BiomacromoleculesPub Date : 2025-03-07DOI: 10.1021/acs.biomac.4c01781
Elizabeth L Aikman, Lauren E Eccles, Whitney L Stoppel
{"title":"Native Silk Fibers: Protein Sequence and Structure Influences on Thermal and Mechanical Properties.","authors":"Elizabeth L Aikman, Lauren E Eccles, Whitney L Stoppel","doi":"10.1021/acs.biomac.4c01781","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01781","url":null,"abstract":"<p><p>Silk fibers produced by arthropods have inspired an array of materials with applications in healthcare, medical devices, textiles, and sustainability. Silks exhibit biodiversity with distinct variations in primary protein constituent sequences (fibroins, spidroins) and structures across taxonomic classifications, specifically the Lepidopteran and Araneae orders. Leveraging the biodiversity in arthropod silks offers advantages due to the diverse mechanical properties and thermal stabilities achievable, primarily attributed to variations in fiber crystallinity and repeating amino acid motifs. In this review, we aim to delineate known properties of silk fibers and correlate them with predicted protein sequences and secondary structures, informed by newly annotated genomes. We will discuss established patterns in repeat motifs governing specific properties and underscore the biological diversity within silk fibroin and spidroin sequences. Elucidating the relationship between protein sequences and properties of natural silk fibers will identify strategies for designing new materials through rational silk-based fiber design.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143571553","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":"Fe-Doped Carbon Dots-Incorporated In Situ Hydrogel for Near Infrared-Triggered Cascading Photothermal/Thermodynamic Therapy to Boost Cancer Immunity Cycle.","authors":"Fengyi Du, Lixia Xu, Haoran Wang, Mengke Lu, Qinxin Wang, Xiaonan Qiu, Baoding Chen, Miaomiao Zhang","doi":"10.1021/acs.biomac.5c00051","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00051","url":null,"abstract":"<p><p>Photothermal therapy-triggered whole-tumor cell antigens release has revolutionized in situ cancer vaccine, but insufficient anticancer immunity cycle activation greatly limits its curative effect. Herein, we designed an NIR-triggered cascading in situ vaccine (FCDs-A/C@HGs) by incorporating the Fe-doped carbon dots (FCDs), azo-initiator (AIPH), and immune adjuvant (cyclophosphamide) into the thermosensitive hydrogel. Due to iron doping, the as-prepared FCDs exhibited high photothermal conversion performance and favorable MR imaging capability. Upon intratumoral injection, local hyperthermia mediated by FCDs-A/C@HGs and the subsequent generation of alkyl radicals from AIPH synergistically induced immunogenic cell death in tumor cells. Remarkably, the FCDs-A/C@HGs elicited strong anticancer immune activation by inhibiting regulatory T cells and promoting dendritic cell maturation, thereby enhancing differentiation of cytotoxic CD8+ T cells and memory T cells. This study presents an effective therapeutic platform for in situ tumor suppression and sustained activation of the anticancer immunity cycle.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143571551","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":"Efficient and Size-Controllable Method and Mechanism for Preparing Cellulose Nanospheres.","authors":"Weixiong Zhao, Yuhang Zhou, Guichao Zhang, Yue Li, Zixuan Liao, Gaorong Lai, Yongze Jiang, Shanshan Jia, Zhiping Su, Jinqiu Qi, Shaobo Zhang","doi":"10.1021/acs.biomac.5c00103","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00103","url":null,"abstract":"<p><p>Cellulose nanosphere (CNS), reported as a novel cellulose material, has encountered significant challenges in achieving efficient and size-controllable preparation, which has considerably constrained its development. In this study, we have developed an innovative and size-controllable method that synthesizes CNS within only 7 min. A detailed investigation into the morphology, chemical structure, and crystalline structure of CNS was conducted, leading to the proposal of a formation mechanism for CNS. The mechanism is described as follows: cellulose dissolution, hydrophobic triethoxymethylsilane hydrolysis, condensation nucleation in supersaturation, growth through hydrogen-bonding interactions and condensation, and CNS forms in the critical supersaturation. The supersaturation level was controlled by adjusting the stirring speed, thus realizing the size-controllable preparation of CNS and verifying the proposed mechanism. The results demonstrate that the particle size of CNS increases from 63.4 ± 14.0 nm to 108.6 ± 27.1 nm as the stirring speed decreases from 1000 r/min to 300 r/min.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555308","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":"Revitalizing Antibiotics with Macromolecular Engineering: Tackling Gram-Negative Superbugs and Mixed Species Bacterial Biofilm Infections In Vivo.","authors":"Sudip Mukherjee, Sayan Chakravarty, Jayanta Haldar","doi":"10.1021/acs.biomac.4c01520","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01520","url":null,"abstract":"<p><p>The escalating prevalence of multidrug-resistant Gram-negative pathogens, coupled with dwindling antibiotic development, has created a critical void in the clinical pipeline. This alarming issue is exacerbated by the formation of biofilms by these superbugs and their frequent coexistence in mixed-species biofilms, conferring extreme antibiotic tolerance. Herein, we present an amphiphilic cationic macromolecule, ACM-A<sub>Hex</sub>, as an innovative antibiotic adjuvant to rejuvenate and repurpose resistant antibiotics, for instance, rifampicin, fusidic acid, erythromycin, and chloramphenicol. ACM-A<sub>Hex</sub> mildly perturbs the bacterial membrane, enhancing antibiotic permeability, hampers efflux machinery, and produces reactive oxygen species, resulting in a remarkable 64-1024-fold potentiation in antibacterial activity. The macromolecule reduces bacterial virulence and macromolecule-drug cocktail significantly eradicate both mono- and multispecies bacterial biofilms, achieving >99.9% bacterial reduction in the murine biofilm infection model. Demonstrating potent biocompatibility across multiple administration routes, ACM-A<sub>Hex</sub> offers a promising strategy to restore obsolete antibiotics and combat recalcitrant Gram-negative biofilm-associated infections, advocating for further clinical evaluation as a next-generation macromolecular antibiotic adjuvant.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555313","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 : 2025-03-05DOI: 10.1021/acs.biomac.5c00225
Mazaher Gholipourmalekabadi, Alexander M Seifalian, Aleksandra M Urbanska, Mir Davood Omrani, John G Hardy, Zahra Madjd, Seyed Mahmoud Hashemi, Hossein Ghanbarian, Peiman Brouki Milan, Masoud Mozafari, Rui L Reis, Subhas C Kundu, Ali Samadikuchaksaraei
{"title":"Correction to \"3D Protein-Based Bilayer Artificial Skin for the Guided Scarless Healing of Third-Degree Burn Wounds in Vivo\".","authors":"Mazaher Gholipourmalekabadi, Alexander M Seifalian, Aleksandra M Urbanska, Mir Davood Omrani, John G Hardy, Zahra Madjd, Seyed Mahmoud Hashemi, Hossein Ghanbarian, Peiman Brouki Milan, Masoud Mozafari, Rui L Reis, Subhas C Kundu, Ali Samadikuchaksaraei","doi":"10.1021/acs.biomac.5c00225","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00225","url":null,"abstract":"","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555307","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 : 2025-03-04DOI: 10.1021/acs.biomac.4c01338
Jiahui Yang, Zhiyuan Wang, Zepeng Li, Haoyang Xu, Bin Xue, Yi Cao, Zhaojie Li, Yiran Li
{"title":"Halogen-Atom-Substituted DOPA with Enhanced Wet Adhesion and Antioxidization Ability.","authors":"Jiahui Yang, Zhiyuan Wang, Zepeng Li, Haoyang Xu, Bin Xue, Yi Cao, Zhaojie Li, Yiran Li","doi":"10.1021/acs.biomac.4c01338","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01338","url":null,"abstract":"<p><p>3,4-Dihydroxyphenylalanine (DOPA) has inspired the development of artificial adhesives, but efforts to enhance its adhesion strength and durability continue to evolve. However, it is tough work to improve DOPA wet adhesion by chemically decorating DOPA itself, despite the potential benefit of a concise and high-quality adhesion unit. Here, we synthesized a series of DOPA substituents by introducing different electron-withdrawing groups at the ortho position of the phenyl ring. This modification allowed us to effectively control the adhesion and antioxidation properties of DOPA. Combining atomic force microscopy (AFM)-based single-molecule force spectroscopy (SFMS) and cyclic voltammetry, we comprehensively investigated DOPA's antioxidation and adhesion capabilities. We found that adding a chlorine or bromine atom to the catechol ring significantly increases the DOPA wet adhesion strength. Additionally, halogen-substituted DOPA exhibited greater stability than dopamine in liquid solutions. Notably, chlorine-substituted DOPA maintained a strong adhesion ability even in salt water, offering potential benefits for bioadhesive applications.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555309","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":"Nanocellulose/Graphene Oxide Composite Beads as a Novel Hemoperfusion Adsorbent for Efficient Removal of Bilirubin Plasma.","authors":"Xuanru Wei, Hengfeng Zhu, Dichan Hong, Xiangxian Li, Zhuqun Shi, Quanling Yang","doi":"10.1021/acs.biomac.4c01838","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01838","url":null,"abstract":"<p><p>Conventional hemoperfusion adsorbents suffer from inefficiency and poor biocompatibility. Cellulose, a natural polysaccharide with biocompatible, biodegradable, and nontoxic properties, was combined with graphene oxide (GO) to fabricate composite beads (TGO) for blood purification. GO synthesized via a modified Hummers method was complexed with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCNs). Increasing GO content (2-20 wt %) enhanced TGO's specific surface area (256.4-289.0 m<sup>2</sup> g<sup>-1</sup>) while retaining an ∼10 nm pore size. TGO demonstrated exceptional adsorption capacities: bilirubin (418.4 mg g<sup>-1</sup>), creatinine (23.5 mg g<sup>-1</sup>), uric acid (146.6 mg g<sup>-1</sup>), and Cu<sup>2+</sup> (171.9 mg g<sup>-1</sup>). The beads exhibited excellent hemocompatibility (hemolysis rate <5%) and prolonged recalcification time (585 ± 5.2 s). Notably, TGO restored blood bilirubin levels to normal within 30 min, highlighting its potential for blood purification.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555310","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":"Protein Interaction with Zwitterionic Spherical Polyelectrolyte Brushes as Observed by Small Angle X-ray Scattering.","authors":"Ziyu Zhang, Yuhua Zhang, Xin Liu, Jiangtao Guo, Li Li, Weihua Wang, Guofeng He, Xuhong Guo","doi":"10.1021/acs.biomac.4c01782","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01782","url":null,"abstract":"<p><p>Understanding how zwitterionic spherical polyelectrolyte brushes (SPB) fulfill their antifouling functions requires knowledge of their interactions with exogenous nanoparticles, such as proteins. In this study, zwitterionic SPB were synthesized by grafting 3-[(2-(methacryloyloxy)ethyl)dimethylammonio]propanoate (CBMA) and [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide (SBMA) onto a polystyrene core via photoemulsion polymerization. Small-angle X-ray scattering was employed to elucidate the interactions and protein adsorption behaviors of the zwitterionic SPB and proteins. SAXS results revealed that both PCBMA SPB and PSBMA SPB exhibit minimal protein adsorption compared with cationic and anionic SPB. PSBMA SPB maintained a consistent resistance to protein adsorption across various conditions. However, PCBMA SPB demonstrated tunable protein adsorption properties, enabled by the controllable ionization of carboxyl groups on the brush chains while maintaining consistently low overall adsorption. These insights enhance our understanding of zwitterionic SPB and offer an experimental and theoretical basis for their application in biomaterials and antifouling technologies.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143555311","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 : 2025-03-03DOI: 10.1021/acs.biomac.4c01474
Jannik Jarms, Nina H Borzęcka, Bruno Serrador Goncalves, Kathirvel Ganesan, Barbara Milow, Ameya Rege
{"title":"Modeling of the Gelation Process in Cellulose Aerogels.","authors":"Jannik Jarms, Nina H Borzęcka, Bruno Serrador Goncalves, Kathirvel Ganesan, Barbara Milow, Ameya Rege","doi":"10.1021/acs.biomac.4c01474","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01474","url":null,"abstract":"<p><p>Cellulose aerogels are the most well-studied biopolymer-based systems in the literature, yet we lack a complete understanding of the underlying gelation mechanism, as well as that of the effect of solvent exchange on the topology of their network. This work presents a coarse-grained model describing the gelation kinetics in cellulose aerogel systems. A discrete element model is employed to generate the cellulose structure, and the solvents are modeled implicitly. Langevin dynamics is applied to solve the system of Newtonian equations. The model successfully generates the structure of the cellulose gel, hydrogel, alcogel, as well as aerogel. A model parameter sensitivity analysis is presented, and the results of the model are validated against the experimental data. The model provides insights into the mechanism of gelation while also shedding light on the morphological alterations resulting from the washing, solvent exchange, and drying steps.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143603020","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":"Upcycling of Livestock Industry Blood Waste into Bioplastics: Plasma Protein-Based Amyloid Fibrils.","authors":"Shuang Ding, Xing Chen, Yixiang Wang, Nana Zhang, Yuan Tao, Huayu Yang, Bowen Yan, Daming Fan","doi":"10.1021/acs.biomac.4c01564","DOIUrl":"https://doi.org/10.1021/acs.biomac.4c01564","url":null,"abstract":"<p><p>This study presents a novel approach to harnessing the underutilized resource of livestock blood plasma proteins to produce bioplastic films based on amyloid fibrils. Upon acidic heating, a 20-h incubation period resulted in mature, semiflexible fibrils with an average length of 0.65 μm and a persistence length of 261 nm. Characterization using Thioflavin T intensity, circular dichroism, and FTIR spectroscopy revealed a cross-β-sheet structure stabilized by hydrogen bonding. The integration of plasma protein amyloid fibrils with poly(vinyl alcohol) (PVA) or methyl cellulose (MC) yielded bioplastic films that exhibit smooth and homogeneous micromorphology, enhanced toughness, and water stability, with PVA-based films demonstrating an exceptional elongation of ∼300%, suitable for food packaging applications. Compared to petroleum-based plastics, plasma amyloid fibril-incorporated films demonstrated a superior sustainability footprint (∼92%). This work underscores the potential of plasma protein amyloid fibrils in bioplastic applications, aligning with the global imperative for eco-friendly waste management and a circular economy.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143536233","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}