{"title":"Thermosensitive Cellulosic Biohybrid Comb Copolymers by the Passerini-3CR: 2-Fold Functionalization and Subsequent Thermal Response.","authors":"Laurent Remy, Valentine Christophe, Clémence Vuillet, Adrien Covelli, Benoit Couturaud, Guillaume Sudre, Etienne Fleury, Aurélia Charlot","doi":"10.1021/acs.biomac.5c00647","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00647","url":null,"abstract":"<p><p>This work showcases the synthesis of unprecedented thermosensitive biohybrid carboxymethyl cellulose (CMC)-based comb copolymers by a Passerini three-component reaction (P-3CR) in aqueous conditions. CMC was concomitantly functionalized by various hydrophobic aldehydes and a set of isocyanide-terminated poly(ethylene oxide-<i>co</i>-propylene oxide) (P(EO-<i>co</i>-PO)) segments, exhibiting a lower critical solution temperature (LCST) in water. The P-3CR allowed us to design a library of copolymers differing in their structural compositions (degrees of substitution up to 0.35). The graft copolymers exhibit a thermoinduced sol-gel transition in water due to the reversible formation of hydrophobic domains between dehydrated polyether segments that behave as stickers. From the structure-function relationship, the pivotal result lies in the possibility to tune the thermal response of the biohybrids by the structure of the grafted aldehyde, whose hydrophobicity strongly promotes the thermoassociation process. Thus, the P-3CR paves the way for targeting thermoresponsiveness that can be cleverly adjusted to specific end-uses, which is highly desired for biological applications.</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":"144493149","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.5c00509
Yilin Wang, Yufeng Yuan, Wei Liao, Zaikai Zhuang, Xueying An, Bo Jiang, Chaofeng Zhang, Sehrish Manan, Peng Wang, Yongcan Jin
{"title":"Functional Lignin with Enhanced Aliphatic Hydroxyl and Carboxyl Groups to Attenuate Osteosarcoma Progression via Promoting Mitochondrial Dysfunction.","authors":"Yilin Wang, Yufeng Yuan, Wei Liao, Zaikai Zhuang, Xueying An, Bo Jiang, Chaofeng Zhang, Sehrish Manan, Peng Wang, Yongcan Jin","doi":"10.1021/acs.biomac.5c00509","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00509","url":null,"abstract":"<p><p>Lignin, a complex biopolymer, has promising biomedical applications due to its unique structure and chemical modifiability. This study shows that lignin modified with hydroxyl and carboxyl groups enhances GSH adsorption, thereby improving cytotoxicity and selectivity against osteosarcoma. The modified lignin induces mitochondrial dysfunction via mPTP activation, resulting in membrane depolarization, cytochrome c release, and ATP depletion, ultimately triggering the pro-apoptotic protein BAX and downregulation of the antiapoptotic protein BCL2. Moreover, lignin treatment significantly increased reactive oxygen species (ROS) levels while depleting intracellular GSH, further promoting oxidative stress-induced apoptosis. <i>In vivo</i> studies confirmed that lignin samples were effective in inhibiting tumor growth with a favorable biosafety profile. Among them, CML showed the strongest anticancer effect. These findings highlight the potential of modified lignin as a safe and effective therapeutic agent for OS treatment, offering a novel strategy to enhance oxidative-stress-mediated tumor cell apoptosis while sparing normal cells.</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":"144493145","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.5c00517
Jingyu Xu, Jinghui Zhou, Xiangli Li, Boyu Du, Jun Chen, Shuangping Xu, Xing Wang
{"title":"Synergistic of Nitrogen Cross-Linking Modification, Fiber Body Preparation, and the Incorporation of Covalent Organic Framework (COF) Result in a Considerable Enhancement of Iodine Capture by Lignin.","authors":"Jingyu Xu, Jinghui Zhou, Xiangli Li, Boyu Du, Jun Chen, Shuangping Xu, Xing Wang","doi":"10.1021/acs.biomac.5c00517","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00517","url":null,"abstract":"<p><p>To fully leverage the potential of lignin for capturing radioactive iodine, this study first involved cross-linking lignin using the nitrogen-rich cross-linking agent diethylenetriamine to obtain a modified product. Subsequently, we employed electrospinning technology to transform the modified product into a fibrous, thereby enhancing lignin's solvent stability and broadening its application scope. Notably, we introduced COF growth sites, <i>para</i>-phenylenediamine (Pa), into the spinning solution. Finally, the Pa-containing nanofibers were reacted with the COF growth ligand 1,3,5-tri(4-formylphenyl)benzene. This reaction facilitated the self-growth of TFB-DB COF on the fiber surface, ultimately yielding lignin nanofibers embedded with TFB-DB COF (L/TFP(X)NF). L/TFP(X)NF is regarded as a reusable iodine-capturing material. L/TFP(1.2)NF exhibited the highest performance, capturing approximately 475.0 mg/g, 4451.7 mg/g and 2191.2 mg/g of iodine in steam, <i>n</i>-hexane solution and aqueous solution, respectively. This study significantly enhanced the iodine capture efficiency of lignin through the synergistic effects of nitrogen cross-linking modification, fiber preparation, and COFs.</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":"144493148","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":"Synergistic Nitric Oxide Therapy and Phototherapy Using a Novel Bacteria Scavenger for Treatment of Acute Rhinosinusitis.","authors":"Maolin Li, Hui Yan, Tong Li, Yin Liu, Haiping Zhang, Dandan Han, Songgu Wu, Junbo Gong","doi":"10.1021/acs.biomac.5c00938","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00938","url":null,"abstract":"<p><p>Acute rhinosinusitis is one of the most prevalent diseases seriously affecting the well-being and quality of life. To address this condition, a novel intelligent liposome nanoparticle (BHL@IR780@LNP) was constructed by coloading the photosensitizer IR780 and a nitric oxide donor (l-arginine-loaded biguanide chitosan-hyaluronic acid composite nanoparticles, BHL) onto liposome nanoparticles composed of cholesterol and soybean phospholipids. Under irradiation with an 808 nm near-infrared laser, BHL@IR780@LNP was able to generate heat and reactive oxygen species, resulting in the precise release of nitric oxide, which effectively killed 97.5% of <i>Escherichia coli</i> and 99.2% of <i>Staphylococcus aureus</i>, respectively. Furthermore, <i>in vivo</i> findings demonstrated that BHL@IR780@LNP+L could effectively eliminate 99.5% of <i>S. aureus</i> at the nasal mucous membrane and significantly reduce inflammatory markers. Overall, this study demonstrates a highly effective antibacterial nanoformulation (BHL@IR780@LNP+L) that innovatively integrates the synergistic effects of heat, reactive oxygen species, and nitric oxide to combat acute rhinosinusitis.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144473412","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 : 2025-06-24DOI: 10.1021/acs.biomac.5c00398
Lucia G Brunel, Chris M Long, Fotis Christakopoulos, Betty Cai, Narelli de Paiva Narciso, Patrik K Johansson, Diya Singhal, Neil J Baugh, Daiyao Zhang, Annika Enejder, David Myung, Sarah C Heilshorn
{"title":"Reinforcement of Fibrillar Collagen Hydrogels with Bioorthogonal Covalent Crosslinks.","authors":"Lucia G Brunel, Chris M Long, Fotis Christakopoulos, Betty Cai, Narelli de Paiva Narciso, Patrik K Johansson, Diya Singhal, Neil J Baugh, Daiyao Zhang, Annika Enejder, David Myung, Sarah C Heilshorn","doi":"10.1021/acs.biomac.5c00398","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00398","url":null,"abstract":"<p><p>Bioorthogonal covalent crosslinking stabilizes collagen type I hydrogels, improving their structural integrity for tissue engineering applications with encapsulated living cells. The chemical modification required for crosslinking, however, interferes with the fibrillar nature of the collagen, leading instead to an amorphous network without fibers. We demonstrate an approach to perform bioconjugation chemistry on collagen with controlled localization such that the modified collagen retains its ability to self-assemble into a fibrillar network while also displaying functional groups for covalent crosslinking with bioorthogonal click chemistry. The collagen matrix is formed through a sequential crosslinking process, in which the modified collagen first physically assembles into fibers and then is covalently crosslinked. This approach preserves the fibrous architecture of the collagen, guiding the behavior of encapsulated human corneal mesenchymal stromal cells while also reinforcing fibers through covalent crosslinks, strengthening the stability of the cell-laden collagen hydrogel against cell-induced contraction and enzymatic degradation.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144482553","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 : 2025-06-24DOI: 10.1021/acs.biomac.5c00577
Vilte Sereikaite, Aukse Navaruckiene, Vita Raudoniene, Danguole Bridziuviene, Paulius Cerkauskas, Saulius Lileikis, Kastytis Pamakstys, Egidija Rainosalo, Anne-Sophie Schuller, Christelle Delaite, Jolita Ostrauskaite
{"title":"Antimicrobial Vitrimers Synthesized from Dipentaerythritol Pentaacrylate and 2-Hydroxy-3-phenoxypropyl Acrylate for LCD 3D Printing.","authors":"Vilte Sereikaite, Aukse Navaruckiene, Vita Raudoniene, Danguole Bridziuviene, Paulius Cerkauskas, Saulius Lileikis, Kastytis Pamakstys, Egidija Rainosalo, Anne-Sophie Schuller, Christelle Delaite, Jolita Ostrauskaite","doi":"10.1021/acs.biomac.5c00577","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00577","url":null,"abstract":"<p><p>In this study, two monomers, dipentaerythritol pentaacrylate and 2-hydroxy-3-phenoxypropyl acrylate, were used to synthesize antimicrobial vitrimers with and without a transesterification catalyst and investigate their properties. The addition of the comonomer 2-hydroxy-3-phenoxypropyl acrylate to the photocurable resin reduced its viscosity and shrinkage but increased the gel point and reduced the brittleness and increased flexibility of the resulting polymers. All vitrimers exhibited self-welding and reprocessability properties and thermoresponsive shape memory, maintaining two permanent shapes. All vitrimers showed high antimicrobial activity against widely spread bacteria and fungal strains, including medically important ones. The resin, composed of dipentaerythritol pentaacrylate (1 mol) and 2-hydroxy-3-phenoxypropyl acrylate (10 mol), was applied to LCD 3D printing technology, and the Y-shaped connector was printed. In addition, the antimicrobial activity makes these vitrimers particularly important for use in areas with high microbial concentrations, such as medical facilities.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144482552","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 : 2025-06-23DOI: 10.1021/acs.biomac.5c00275
Qing Huang, Xiaonuo Hu, Xinyu Fan, Yuchen Li, Ming Wei, Xinning Li, Kecen Liu, Zihan Lin, Yi Li, Zhaoming Dong, Ping Zhao, Qingyou Xia, Xin Wang
{"title":"Longer Duct, Better Silk: Unveiling How Anterior Silk Gland Length Boosts Fiber Performance.","authors":"Qing Huang, Xiaonuo Hu, Xinyu Fan, Yuchen Li, Ming Wei, Xinning Li, Kecen Liu, Zihan Lin, Yi Li, Zhaoming Dong, Ping Zhao, Qingyou Xia, Xin Wang","doi":"10.1021/acs.biomac.5c00275","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00275","url":null,"abstract":"<p><p>The mechanical performance of silk is closely tied to the fibrillization process within the anterior segment of silk gland (ASG). While a long and narrow ASG is conserved across silk-spinning species, its biological role remains unclear. Here, we performed a comprehensive structure-function analysis of the silkworm ASG and revealed that its long and narrow morphology plays an essential role in silk fibrillization and fiber performance. A steep reduction in duct diameter at the ASG's onset initiates silk protein transformation, while the extended duct length promotes molecular alignment, crystallization, and orientation. Genetic manipulation to extend ASG length significantly increased the Young's modulus and toughness of silkworm silk fibers. These findings demonstrate the potential of ASG length modulation as an effective strategy to improve silk fiber performance and provide valuable insights into the biological and functional importance of silk gland morphology.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144473410","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 : 2025-06-23DOI: 10.1021/acs.biomac.5c00427
Hongli Li, Xueqin Wang, Xiaoyu Song, Hanyuan Fu, Lige Yang, Dachao Deng, Kedong Xu, Lili Li, Fei Li
{"title":"Sustainably Polyanionic Hyaluronic Acid-Based Hydrogel for Efficient Removal of Fe<sup>3+</sup>, Cd<sup>2+</sup>, and Pb<sup>2+</sup> Ions in Soil with Enhanced Sorghum Growth.","authors":"Hongli Li, Xueqin Wang, Xiaoyu Song, Hanyuan Fu, Lige Yang, Dachao Deng, Kedong Xu, Lili Li, Fei Li","doi":"10.1021/acs.biomac.5c00427","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00427","url":null,"abstract":"<p><p>Toxic metals damage soil quality and harm human health via bioaccumulation, necessitating eco-friendly removal techniques. Hydrogel-based adsorption offers a promising approach for heavy metal extraction. Nevertheless, the potential of innovative hyaluronic acid (HA)-based hydrogels has not been fully investigated. In this study, levodopa and tannic acid were first grafted onto HA using condensation reactions. Subsequently, the HLDT hydrogel was developed by grafting Na-AMPS onto the HA derivative through free radical polymerization, which enhanced its mechanical properties for metal ion adsorption. The HLDT hydrogel shows superior metal adsorption capacities of 193.3, 316.9, and 49.6 mM/g for Cd, Fe, and Pb, respectively. Notably, the exceptional adsorption, desorption, and regeneration capabilities, make it ideal for recycling. Additionally, the HLDT hydrogel can remove heavy metals from polluted soil efficiently and enhance the sorghum growth characteristics. Our findings provide a potential solution for the sustainable recovery of contaminated farmland while enhancing productivity.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144473411","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 : 2025-06-23DOI: 10.1021/acs.biomac.5c00026
Jui Shivaji Chaugule, Yujia Xu
{"title":"Designed Fibril-Forming Mini-Collagens Engineered to Exhibit up to Two Orders of Magnitude Differences in Rates of Matrix Metalloproteinase I Susceptibility.","authors":"Jui Shivaji Chaugule, Yujia Xu","doi":"10.1021/acs.biomac.5c00026","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00026","url":null,"abstract":"<p><p>The susceptibility to matrix metalloproteinases (MMPs) directly affects the functions and applications of collagen biomaterials. In this work, we demonstrated that this property can be manipulated in collagen-mimetic biomaterials created using designed peptides. We developed three fibril-forming mini-recombinant collagens (MRCs) using bacterial expression and designed genes that model a 108-residue section of human type III collagen surrounding the MMP-1 recognition site. Notably, the MRCs can form a native-like fibrillar structure representing the natural substrate of MMP-1. By altering the number of digestion sites or mutating the residues at the canonical scissile bond of MMP-1, the sensitivity to proteolysis of the MRCs varied by two orders of magnitude despite having homologous amino acid sequences and a similar fibrillar structure, and regardless of whether the peptides were in the triple helix conformation or as fibrils. These MRCs can be a versatile collagen alternative for regenerative medicine offering a regulated turnover rate catering to specific applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144473409","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 : 2025-06-21DOI: 10.1021/acs.biomac.5c00551
Guilu Xu, Ying Wu, Xichao Liang, Yakun Zong, Lei Pang, Lu Gan, Lin Tan
{"title":"Multifunctional Macrofibers via Wet Spinning: Integrating Antibacterial, Flame-Retardant, and UV Shielding Properties Using Multinetwork Cellulose-Based Aqueous Colloids.","authors":"Guilu Xu, Ying Wu, Xichao Liang, Yakun Zong, Lei Pang, Lu Gan, Lin Tan","doi":"10.1021/acs.biomac.5c00551","DOIUrl":"10.1021/acs.biomac.5c00551","url":null,"abstract":"<p><p>Wet spinning of nanocellulose in purely aqueous systems for functionalized filament formation represents a significant yet challenging research frontier. This study develops a sustainable wet-spinning approach to produce high-performance macrofibers using TEMPO-oxidized bacterial cellulose nanofibers (TOBCN), sodium alginate (Alg), and metal-phenolic networks (MPNs). The system utilizes Fe<sup>3+</sup>-mediated cross-linking in MPNs combined with Ca<sup>2+</sup>-induced ionic bonding with TOBCN to achieve enhanced mechanical properties. The optimized Alg/TAFe<sub>1</sub>-TOBC<sub>2</sub> fiber demonstrates remarkable multifunctional characteristics, including photothermal antibacterial efficacy exceeding 99% against both <i>Escherichia coli</i> and <i>Staphylococcus aureus</i>, superior flame retardancy with 61.05% lower heat release compared to cotton, and excellent UV protection with UV protection factor values surpassing 100, which exceed standard textile requirements. The purely aqueous processing and biomass-based composition ensure environmental compatibility and biocompatibility. These macrofibers hold promise for protective textiles, combining sustainability with high performance.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144339692","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}