Young-Ae Choi, , , Jun Young Park, , , Jinjoo Kang, , , Na-Hee Jeong, , , Soyoung Lee, , , Dongwoo Khang*, , and , Sang-Hyun Kim*,
{"title":"Topical Nanocarrier-Assisted Corticosteroid Delivery Combined with Phototherapy for Effective Atopic Dermatitis Treatment","authors":"Young-Ae Choi, , , Jun Young Park, , , Jinjoo Kang, , , Na-Hee Jeong, , , Soyoung Lee, , , Dongwoo Khang*, , and , Sang-Hyun Kim*, ","doi":"10.1021/acsabm.5c01594","DOIUrl":"10.1021/acsabm.5c01594","url":null,"abstract":"<p >Topical corticosteroids are widely used to manage chronic inflammatory skin diseases, such as atopic dermatitis (AD). However, their limited skin penetration necessitates high doses and prolonged use, which increases the risk of local and systemic side effects. To address these limitations, we developed a gold nanorod–conjugated dexamethasone (AuNR-DEX) system combined with red light-emitting diode (LED) irradiation to enhance transdermal drug delivery and therapeutic efficacy. AuNR conjugation enhanced the physicochemical properties of DEX, including its hydrodynamic diameter and surface charge, thereby facilitating increased skin penetration. In an AD mouse model, topical AuNR-DEX significantly alleviated disease symptoms at only 20% of the dose required for free DEX. While AuNR-DEX alone showed limited dispersion across the skin, cotreatment with red LED irradiation facilitated broader spreading and improved drug distribution. The combination therapy markedly restored epidermal differentiation, collagen fiber integrity, and calcium homeostasis in AD skin lesions. In vitro, AuNR-DEX plus LED treatment enhanced keratinocyte survival, restored the localization of tight junction proteins, and reduced mitochondrial calcium overload and reactive oxygen species levels. Overall, the synergistic effect of AuNR-DEX and red LED irradiation enhanced drug delivery, targeted dispersion, and therapeutic outcomes, offering a promising strategy for treating AD with reduced corticosteroid dosage and minimized side effects.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":"8 10","pages":"9464–9479"},"PeriodicalIF":4.7,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Harnessing Quintuple Layer Dependent Antisuperbug Properties from 2D Bi2Se3 Topological Quantum Material for Targeted Eradication of MRSA Biofilms","authors":"Olorunsola Praise Kolawole, , , Avijit Pramanik, , , Shivangee Rai, , , Sanchita Kundu, , , Kaelin Gates, , and , Paresh Chandra Ray*, ","doi":"10.1021/acsabm.5c01384","DOIUrl":"10.1021/acsabm.5c01384","url":null,"abstract":"<p ><i>Staphylococcus aureus</i> (MRSA) biofilms significantly hinder the effectiveness of conventional antimicrobial agents, which pose a major challenge in treating biofilm infections in clinics. In the current paper, we unveiled targeted superbug biofilm eradication using Bi<sub>2</sub>Se<sub>3</sub> nanoplate based quantum material, where antisuperbug properties are strongly influenced by its unique layered structure composed of quintuple layers (QLs). We show that control over targeted eradication of MRSA superbugs can be achieved by harnessing QL dependent anti-MRSA properties for the Bi<sub>2</sub>Se<sub>3</sub> nanoplate. Reported data demonstrated that the quantum material has the capability for 100% selective eradication of MRSA by selectively targeting the lipoteichoic acid (LTA) of Gram-positive bacteria. However, due to the lack of binding with lipopolysaccharide of Gram-negative superbugs, the quantum material lacks effective eradication of carbapenem-resistant <i>E. coli</i> and <i>Salmonella DT104</i> superbugs. Experimental data show that the 3QL thick Bi<sub>2</sub>Se<sub>3</sub> nanoplate has the capability for wrapping MRSA bacteria very strongly via binding with LTA, which can physically enclose the MRSA and allow superbugs to effectively isolate them from their environment, ultimately inhibiting bacterial proliferation. In addition, the minimum inhibitory concentration (MIC) value changes by an order of magnitude (∼10 to ∼100 μg mL<sup>–1</sup>) as the thickness of the nanoplate varies from 3 to 15 QLs. Moreover, the nanoplate has the capability for the selective inhibition of MRSA biofilm growth, where the minimum biofilm eradication concentration (MBEC) varies by more than an order of magnitude with the variation of QLs. These findings demonstrate the potential of quantum materials to address the growing threat of MRSA infections.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":"8 10","pages":"9254–9267"},"PeriodicalIF":4.7,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237513","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Multifunctional Mn–Cu Bimetallic DNAsome for Photothermal-Assisted Chemodynamic Cancer Therapy","authors":"Gowtham Raj, , , Justin Prasad, , , Tamraparni Ghosh, , , Devu B. Kumar, , , Athul V. Beena, , , Harsha Perozhy, , , Joyraj Kalita, , , Vasudev D. Sreekumar, , , Anusree Krishna, , and , Reji Varghese*, ","doi":"10.1021/acsabm.5c00519","DOIUrl":"10.1021/acsabm.5c00519","url":null,"abstract":"<p >The efficacy of chemodynamic cancer therapy is drastically reduced due to the sluggish reaction kinetics of Fenton reactions inside the tumor microenvironment (TME). Hence, it is highly desirable to develop strategies that can improve the reaction kinetics of the Fenton reaction at the TME. Herein, a supramolecular approach for the crafting of a DNA-based chemodynamic therapy (CDT) agent containing dual Fenton reaction centers and a photothermal agent (<b>DNA1some/PDMn/DNA2</b>) for the targeted and enhanced chemodynamic cancer therapy is reported. The nanoformulation exhibited targeted cellular internalization via a receptor-mediated endocytosis mechanism and underwent disassembly at the lysosome, leading to the release of individual components of the nanoformulation, which include (i) Cu<sup>2+</sup>, (ii) Mn<sup>4+</sup>, and polydopamine. Reduction of Cu<sup>2+</sup> and Mn<sup>4+</sup> with intracellular GSH yielded two Fenton reaction centers, Cu<sup>+</sup> and Mn<sup>2+</sup>, respectively, which underwent Fenton reaction with H<sub>2</sub>O<sub>2</sub> to produce <sup>•</sup>OH. Further, photoirradiation of the nanoformulation using an 808 nm laser resulted in a photothermal effect due to the presence of polydopamine. This not only facilitates the cellular apoptosis via the photothermal effect but also improves the efficiency of both Cu<sup>+</sup>- and Mn<sup>2+</sup>-based Fenton reactions. The enhanced therapeutic outcome was due to the synergetic combination of PTT and CDT.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":"8 10","pages":"8631–8642"},"PeriodicalIF":4.7,"publicationDate":"2025-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145243251","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Anastasia Vlachou, , , Om Shanker Tiwari, , , Sonika Chibh, , , Jake R. Remmert, , , Ehud Gazit*, , and , Phanourios Tamamis*,
{"title":"Minimalistic Peptide Nanocarriers for Multiple Cancer Drugs","authors":"Anastasia Vlachou, , , Om Shanker Tiwari, , , Sonika Chibh, , , Jake R. Remmert, , , Ehud Gazit*, , and , Phanourios Tamamis*, ","doi":"10.1021/acsabm.5c01234","DOIUrl":"10.1021/acsabm.5c01234","url":null,"abstract":"<p >The co-assembly of minimalistic peptides with cancer drugs, leading to the formation of nanocarriers for drug delivery, comprises a promising direction in chemotherapeutics. We computationally designed fluorescent minimalistic four-residue peptide nanocarriers for multiple cancer drugs: Epirubicin, Doxorubicin, Methotrexate, Mitomycin-C, 5-Fluorouracil, Camptothecin, and Cyclophosphamide. The optimally designed resulting nanocarriers formed by FFWH have notable drug encapsulation properties for the drugs investigated, according to both computational and experimental studies. Additionally, the nanocarriers possess biocompatibility, enhanced fluorescence, and uptake into HeLa cells using live cell confocal microscopic images. Our simulations demonstrate how the same peptide can efficiently be used to encapsulate these drugs as well as provide structural and biophysical understanding of their properties. We suggest that the designed nanocarriers can serve as programmable nanostructures for the future design of new generations of advanced nanocarriers with potential cancer- and patient-specific targeting properties.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":"8 10","pages":"9093–9108"},"PeriodicalIF":4.7,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsabm.5c01234","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237515","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mingyang Mao, Forest Thompson, Katherine Ballard, Hosein Mirazi, Noah Terkildsen, Roman Shchepin, Scott Wood, Tugba Ozdemir
{"title":"Developing an Artificial Synovial Membrane Model Using Hyaluronic Acid-Binding Peptides.","authors":"Mingyang Mao, Forest Thompson, Katherine Ballard, Hosein Mirazi, Noah Terkildsen, Roman Shchepin, Scott Wood, Tugba Ozdemir","doi":"10.1021/acsabm.5c01205","DOIUrl":"https://doi.org/10.1021/acsabm.5c01205","url":null,"abstract":"<p><p>In normal synovial membranes, CD68-fibroblast-like synoviocytes (FLSs) and CD68+ macrophage-like synoviocytes (MLSs) form a bilayer structure and secrete heteroglycans and proteins (primarily hyaluronic acid [HA] and lubricin [PRG4]) that lubricate the joint and produce synovial fluid. Notably, despite the important role of synovial membrane cells in rheumatological diseases, such as osteoarthritis (OA) and rheumatoid arthritis (RA), relatively few artificial synovial membrane models exist in the literature, and those that have been presented are often minimally biomimetic. HA is an integral part of a healthy synovial membrane and synovial fluid. Utilization of strategies introducing HA has been studied earlier; however, no such study exists utilizing endogenous HA for tissue engineering of the synovial membrane. In this study, we utilized hyaluronic acid binding peptide (HABPs) functionalized onto nanofibrous poly-ε-caprolactone (PCL) scaffolds following electrospinning. The physical properties, such as surface morphology and surface tribology, of these scaffolds were tested to ensure they exhibit characteristics reminiscent of the native synovial membranes. To further mimic the native synovial membranes, human dermal fibroblasts (hDFs) were seeded onto the surfaces of the HABP-functionalized scaffolds. In the study, the development of cells and their production of HA were tested to evaluate the therapeutic effect of artificial synovial membranes. The results showed that HABP-functionalized scaffolds aid in cell proliferation, HA retention on scaffolds, and HA secretion into the cell culture supernatant by hDFs. We conclude that HABP-functionalized artificial synovial membranes cultured with fibroblasts can serve as a suitable scaffold toward tissue engineering of human synovial membranes.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":" ","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237423","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Electric Field-Driven Bacterial Membrane Disintegration with Real-Time Electrical Response in SWCNT Bioelectronic Platforms","authors":"Sovanlal Mondal, , , Asima Pradhan, , , Suman Mandal, , , Shiv Prakash Verma, , , Subhamay Pramanik, , , Ajoy Mandal, , , Madhuchanda Banerjee, , and , Dipak K. Goswami*, ","doi":"10.1021/acsabm.5c00912","DOIUrl":"10.1021/acsabm.5c00912","url":null,"abstract":"<p >We report a bioelectronic platform that integrates hydrophilically functionalized single-walled carbon nanotubes (SWCNTs) with <i>Escherichia coli</i> and gold (Au) electrodes to investigate real-time charge transport at microbial–electrode interfaces. Acid-functionalized SWCNTs enhance aqueous dispersibility and facilitate electron transfer in a deionized water environment under applied bias. Upon bacterial introduction, the device exhibits a sharp transient current spike followed by a stabilization phase, indicative of dynamic bacterial attachment and interfacial electron exchange. Kelvin probe force microscopy (KPFM) mapping reveals changes in contact potential difference (CPD) among the SWCNTs, bacteria, and Au electrodes, confirming localized charge redistribution. Additionally, the formation of depletion regions near electrode edges─driven by bacterial repulsion and ionic interactions, generates capacitive effects that modulate device conductivity. Systematic variation of bacterial concentration demonstrates a direct influence on device response, providing mechanistic insight into microbial charge transfer behavior. These findings establish a foundational understanding of nanobioelectronic interactions and highlight the potential of SWCNT-based platforms in real-time microbial sensing, environmental biosurveillance, and next-generation bioelectronic applications.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":"8 10","pages":"8794–8804"},"PeriodicalIF":4.7,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145230995","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Fabrication of P25@MIL-101(Fe)@Ag Composite Material with Enhanced Antibacterial Activity","authors":"Qi Cao, , , Shuang Xu, , , Xianfu Wang, , , Boxi Jia, , , Lan Zhou, , , Shuyu Xie*, , and , Zhexue Lu*, ","doi":"10.1021/acsabm.5c01510","DOIUrl":"10.1021/acsabm.5c01510","url":null,"abstract":"<p >The issue of bacterial resistance poses a serious threat to human health, and the synthesis and application of silver-based nanomaterials with broad-spectrum antimicrobial activity have attracted widespread attention. To address the instability and limited antibacterial efficacy of silver nanoparticles (AgNPs), this study developed a composite material with enhanced antibacterial performance─P25@MIL-101(Fe)@Ag─by using commercial P25 titanium dioxide coated with MIL-101(Fe) as a support and loading AgNPs via an <i>in situ</i> tannic acid reduction method. Peroxidase-like activity assays revealed that the composite exhibited superior enzyme-mimicking activity compared to AgNPs alone. <i>In vitro</i> antibacterial experiments demonstrated that the composite showed significantly enhanced broad-spectrum antibacterial activity compared to AgNPs, and its bactericidal efficacy was further improved when used in combination with hydrogen peroxide. <i>In vivo</i> wound healing experiments on mice infected with methicillin-resistant <i>Staphylococcus aureus</i> (MRSA) showed that the composite effectively eliminated MRSA from the wound site and promoted wound healing, highlighting its promising potential for practical applications in treating drug-resistant bacterial infections.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":"8 10","pages":"9414–9423"},"PeriodicalIF":4.7,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145237492","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kun Wang, , , Jing Sun, , , Hongyu Zhang, , , Liang Li, , , Ning Zhang, , , Zhiqi Liu, , , Ming Shi, , , Jiexia Wen, , , Yimin Wang*, , and , Kun Li*,
{"title":"Research on the Effect of NK Cells Based on Functionalized Magnetic Beads on Cervical Cancer Mice","authors":"Kun Wang, , , Jing Sun, , , Hongyu Zhang, , , Liang Li, , , Ning Zhang, , , Zhiqi Liu, , , Ming Shi, , , Jiexia Wen, , , Yimin Wang*, , and , Kun Li*, ","doi":"10.1021/acsabm.5c00811","DOIUrl":"10.1021/acsabm.5c00811","url":null,"abstract":"<p >In recent years, the incidence of tumors has shown an increasing trend, while traditional treatment methods such as surgery, radiotherapy, and chemotherapy exhibit certain limitations. Immunotherapy has been extensively investigated in the field of cancer treatment due to its advantages of high specificity in recognition, significant inhibition of tumor growth and proliferation, and the absence of adverse effects on the structure and function of normal tissue cells. Natural killer (NK) cells, as crucial components of the innate immune system, play a pivotal role in antitumor immune responses. In this study, a magnetic nanocarrier loaded with NK cells was constructed to combine magnetic targeting with NK immunotherapy. By integrating magnetic targeting with NK cell immunotherapy, this system enhances NK cell infiltration at tumor sites through external magnetic field guidance, thereby improving the tumor-killing efficacy. The main research contents are as follows: nanoscale Fe<sub>3</sub>O<sub>4</sub>@Agarose beads (AMbs) were fabricated and carboxylated to obtain carboxylated Fe<sub>3</sub>O<sub>4</sub>@Agarose-COOH beads with a particle size of approximately 200 nm. Using these carboxylated beads as carriers, the “AMbs-MCD16-NK” magnetic targeting system was constructed by conjugating the aptamer MCD16, which corresponds to the CD16 surface protein on NK cells. A U14 mouse cervical cancer tumor-bearing model was established to evaluate the in vivo antitumor efficacy and biosafety of the system. The results demonstrated that the “AMbs-MCD16-NK” system exhibited excellent tumor-targeting capability at the tumor site under magnetic field regulation, achieving a tumor inhibition rate of 57.32 ± 12.98% in mice. This system effectively inhibited tumor cell proliferation, induced apoptosis and necrotic lesions in tumor tissues, promoted NK cell infiltration into the tumor site, and regulated the release of proinflammatory cytokines (e.g., interferon-γ (IFN-γ) and granzyme B (GZMB)), thereby enhancing NK cell cytotoxicity against tumor cells. Detection of a series of biological indicators in mice confirmed that the “AMbs-MCD16-NK” system possessed favorable biosafety. Collectively, the “AMbs-MCD16-NK” system developed in this study enhances NK cell-based immunotherapy through magnetic targeting, providing a strategy for NK cell-mediated cancer treatment.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":"8 10","pages":"8721–8734"},"PeriodicalIF":4.7,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145211088","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Neha Dubey, , , Sonali Gupta, , , Sandeep B. Shelar, , , Bijaideep Dutta, , , Kanhu C. Barick*, , and , Sudeshna Chandra*,
{"title":"Stimuli-Responsive Upconversion Nanoparticles-Embedded Mesoporous SiO2 Nanospheres for Delivery of Hydrophilic and Hydrophobic Anticancer Drugs and Cellular Imaging","authors":"Neha Dubey, , , Sonali Gupta, , , Sandeep B. Shelar, , , Bijaideep Dutta, , , Kanhu C. Barick*, , and , Sudeshna Chandra*, ","doi":"10.1021/acsabm.5c00966","DOIUrl":"10.1021/acsabm.5c00966","url":null,"abstract":"<p >Core–shell architectures are widely reported for enhancing the luminescence properties of upconversion nanoparticles (UCNPs) by minimizing surface quenching and optimizing energy transfer pathways. However, this study demonstrates a hybrid structure in which UCNPs (CaF<sub>2</sub>:Yb<sup>3+</sup>, Er<sup>3+</sup>) are embedded in a mesoporous silica (<i>m</i>-SiO<sub>2</sub>) nanosphere using a soft chemical approach, offering an alternative to conventional core–shell structures. The structural analysis by X-ray diffraction (XRD) and transmission electron microscopy (TEM) confirmed the successful entrapment of highly crystalline cubic phase fluorite-type UCNPs in a mesoporous SiO<sub>2</sub> framework (UCNPs@m-SiO<sub>2</sub>). These UCNPs@m-SiO<sub>2</sub> exhibited a high surface area, porous nature, good colloidal stability, and pH-dependent charge-converting characteristics, which made them extremely conducive for drug delivery application. This matrix-based design not only stabilizes the nanoparticles but also significantly enhances their upconversion luminescence properties upon near-infrared (NIR) light irradiation (980 nm). Furthermore, the porous nature of the silica matrix allows efficient encapsulation of anticancer drugs, doxorubicin hydrochloride (DOX) and curcumin (CUR), and demonstrates their sustained and controlled pH-responsive release with higher release in a mildly acidic environment. The-drug loaded systems showed enhanced toxicity toward breast (MCF-7) and lung (A549) cancer cells over their individual counterparts (DOX and CUR). Moreover, the developed UCNPs@m-SiO<sub>2</sub> retained their red emission capability upon internalization into cancer cells and thus can also be used for cellular imaging purposes. Specifically, this work demonstrated the development of water-dispersible, biocompatible, and photostable UCNPs for image-guided drug delivery applications.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":"8 10","pages":"8815–8828"},"PeriodicalIF":4.7,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145211071","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Adrian Wittrock, , , Christian Beckmann, , , Markus A. Wimmer, , , Alfons Fischer, , , Saurabh M. Das, , , Christian H. Liebscher, , and , Jörg Debus*,
{"title":"Fretting-Induced Formation of Nanocrystalline CoSx Tribomaterial at the Hip Implant Taper Junction","authors":"Adrian Wittrock, , , Christian Beckmann, , , Markus A. Wimmer, , , Alfons Fischer, , , Saurabh M. Das, , , Christian H. Liebscher, , and , Jörg Debus*, ","doi":"10.1021/acsabm.5c01185","DOIUrl":"10.1021/acsabm.5c01185","url":null,"abstract":"<p >Gross-slip fretting corrosion occurs frequently inside taper joints of endoprosthetic implants and is expected to be accompanied by the formation of a metal-organic tribomaterial, which may influence the friction and wear behavior of implants. While it is hypothesized that it contains compounds of the surrounding human body fluid and worn particles of the implant materials, its structure, composition, formation mechanism, and distribution inside the wear area remain elusive. In a multiscale structural-chemical study using Raman scattering spectroscopy and transmission electron microscopy, we reveal the tribological formation of nanocrystalline cobalt sulfide for a CoCrMo/TiAlV couple that was subjected to <i>in vitro</i> gross-slip fretting in bovine calf serum. We demonstrate that sulfur atoms released from the mechanochemical decomposition of cysteine/cystine disulfide bonds in serum proteins ─ as evidenced by the complete absence of characteristic S–S Raman modes and concurrent protein unfolding from α-helix to β-sheet structures ─ react with cobalt ions released tribocorrosively from the alloy to form the CoS<sub><i>x</i></sub> tribomaterial. The resulting tribofilm is substoichiometric (<i>x</i> < 2) with a primary cubic structure partially mixed by a hexagonal phase. It perfectly adheres to the Co alloy through mechanical mixing, thus exhibiting the structural features of extreme-pressure antiwear additives. The CoS<sub><i>x</i></sub> tribofilm covers 12.2% of the fretting track in the CoCrMo alloy, while maintaining a consistent thickness of approximately 15 nm. Multiple mechanisms driving this transformation are discussed: mechanical protein unfolding exposes disulfide bonds to forces that reduce their cleavage activation energy, local temperatures allow for thermal decomposition, and the acidic crevice environment facilitates chemical cleavage. The observations on the fretting-generated CoS<sub><i>x</i></sub> tribomaterial provide the first comprehensive structural-chemical insight into tribologically beneficial features of transition metal sulfides formed in medical alloys through protein-derived sulfur. Understanding this mechanism may enable strategies to deliberately promote such protective film formation to improve the longevity of taper junctions in medical applications.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":"8 10","pages":"9019–9030"},"PeriodicalIF":4.7,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145211141","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}