract":"<p><p>Growing interest has focused on next-generation flexible adhesive sensors (FAS) integrated with deep learning for intelligent electronics. Existing conductive hydrogels, however, fail to concurrently achieve high stretchability, transparency, robust adhesion, and interactive precision. Here, a novel class of high-performance ionic hydrogels (AGG-M<sup>n+</sup> hydrogels, with M<sup>n+</sup> being Cu<sup>2+</sup>, Zn<sup>2+</sup>, Fe<sup>3+</sup>, and Zr<sup>4+</sup>) that synergistically combines the above features is developed. The hydrogel is fabricated by incorporating aldehyde-modified sodium alginate (Ald-alginate), gelatin methacrylate (GelMA), and glycerol into the poly(acrylic acid) network through free-radical polymerization plus an ionic coordination strategy. This endows the hydrogel with remarkable properties required for FAS applications, including excellent stretchability (1038%), optimal ionic conductivity (3.25 S/m), and high sensitivity (gauge factor = 1.932, 0%-600% strain range), accompanied by reliable long-term stability over 300 cycles. We also demonstrated its efficiency through the real-time monitoring of diverse physiological signals. Furthermore, the hydrogel was integrated with a deep learning algorithm into a wearable electronic control system, which can instantaneously recognize a diverse array of complex gestures with up to 99.4% accuracy. This work provides new insights for the future development of multifunctional hydrogels, wearable electronics, and human-machine interactions.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144493150","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 : 2025-06-25DOI: 10.1021/acs.biomac.5c00558
Yin Mei Chan, Nicola G Judge, Yang Hu, Rebecca K Willits, Neill Li, Matthew L Becker
{"title":"Review of Gaps in the Clinical Indications and Use of Neural Conduits and Artificial Grafts for Nerve Repair and Reconstruction.","authors":"Yin Mei Chan, Nicola G Judge, Yang Hu, Rebecca K Willits, Neill Li, Matthew L Becker","doi":"10.1021/acs.biomac.5c00558","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00558","url":null,"abstract":"<p><p>Peripheral nerve injuries remain a significant clinical challenge, with limited tools available to physicians and patients. Although autografts are the gold standard for nerve reconstruction, they are limited by donor-site morbidity and availability. Commercially available nerve guidance conduits offer alternatives, yet their clinical application remains largely restricted to short nerve gaps with limited success beyond 1 cm. This review provides a summary of the clinical studies on nerve injury repair using commercial nerve guidance conduits and discusses the shortcomings of such devices, including suboptimal mechanical properties, lack of internal guidance structures and bioactivity, and insufficient clinical data. To address these challenges, emerging innovations, such as biofunctionalized materials, conductive scaffolds, and topographically engineered architectures, are readily being explored to improve regenerative outcomes following neural injury. Overall, this work highlights the gaps in commercial devices utilized clinically and brings attention to the evolving landscape of biomaterials research that can transform clinical nerve repair.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144493147","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}