ACS Biomaterials Science & Engineering最新文献

{"title":"Divergent Outcomes in Resilin-Like Peptide Cross-linking: Unexpected Photocatalytic Damage vs Enzymatic Success","authors":"Sradha M. Thomas,&nbsp;Che Zhang,&nbsp;Haixin Zhang,&nbsp;Yuxiang Wang,&nbsp;Sanaz Farajollahi,&nbsp;Patrick M. Dennis,&nbsp;Kun Wang,&nbsp;Marc R. Knecht,&nbsp;Tiffany R. Walsh","doi":"10.1021/acsbiomaterials.6c01174","DOIUrl":"10.1021/acsbiomaterials.6c01174","url":null,"abstract":"<p>Highly elastomeric materials are routinely found in nature that are generated from enzymatic cross-linking of proteins such as resilin. This process can be recreated on the benchtop using conventional photocatalytic approaches, which can be highly efficient; however, due to the large size of the elastomer generated via protein cross-linking, confirmation of the final structure remains elusive. Herein, we explore photocatalytic cross-linking of smaller resilin-like peptides (RLPs), taken from the resilin protein, which do not precipitate upon cross-linking. Using a [Ru(bpy)₃]²⁺-based photocatalytic process, significant peptide degradation was observed, which dominated the reaction. Alternatively, enzymatic cross-linking of the peptides was observed to generate the anticipated product. Similar studies were conducted on a larger peptide construct where both the photocatalytic and enzymatic cross-linking process generated elastomeric materials with differing morphologies. AFM-based analysis confirmed vastly different Young’s moduli based upon the cross-linking strategy. Computational modeling was used to predict likely molecular-level structures and mechanical properties of the elastomer materials based on both the photocatalytic and enzymatic preparation processes, indicating that the case where the rate of cross-linking is greater than that of chain fragmentation is the more likely photocatalytic scenario, based on the trends in predicted Young’s modulus.</p>","PeriodicalId":8,"journal":{"name":"ACS Biomaterials Science & Engineering","volume":"12 10","pages":"5323–5332"},"PeriodicalIF":6.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149078963","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrophoretic Deposition and Characterization of Multicomponent Chitosan/Eudragit or Poly(4-vinylpyridine) Coatings Incorporating Mesoporous Bioactive Glass and Silver Nanoparticles on Ti-13Nb-13Zr Alloy","authors":"Łukasz Pawłowski,&nbsp;Yi-Xin Liu,&nbsp;Chen-Ying Su,&nbsp;Aleksandra Mirowska,&nbsp;Muhammad Asim Akhtar,&nbsp;Magdalena Narajczyk,&nbsp;Joanna Sypniewska,&nbsp;Agata Knabe,&nbsp;Anna Ronowska,&nbsp;Adrianna Banach-Kopeć,&nbsp;Oskar Ronda,&nbsp;Aleksandra Mielewczyk-Gryń,&nbsp;Aldo Roberto Boccaccini,&nbsp;Hsu-Wei Fang","doi":"10.1021/acsbiomaterials.6c00944","DOIUrl":"10.1021/acsbiomaterials.6c00944","url":null,"abstract":"<p>In this study, multifunctional composite coatings based on chitosan (CS), mesoporous bioactive glass nanoparticles (MBGNPs), and silver nanoparticles (AgNPs) were successfully deposited on Ti-13Nb-13Zr alloy by electrophoretic deposition (EPD). Two coating systems containing Eudragit E100 (EE100) or poly(4-vinylpyridine) (P4VP) were developed to tailor physicochemical and biological properties. The synthesized MBGNPs exhibited a spherical morphology with an average particle size of approximately 80 nm, as observed by TEM, while XRD analysis confirmed their amorphous structure. Both coatings formed uniform porous layers (∼10 µm thick) with excellent adhesion to the substrate (class 1, EN ISO 2409). Surface characterization revealed significantly increased roughness and distinct wettability behavior depending on polymer composition. CS/EE100 coatings exhibited hydrophobic character and low surface free energy, whereas CS/P4VP coatings showed highly hydrophilic behavior with increased surface energy. Electrochemical studies demonstrated enhanced electrochemical activity of coated samples, particularly for the P4VP-based system, associated with its porous and hydrophilic structure. Ion release studies confirmed time-dependent calcium release from MBGNPs and significantly higher silver ion release from CS/P4VP coatings, especially under acidic conditions. Both coatings exhibited strong antibacterial activity against <em>Escherichia coli</em> and <em>Staphylococcus aureus</em>, achieving up to ∼2.4 log reduction. Cytocompatibility studies using hFOB 1.19 osteoblast-like cells demonstrated that the CS/P4VP/MBGNPs/AgNPs coating maintained high cell viability (&gt;80%) despite increased Ag⁺ release, while both coatings maintained alkaline phosphatase activity. Overall, the P4VP-based coating demonstrated the most favorable balance between antibacterial activity, ion release, and cytocompatibility, highlighting its potential for advanced biomedical implant applications.</p>","PeriodicalId":8,"journal":{"name":"ACS Biomaterials Science & Engineering","volume":"12 10","pages":"5303–5322"},"PeriodicalIF":6.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148872313","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multidimensional Regulatory Network of Cellular Senescence: From Mechanisms to Theranostics","authors":"Zexiang Lv,&nbsp;Yanfei Liu,&nbsp;Yongbo Liu,&nbsp;Yifu Tan,&nbsp;Yunqi Man,&nbsp;Shuqing Du,&nbsp;Zhirou Zhang,&nbsp;Luke P. Lee,&nbsp;Qi-Wen Chen,&nbsp;Zhenbao Liu","doi":"10.1021/acsbiomaterials.6c00849","DOIUrl":"10.1021/acsbiomaterials.6c00849","url":null,"abstract":"<p>Cellular senescence is orchestrated by a complex and multidimensional regulatory network, whose functional outputs shift dynamically with disease stage and tissue context. This review systematically maps the molecular architecture of this network. The network encompasses the p53/p21 and p16/RB axes, mitochondrial stress pathways, and the cGAS–STING and mTOR-driven SASP programs. In parallel, the review traces how these mechanisms are rewired across a spectrum of pathological contexts, including cancer, metabolic and skeletal disorders, and organ-specific degenerative diseases. Building on this mechanistic foundation, we highlight theranostic innovations that integrate detection with intervention. These include enzyme-activatable prodrugs and probes that exploit senescence-associated markers such as SA-β-gal, enabling simultaneous imaging and cell clearance. Other examples are smart nanocarriers, which achieve spatiotemporally controlled drug delivery, and engineered immune cells, which restore immunosurveillance against senescent cells. Additionally, we discuss emerging platforms for dynamic quantification of senescent burden <em>in vivo</em>, including molecular imaging probes and liquid biopsy signatures. Despite promising preclinical progress, clinical translation remains limited by senescent-cell heterogeneity, off-target toxicity, and the lack of standardized biomarkers. By integrating mechanistic insights with theranostic design principles, this review provides a framework for developing precision strategies to detect, modulate, or eliminate senescent cells in a context-appropriate manner.</p>","PeriodicalId":8,"journal":{"name":"ACS Biomaterials Science & Engineering","volume":"12 10","pages":"5228–5249"},"PeriodicalIF":6.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148965755","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Genipin-Cross-Linked Decellularized Amnion Membrane with Antioxidant and Anti-Inflammatory Properties","authors":"Tong Zhang,&nbsp;Mingfei Shao,&nbsp;Jingwen Wu,&nbsp;Yanchuan Guo","doi":"10.1021/acsbiomaterials.6c01480","DOIUrl":"10.1021/acsbiomaterials.6c01480","url":null,"abstract":"<p>The regulation of post-implantation inflammatory responses is essential for biomaterials to achieve their intended functions, with macrophages playing a pivotal role in this process. The persistence of M1 macrophages impairs the timely resolution of acute inflammation, thereby delaying tissue healing and compromising biomaterial performance. The decellularized amnion membrane (DAM) exhibits notable anti-inflammatory properties. However, its limited mechanical strength and poor degradation resistance restrict its clinical applications. This study employed genipin cross-linking to improve the mechanical strength and enzymatic degradation resistance of DAM, resulting in a genipin-cross-linked DAM scaffold (GED) with enhanced anti-inflammatory properties. GED demonstrated markedly enhanced mechanical strength, thermal stability, and degradation resistance, retaining its structural integrity even after 28 days of collagenase-mediated degradation in vitro. Moreover, GED exhibited the ability to scavenge excess reactive oxygen species (ROS) and suppress LPS-induced pro-inflammatory cytokine expression in macrophages, thereby effectively mitigating inflammation. This research provides new insights into the development of extracellular matrix-based materials and highlights GED as a promising multifunctional anti-inflammatory scaffold for tissue engineering applications.</p>","PeriodicalId":8,"journal":{"name":"ACS Biomaterials Science & Engineering","volume":"12 10","pages":"5697–5708"},"PeriodicalIF":6.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148965785","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Salvianic Acid A-Loaded Layered Double Hydroxide Nanosheets Boost T-Cell Infiltration through Tumor Vascular Normalization for Enhanced Immunotherapy","authors":"Yuxi Xiang,&nbsp;Junyu Tan,&nbsp;Xicheng Yan,&nbsp;Yunyun Wu,&nbsp;Chang Yu,&nbsp;Daqing Xia,&nbsp;Jing Zhu,&nbsp;Hongrui Zhu,&nbsp;Jixi Zhang","doi":"10.1021/acsbiomaterials.6c01291","DOIUrl":"10.1021/acsbiomaterials.6c01291","url":null,"abstract":"<p>Abnormal tumor vasculature impedes T-cell migration and compromises immunotherapy. Conventional anti-angiogenic strategies fail to restore the endothelial barrier and adhesion molecules. This limitation hinders long-term therapeutic benefits. Therefore, simultaneously restoring vascular function and activating immunity is essential. Herein, a pH-responsive, salvianic acid A-loaded manganese-aluminum layered double hydroxide nanosystem (S-LDH) was developed for synergistic regulation. In the acidic tumor microenvironment, S-LDH degrades in situ to release salvianic acid A and manganese ions. Released salvianic acid A directly repairs endothelial junctions via the β-catenin/claudin-5 pathway, restoring vascular integrity to promote immune cell infiltration. Concurrently, released manganese ions induce oxidative stress and trigger ICD via Fenton-like reactions while amplifying the cGAS-STING pathway to promote dendritic cell maturation and cytotoxic T-cell responses. Furthermore, STING activation upregulates endothelial adhesion molecules, further facilitating T-cell infiltration. In a 4T1 murine breast cancer model, S-LDH increased CD8⁺ T-cell infiltration by 10.9-fold and CD4⁺ T-cell infiltration by 4.3-fold compared with free salvianic acid A, confirming that simultaneous vascular repair and immune activation overcome the endothelial barrier. This work establishes a strategy that repairs tumor endothelial integrity and upregulates adhesion molecules to overcome this limitation by enabling T-cell infiltration.</p>","PeriodicalId":8,"journal":{"name":"ACS Biomaterials Science & Engineering","volume":"12 10","pages":"5450–5464"},"PeriodicalIF":6.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149023359","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Dynamic Modeling Framework for Real-Time Monitoring of Porcine Lung Tissue Decellularization","authors":"Ziyu Wang,&nbsp;Annmarie Bedsaul,&nbsp;Chloe G. Hincher,&nbsp;Maria Jimenez-Socha,&nbsp;Shelby E. White,&nbsp;Daphne Sze,&nbsp;Joel Ducoste,&nbsp;Camilo Mora,&nbsp;Donald O. Freytes","doi":"10.1021/acsbiomaterials.6c00414","DOIUrl":"10.1021/acsbiomaterials.6c00414","url":null,"abstract":"<p>Decellularized extracellular matrix (dECM) scaffolds are critical for tissue engineering and regenerative medicine, yet standardized methods for real-time monitoring of decellularization remain lacking. Current protocols typically use fixed treatment durations to match endpoint control quality attributes (CQAs), such as final dsDNA content in the scaffold, without a mechanistic understanding of DNA removal kinetics. This knowledge gap leads to either incomplete decellularization (CQA rejections) or unnecessary processing time, compromising dECM scaffold quality and process efficiency. In this paper, we develop a model-based mathematical monitoring framework for rapid assessment of DNase-treated porcine lung tissue that integrates dual-optical sensing of supernatant DNA release via ultraviolet–visible (UV–vis) absorbance and fluorescence. Decellularization supernatant was collected every 10 min over a 100-min treatment window in each sample group. Signals were well described by a first-order accumulation model <em>C</em>(<em>t</em>) = <em>C</em>₀ + (<em>C</em>_max – <em>C</em>₀) (1 – e^{–<em>kt</em>}), yielding an interpretable kinetic descriptor <em>k</em> and a model-based progress metric. A linear relationship was observed between the initial tissue mass and rate constant (<em>R</em>² = 0.9998), enabling mass-aware prediction of release kinetics. When explored in dimensionless coordinates, normalized trajectories collapsed onto the universal curve <em>f</em>(τ) = 1 – e^–τ that supports shared kinetics across sensing modalities. Model-derived in-process metrics were associated with endpoint residual tissue dsDNA quantified by QuantiFluor tissue digests and revealed an accessibility-limited gap between supernatant signal completion and tissue-level DNA removal within the treatment window. Together, these results provide the foundation of a practical process analytical technology style framework for quantitative decellularization monitoring and quality control, supporting mass-aware forecasting of process progress and adaptive protocol development.</p>","PeriodicalId":8,"journal":{"name":"ACS Biomaterials Science & Engineering","volume":"12 10","pages":"5527–5540"},"PeriodicalIF":6.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148885611","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Defect-Engineered Tetragonal ZrO2 Nanoparticles for Biomaterial Interfaces: Green Synthesis, Biointerfacial Interactions, and SERS Biosensing","authors":"Edyta Proniewicz,&nbsp;Olga Surma,&nbsp;Marta Gajewska,&nbsp;Marcin Molenda","doi":"10.1021/acsbiomaterials.6c00755","DOIUrl":"10.1021/acsbiomaterials.6c00755","url":null,"abstract":"<p>Zirconia (ZrO₂) is a widely used biomaterial in dental and orthopedic applications due to its excellent biocompatibility, chemical stability, and mechanical properties. However, the role of defect structure and phase composition in governing biomolecule–surface interactions at the biointerface remains insufficiently understood. In this work, we demonstrate a synthesis-driven strategy for engineering defect-rich tetragonal ZrO₂ nanoparticles via conventional wet-chemical and plant-extract-mediated green routes using <em>Laurus nobilis</em>, <em>Salvia rosmarinus</em>, and <em>Ficus benghalensis</em>. Plant-mediated synthesis using rosemary extract promotes the formation of phase-pure tetragonal ZrO₂ with increased surface heterogeneity and a higher density of oxygen vacancy-related defect states. To probe biomolecule–surface interactions, surface-enhanced Raman spectroscopy (SERS) measurements were performed using L-phenylalanine as a model system. This approach provides a simplified model of amino acid adsorption relevant to early-stage protein–surface interactions. Defect-rich tetragonal ZrO₂ exhibits enhanced SERS response driven by charge-transfer interactions associated with oxygen vacancies and surface states. This represents one of the first demonstrations of amino-acid-based probing of zirconia SERS substrates in a biomaterial-relevant context, extending beyond conventional symmetric aromatic probe systems. In addition, the materials exhibit photocatalytic activity, interpreted as defect-driven surface reactivity and the ability to generate reactive oxygen species relevant for antibacterial functionality and prevention of biofilm formation at biomaterial interfaces in clinical environments. Overall, this work establishes a structure–property–function framework linking synthesis strategy with defect structure and interfacial performance, providing a framework for the rational design of zirconia-based biomaterials with controlled biointerface functionality.</p>","PeriodicalId":8,"journal":{"name":"ACS Biomaterials Science & Engineering","volume":"12 10","pages":"5390–5405"},"PeriodicalIF":6.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148954541","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Calcium-Specific-Binding PLGA Microspheres with Embedded BMP-2 for Bone Regeneration","authors":"Minjae Kim,&nbsp;Jun Ho Park,&nbsp;Min-Ha Choi,&nbsp;Yan Lee,&nbsp;Ji-Ung Park","doi":"10.1021/acsbiomaterials.6c00581","DOIUrl":"10.1021/acsbiomaterials.6c00581","url":null,"abstract":"<p>Bone morphogenetic protein-2 (BMP-2) is a potent osteoinductive factor for bone regeneration, but its rapid clearance and dose-dependent adverse effects limit its clinical use. This study developed calcium-binding poly(butyl methacrylate-<em>co</em>-methacryloyloxyethyl phosphate) (PBMP)-coated poly(lactide-<em>co</em>-glycolide) (PLGA) microparticles to enhance calcium-rich surface anchoring and enable sustained BMP-2 release. Microparticles were characterized for morphology, zeta potential, encapsulation efficiency, release kinetics, and hydroxyapatite (HA)-binding affinity, and were further evaluated for <em>in vivo</em> efficacy. PBMP coating markedly increased the HA-binding affinity of PLGA microparticles. Encapsulation efficiency was over 55%, and BMP-2 was released in a sustained manner over 30 days, with the cumulative release gradually approaching a plateau during the later incubation period. When applied to a rat calvarial defect model, the PBMP-coated microparticle (BMP-2-PLGA/PBMP) group showed the greatest bone volume fraction, bone surface area, and trabecular number, along with the lowest trabecular separation compared to the free BMP-2 and control groups. Histological analysis confirmed denser and more mature bone matrix formation in the BMP-2-PLGA/PBMP group. These findings demonstrate that PBMP-coated PLGA microparticles provide HA-targeted, sustained BMP-2 delivery, resulting in improved bone regeneration and microarchitecture. This delivery platform represents a promising strategy for more effective bone defect repair.</p>","PeriodicalId":8,"journal":{"name":"ACS Biomaterials Science & Engineering","volume":"12 10","pages":"5465–5477"},"PeriodicalIF":6.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149023336","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bioactive Zein–Nondigestible Oligosaccharide Nanofibers Enable Rapid Tissue Regeneration and Antibacterial Defense","authors":"Renugaa Suresh Babu,&nbsp;Piotr Gierlich,&nbsp;Ramakrishnan Swaminathan,&nbsp;Vimalraj Selvaraj,&nbsp;Wendy W. J. Unger,&nbsp;Swathi Sudhakar","doi":"10.1021/acsbiomaterials.6c00314","DOIUrl":"10.1021/acsbiomaterials.6c00314","url":null,"abstract":"<p>Chronic wounds pose a significant clinical challenge due to persistent inflammation, microbial infection, and impaired tissue regeneration. Conventional wound dressings often lack the multifunctionality needed for comprehensive wound management. In this study, we engineered a nanofibrous wound patch composed of zein (ZM) integrated with nondigestible oligosaccharides (ZM-NDOs), such as Chito-oligosaccharides (ZMC), guluronic and mannuronic-rich alginate-oligosaccharides (ZMAGM), and guluronic-rich alginate-oligosaccharides (ZMAG), to address these limitations. Structural and physicochemical analyses (SEM, FTIR, UTM, and water contact angle) confirmed the formation of bead-free, interconnected fibers with enhanced mechanical strength and hydrophilicity. <em>In vitro</em> cytocompatibility assays using HEK 293T cells demonstrated excellent biocompatibility for both ZM and ZM-NDO patches. Notably, ZMC significantly promoted cellular proliferation and migration in wound scratch assays, accelerating wound closure. <em>In vivo</em> evaluation using a Wistar rat excision wound model further substantiated the therapeutic efficacy of the ZM-NDO patches, showing improved collagen deposition, vascularization, and epithelial regeneration, accompanied by upregulated expression of <em>VEGF, TGF-β,</em> and <em>Col-I</em> mRNA. Moreover, the ZMC scaffolds exhibited significant antibacterial activity against <em>Pseudomonas aeruginosa</em> and methicillin-resistant <em>Staphylococcus aureus</em>. Collectively, these findings highlight ZM-NDO, particularly ZMC, as a promising, multifunctional, and scalable platform for advanced wound-healing applications.</p>","PeriodicalId":8,"journal":{"name":"ACS Biomaterials Science & Engineering","volume":"12 10","pages":"5498–5514"},"PeriodicalIF":6.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149072785","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Casting Environment and Water Retention Modulate β-Sheet Crystallization and Shelf Stability of Native Bombyx mori Silk Fibroin Films","authors":"John M. Malki,&nbsp;Kevin Chalek,&nbsp;Natali M. Ulloa,&nbsp;Bethany N.Q. Tran,&nbsp;Gregory P. Holland","doi":"10.1021/acsbiomaterials.6c01363","DOIUrl":"10.1021/acsbiomaterials.6c01363","url":null,"abstract":"<p>The performance and shelf life of <em>Bombyx mori</em> silk fibroin biomaterials are governed by β-sheet crystallinity, which determines solubility, degradation, and mechanical properties. However, controlling β-sheet crystallinity during processing and storage remains a major challenge because the metastable Silk I structure can convert to the β-sheet-rich, insoluble Silk II form. Here, native silk fibroin dope extracted directly from the gland was dissolved in water and cast into films under ambient or vacuum conditions, then aged and stored under controlled environments to identify the processing variables governing β-sheet formation. Differential scanning calorimetry (DSC) showed that freshly cast films were amorphous and that a crystallization exotherm emerged only after prolonged aging (≥2 months) of ambient-cast films, whereas vacuum-cast films were more resistant to crystallization across concentrations and storage conditions. Thermogravimetric analysis (TGA) revealed that ambient-cast films retained more loosely bound water than vacuum-cast films, while tightly bound water remained comparable, implicating loosely bound water as the plasticizer that enables molecular rearrangement. Quantitative magic angle spinning (MAS) solid-state NMR of ¹³C-Ala-labeled films confirmed that fresh and aged films remained predominantly amorphous (10–24% Ala β-sheet), demonstrating that the DSC exotherm arises from thermally induced crystallization of a water-plasticized precursor rather than from a pre-existing β-sheet order. Upon thermal annealing, fresh ambient-cast films reached 75% Ala β-sheet compared with only 38% for vacuum-cast films, demonstrating that the casting environment establishes the upper limit of β-sheet conversion. These findings provide a practical processing strategy for tailoring crystallinity and shelf stability: ambient casting promotes subsequent crystallization, vacuum casting preserves a low-crystallinity amorphous state, and dry storage minimizes β-sheet crystallization.</p>","PeriodicalId":8,"journal":{"name":"ACS Biomaterials Science & Engineering","volume":"12 10","pages":"5333–5343"},"PeriodicalIF":6.0,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149100932","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}