Mohadeseh Zare, Laura Colomina Alfaro, Antonella Bandiera, Esra Cansever Mutlu, David Grossin, Fernando Albericio, Sarah A Kuehne, Zubair Ahmed, Artemis Stamboulis
{"title":"Immobilization of KR-12 on a Titanium Alloy Surface Using Linking Arms Improves Antimicrobial Activity and Supports Osteoblast Cytocompatibility.","authors":"Mohadeseh Zare, Laura Colomina Alfaro, Antonella Bandiera, Esra Cansever Mutlu, David Grossin, Fernando Albericio, Sarah A Kuehne, Zubair Ahmed, Artemis Stamboulis","doi":"10.1021/acsabm.4c01731","DOIUrl":"https://doi.org/10.1021/acsabm.4c01731","url":null,"abstract":"<p><p>Implant-associated infections pose significant challenges due to bacterial resistance to antibiotics. Recent research highlights the potential of immobilizing antimicrobial peptides (AMPs) onto implants as an alternative to conventional antibiotics for the prevention of bacterial infection. While various AMP immobilization methodologies have been investigated, they lack responsiveness to biological cues. This study proposes an enzyme-responsive antimicrobial coating for orthopedic devices using KR-12, an AMP derived from Cathelicidin LL-37, coupled with the Human Elastin-Like Polypeptide (HELP) as a biomimetic and stimuli-responsive linker, while mimicking the extracellular matrix (ECM). During implantation, these customized interfaces encounter the innate immune response triggering elastase release, which degrades HELP biopolymers, enabling the controlled release of KR-12. After coupling KR-12 with HELP to titanium surfaces, the antimicrobial activity against four pathogenic bacterial strains (<i>Staphylococcus aureus</i>, <i>Staphylococcus epidermidis</i>, <i>Escherichia coli</i>, and <i>Pseudomonas aeruginosa</i>) was assessed, revealing an inhibition ratio of bacterial adhesion and colonization exceeding 92% for all tested strains, compared with surfaces functionalized with KR-12 only. It is thought that the enhanced antimicrobial activity was due to the improved mobility of KR-12 when coupled with HELP. Furthermore, the prepared coatings boosted the adhesion and proliferation of human osteoblasts, confirming the cytocompatibility. These findings suggest the potential for smart coatings that combine the antimicrobial functions of AMPs with HELP's biological properties for use in a variety of settings, including medical devices.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143726985","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":"β-Cyclodextrin Encapsulated Platinum(II)-Based Nanoparticles: Photodynamic Therapy and Inhibition of the NF-κB Signaling Pathway in Glioblastoma.","authors":"Sakira Tabassum Borah, Anushka Mondal, Bishnu Das, Sanchari Saha, Jayasri Das Sarma, Parna Gupta","doi":"10.1021/acsabm.5c00103","DOIUrl":"https://doi.org/10.1021/acsabm.5c00103","url":null,"abstract":"<p><p>This study explores cell death through photodynamic therapy (PDT) with β-cyclodextrin-encapsulated platinum(II)-based nanoparticles (<b>Pt-NPs</b>) and the effect on the NF-κB and stress pathways in glioblastoma. The encapsulation of the cyclometalated Pt(II) complex <b>Pt(LL')</b> within β-cyclodextrin (β-CD) enhances its biocompatibility, improves cellular penetration, and boosts emission, thereby increasing the effectiveness of PDT. Both <b>Pt(LL')</b> and <b>Pt-NPs</b> show minimal toxicity in the dark; however, <b>Pt-NPs</b> significantly increase toxicity toward glioblastoma Kr158 cells upon irradiation at 390 nm. The PDT-induced cell death is further validated through apoptosis assays and the modulation of some key survival pathways like NF-κB/p65, DJ-1, and ERp29. This is the first report of β-cyclodextrin-encapsulated platinum(II)-based nanoparticles designed to target glioblastoma cells through PDT, offering a promising strategy for enhancing therapeutic efficacy.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143726989","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":"Graphene Oxide-Modified Resin for Selective dsRNA Removal from In Vitro-Transcribed mRNA.","authors":"Junhyung Ryu, Jayoung Namgung, Jinmin Jang, Goeun Lee, Kwanghee Yoo, Bong-Hyun Jun, Dong-Eun Kim","doi":"10.1021/acsabm.5c00320","DOIUrl":"https://doi.org/10.1021/acsabm.5c00320","url":null,"abstract":"<p><p>Messenger RNA (mRNA) has proven to be an effective vaccine agent against unexpected pandemics, offering the advantage of rapidly producing customized therapeutics targeting specific pathogens. However, undesired byproducts, such as double-stranded RNA (dsRNA), generated during <i>in vitro</i> transcription (IVT) reactions may impede translation efficiency and trigger inflammatory cytokines in cells after mRNA uptake. In this study, we developed a facile method using PEGylated polystyrene resins that were further surface-modified with graphene oxide (GO@PEG-PS) for the removal of dsRNA from IVT mRNA. The GO@PEG-PS resin adsorbed mRNA due to the property of graphene oxide (GO), which preferentially adsorbs single-stranded nucleic acids over double-stranded nucleic acids in the presence of Mg<sup>2+</sup>. The resin-bound single-stranded (ss) RNA was readily desorbed with a mixture of EDTA and urea, possibly by chelating Mg<sup>2+</sup> and disrupting hydrogen bonding, respectively. Spin-column chromatography with GO@PEG-PS for IVT mRNA eliminated at least 80% of dsRNA, recovering approximately 85% of mRNA. Furthermore, this procedure precluded the salt precipitation step after the IVT reaction, which fractionates mRNAs from the IVT components, including nucleotides and enzymes. The purified mRNA exhibited enhanced protein translation with reduced secretion of interferon (IFN)-β upon mRNA transfection. We anticipate that the mRNA purification chromatography system employing GO@PEG-PS resin will facilitate the removal of dsRNA contamination during mRNA production.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143726982","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":"Targeting Lysozyme-Linked Amyloidosis through Piperine-Functionalized Gold Nanoparticles.","authors":"Anubhuti Bhatia, Nishant Mishra, Kailash Prasad Prajapati, Venkat Ramanan Srinivasan, Sindhujit Roy, Ridhiee Bonda, Shikha Mittal, Priyadharshini M, Sabitri Dash, Om Prakash Mahato, Aditya Acharya, Masihuzzaman Ansari, Karunakar Kar, Bibin Gnanadhason Anand","doi":"10.1021/acsabm.4c01841","DOIUrl":"https://doi.org/10.1021/acsabm.4c01841","url":null,"abstract":"<p><p>Excess accumulation of misfolded and mutated human lysozyme (HuL) is the pathological hallmark of non-neuropathic systemic amyloidosis. These deposits are rich in cross β-sheet conformers and often exist as polymorphic fibrillar structures, which makes it a tricky and challenging task to design therapeutic interventions toward HuL-linked amyloidopathy. Here we aimed to design an effective antiamyloid metal nanoparticle formulation to target the exposed hydrophobic and aggregation-prone stretches in HuL. Initially, we synthesized and characterized piperine-coated gold nanoparticles (AuNPs<sup>Pip</sup>). ThT-probed aggregation studies of HuL in the presence and absence of AuNPs<sup>Pip</sup> revealed an inhibition of lysozyme aggregation. This inhibition effect was confirmed through dynamic light scattering (DLS) and fluorescence microscopy analyses. We further investigated whether AuNPs<sup>Pip</sup> could bind to preformed fibrils and prevent the secondary nucleation process, which is a crucial step in amyloidogenesis. Our results showed that AuNPs<sup>Pip</sup> not only prevented seed-induced aggregation but also disassembled preformed amyloid aggregates, which was not observed with AuNPs or piperine. Experimental and computational studies suggest that the retention of the lysozyme native structure and the ability of AuNPs<sup>Pip</sup> to interact with the aggregation-prone residues are key factors in the inhibition mechanism. The findings of this work may aid in developing nanoparticle-based formulations to prevent pathologies linked to lysozyme aggregation.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143717566","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}
Geneva Indongo, Susan Varghese, Merin K Abraham, Greeshma Rajeevan, Arathy B Kala, Dheyaa Mohammed Dhahir, Dr Sony George
{"title":"Fluorescence Turn-On Sensing of Leucine Using Bimetallic Cu-Ag Nanoclusters: A Potential Non-Invasive Biomarker for Cancer Detection.","authors":"Geneva Indongo, Susan Varghese, Merin K Abraham, Greeshma Rajeevan, Arathy B Kala, Dheyaa Mohammed Dhahir, Dr Sony George","doi":"10.1021/acsabm.5c00102","DOIUrl":"https://doi.org/10.1021/acsabm.5c00102","url":null,"abstract":"<p><p>This study investigates the use of bimetallic copper-silver nanoclusters (Cu-AgNCs) for fluorescence turn-on sensing of leucine, a potential biomarker for cancer detection. These nanoclusters exhibit high fluorescence tunability and specificity, with Fe<sup>3+</sup> serving as a quencher to facilitate leucine detection. The fluorescence recovery mechanism is attributed to the interaction of leucine with Fe<sup>3+</sup>, alleviating the quenching effect on the metal nanoclusters. This bimetallic nanocluster is a promising platform for biomarker identification in cancer diagnosis. The fluorescence enhancement upon leucine binding provides a measurable signal, confirming the feasibility of these nanoclusters as noninvasive sensors for cancer biomarkers. The sensor achieves a detection limit of 0.58 μM and demonstrates a linear response within the range of 110-657 μM. This approach offers a promising method for noninvasive cancer diagnostics using saliva and urine samples. Additionally, the method's reproducibility and robustness further support its potential in clinical applications, providing a cost-effective and accessible technique for early cancer detection.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143707749","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":"Naphthazarin Mounted on the Manganese Carbonate Nanocube Induced Enrichment of Endogenous Copper and Fenton-like Reaction for Enhanced Chemodynamic Therapy.","authors":"Zhichao Wang, Yuan Zeng, Susu Gao, Ziwei Chen, Chunying Chen, Yaling Wang","doi":"10.1021/acsabm.5c00089","DOIUrl":"https://doi.org/10.1021/acsabm.5c00089","url":null,"abstract":"<p><p>Chemodynamic therapy (CDT), which utilizes transition metal ions to catalyze Fenton-like reactions for the eradication of tumor cells, has attracted substantial attention in the field of nanocatalysis. However, the therapeutic efficacy of CDT as a monotherapy is often limited by an insufficient level of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) and the overexpressed glutathione (GSH) within tumor cells. Because of the high copper content in tumor tissues, a copper ionophore was strategically employed to enhance the intracellular accumulation of copper, thereby potentiating the CDT effect. Additionally, bovine serum albumin (BSA) was used to modify the copper ionophore, naphthazarin (Nap), to promote its targeting efficacy for tumor cells and to ensure its biosafety. The BSA-coated Nap nanoparticles, which could recruit Cu<sup>2+</sup> in situ, were further deposited onto the surface of a manganese carbonate nanocube (Nap-BM NPs). The synergistic action of copper and manganese ions accelerated the decomposition of H<sub>2</sub>O<sub>2</sub> into hydroxyl radicals (•OH) and consumed intracellular GSH, leading to cellular mortality via mitochondrial pathways. With low cytotoxicity and good biocompatibility in normal cells, the developed Nap-BM NPs significantly enhanced therapeutic outcomes by leveraging multiple Fenton-like reaction mechanisms to augment CDT, offering promising potential for clinical applications and contributing valuable insights into the field.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699122","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":"Self-Assembling Nucleopeptides Exhibiting Strong Antimicrobial Activity against Multidrug-Resistant Clinically Isolated Strains and In Vitro Wound Healing Compatibility.","authors":"Swapnendu Deb, Shalini Gupta, Supratim Bose, Tanushree Mondal, Biplab Mondal, Arindam Banerjee","doi":"10.1021/acsabm.4c01891","DOIUrl":"https://doi.org/10.1021/acsabm.4c01891","url":null,"abstract":"<p><p>To combat the emerging threat of antimicrobial resistance (AMR), in this study, two amphiphilic nucleopeptides (NPs) were synthesized by conjugating the nucleobase thymine with peptide amphiphiles. These compounds were fully characterized using various analytical techniques. Notably, both nucleopeptides formed hydrogels in milli-Q water at neutral pH (pH 6.9). X-ray diffraction further confirmed antiparallel β-sheet-like structures, along with aromatic π-π stacking and hydrogen-bonding (H-bonding) interactions between the thymine moieties in the gel phase. Field emission gun transmission electron microscopy revealed a nanofibrillar network structure in these self-assembled peptides. A significant feature of these peptide supramolecular self-assemblies is their potent antimicrobial activity against both types of bacteria, such as Gram-positive and Gram-negative standard American Type Culture Collection (ATCC) bacteria, including <i>Bacillus subtilis</i>, <i>Escherichia coli</i>, and multidrug-resistant clinically isolated ATCC strains such as methicillin-resistant <i>Staphylococcus aureus</i> (MRSA), <i>Klebsiella pneumoniae</i>, and <i>Pseudomonas aeruginosa</i>. Among these, both peptides demonstrated remarkable inhibition of MRSA (MIC: 15.92-16.86 μM) and <i>K. pneumoniae</i> (MIC: 8.8-50 μM), highlighting their potential as antimicrobial agents against deadly multidrug-resistant (MDR) bacteria. Additionally, these peptide assemblies were found to be highly biocompatible, as demonstrated by MTT assays on HEK-293 cells, showing IC<sub>50</sub> values in the range of 0.5-1.1 mM. In an in vitro wound healing assay using HeLa cells, fluorescence microscopy confirmed that treatment with these nucleopeptides did not disrupt the cell or mitochondrial membranes in HEK-293 cells. This work presents two nucleopeptides with broad-spectrum antimicrobial efficacy against MDR strains and demonstrates high biocompatibility, supporting their potential use as antimicrobial agents.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699123","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}
Ronak Lazarus, Rupal Kothari, Venkata Vamsi Krishna Venuganti, Amit Nag
{"title":"Intracellular Temperature Sensing with Remarkably High Relative Sensitivity Using Nile Red-Loaded Biocompatible Niosome.","authors":"Ronak Lazarus, Rupal Kothari, Venkata Vamsi Krishna Venuganti, Amit Nag","doi":"10.1021/acsabm.4c01856","DOIUrl":"https://doi.org/10.1021/acsabm.4c01856","url":null,"abstract":"<p><p>Accurate temperature sensing at the nanoscale within biological systems is crucial for understanding various cellular processes, such as gene expression, metabolism, and enzymatic reactions. Current temperature-sensing techniques either lack the temperature resolution and sensitivity necessary for intracellular applications or require invasive procedures that can disrupt cellular activities. In this study, we present Nile Red (NR)-loaded hybrid (span 60-L64) niosomes and Nile Red-loaded L64 niosomes as highly sensitive fluorescent nanothermometers. These niosomes are synthesized via the thin-layer evaporation method, forming thermoresponsive vesicles, and they demonstrate reversible phase transition behavior with temperature. When loaded with polarity-sensitive Nile Red, vesicles exhibit a strong temperature-dependent fluorescence response (change in intensity, emission maximum, and lifetime), suitable for noncontact temperature sensing in the biologically important temperature range of 25 to 50 °C. While NR-hybrid niosomes exhibit a high relative sensitivity of 19% °C<sup>-1</sup> at 42 °C, NR-L64 niosomes achieved extraordinary relative sensitivity of 36% °C<sup>-1</sup> at 40 °C. Using NR-L64 niosomes, the temperature resolution is found to be 0.0004 °C at 40 °C. The nanothermometers displayed excellent photostability, thermal reversibility, and resistance to variations in ion concentration and pH. Temperature-dependent confocal microscopy using FaDu cells confirmed the biocompatibility and effectiveness of the designed nanothermometers for precise intracellular temperature sensing. The results demonstrate the significant potential of Nile Red-loaded niosomes for temperature monitoring using live cell imaging in biological media.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699120","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":"Microstructural Effects of Melt Electrowritten-Reinforced Hydrogel Scaffolds for Engineering Thick Skin Substitutes.","authors":"Ferdows Afghah, Mine Altunbek, Mahdiyeh Zahrabi, Bahattin Koc","doi":"10.1021/acsabm.4c01541","DOIUrl":"https://doi.org/10.1021/acsabm.4c01541","url":null,"abstract":"<p><p>Engineering thick skin tissue substitutes resembling the physiochemical and mechanical properties of native tissue is a significant challenge. Melt electrowriting (MEW) is a powerful technique with the capability of fabricating highly ordered structures with fine fiber diameters, closely replicating the native extracellular matrix (ECM). In this study, we constructed melt electrowritten porous polycaprolactone (PCL) scaffolds with three different geometries by depositing fibers at 0-90 and 60-120° in a mesh structure and in a honeycomb-like orientation to assess the effects of the microstructure on the mechanical strength of the scaffold and cellular behavior. These scaffolds were subsequently infilled with gelatin hydrogel, encapsulating human skin dermal fibroblasts (HSFs) and human umbilical vein endothelial cells (HUVECs). Mechanical tensile tests revealed that the honeycomb microstructure of the hybrid PCL/gelatin scaffold exhibited greater elongation at failure, along with an acceptable elastic modulus suitable for skin tissue applications. All scaffolds provided a cytocompatible microenvironment that maintained over 90% cell viability and preserved typical cell morphology. HSFs were guided through the PCL fibers to the apical surface, while HUVECs were distributed within the gelatin hydrogel within the hybrid structure. Additionally, HSFs' alignment was regulated by the scaffold geometry. Notably, the expression of CD31 in HUVECs─a key transmembrane protein for capillary formation─increased significantly over a 14 day incubation period. Among those, 0-90° mesh and honeycomb geometries showed the greatest effects on the upregulation of CD31. These findings demonstrate that the microstructural guidance of HSFs and their interaction with HUVECs in hybrid structures play a crucial role in promoting vascularization. In conclusion, the honeycomb MEW-gelatin hybrid scaffold demonstrates significant potential for effectively replicating both the mechanical and physicochemical properties essential for full-thickness skin tissue substitutes.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699121","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}
Utsab Ayan, Madara Mohoppu, John Adams Sebastian, Rasha Elkanayati, Veeresh B Toragall, Ahmed Wadi, Sasan Nouranian, Thomas Werfel, Byron S Villacorta
{"title":"Cytocompatible 2D Graphitic Carbon Nitride-Modified Polybutylene Adipate Terephthalate/Polylactic Acid Hybrid Nanobiocomposites.","authors":"Utsab Ayan, Madara Mohoppu, John Adams Sebastian, Rasha Elkanayati, Veeresh B Toragall, Ahmed Wadi, Sasan Nouranian, Thomas Werfel, Byron S Villacorta","doi":"10.1021/acsabm.4c02009","DOIUrl":"https://doi.org/10.1021/acsabm.4c02009","url":null,"abstract":"<p><p>Polymer nanobiocomposites (PNCs) prepared with graphitic carbon nitride (GCN) nanosheets in polybutylene adipate terephthalate (PBAT)/polylactic acid (PLA) bioblends were processed using a three-step processing technique that involved: (1) a solution-based GCN exfoliation step; (2) a masterbatching step of GCN in PBAT by solution processing; and (3) a melt-compounding step where the masterbatch was mixed with pristine PLA to delaminate the 2D GCN layers by extrusion high-shear mixing and to deposit them onto the biphasic PLA/PBAT morphology. Due to the partial exfoliation of GCN, this process led to a concurrent presence of three distinct morphologies within the PNCs' microstructure: (1) Type 1, characterized by an unaltered interface and PLA matrix, with minimal GCN deposition within the PBAT phase; (2) Type 2, distinguished by a diffused and stiff interface with GCN distribution in both the dispersed (PBAT) and matrix (PLA) phases; and (3) Type 3, featuring unmodified interfaces and GCN localization across both PLA and PBAT phases with a stair-like morphological texture. Such a morphological combination generates distinct crack propagation micromechanics, thereby influencing the variability of the plastic deformational behavior of their PNCs. Particularly, the Type 1 morphology enables GCN to act as a secondary stress-dissipating agent, whereas the PBAT domains serve as the primary stress-absorbing sites, contributing to enhanced crack propagation energy requirements. Contrarily, Type 3 (slightly) and Type 2 (predominantly) morphologies invert GCN's role from stress dissipation to stress concentration due to its localization within the PLA matrix. Differential scanning calorimetry revealed a crystallinity increase in the PNCs until 0.1 wt % GCN, followed by a decline, likely due to agglomeration at higher contents. Thermogravimetric analysis showed that GCN addition improved the thermostability of the bioblends, attributed to the GCN's nanophysical and pyrolytic barrier effect. Moreover, using both direct and indirect methods, GCN did not impair the biocompatibility of the bioblends as confirmed via cytocompatibility assays.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699119","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}