ACS Applied Materials & Interfaces最新文献

{"title":"In Situ Anchoring of Co Single Atoms within Keto-Enamine COFs via the Coordination of an Interlayer N Atom with Co for the Enhanced Photocatalytic CO2 Reduction Efficiency","authors":"Yueli Liu, Luxia Shao, Lingling Ding, Xueyi Chen, Yunan Bao, Wen Chen","doi":"10.1021/acsami.5c02762","DOIUrl":"https://doi.org/10.1021/acsami.5c02762","url":null,"abstract":"Single-atom catalysts (SACs) are prone to agglomeration or migration during catalytic processes, making the development of highly dispersible SACs greatly essential for the performance of photocatalytic CO₂ reduction. Herein, cobalt-containing keto-enamine covalent organic frameworks (COFs) (Co/TpPa-1) are successfully in situ synthesized by utilizing the interlayer nitrogen atom coordinated with metallic cobalt, which is used to effectively prevent the agglomeration of monometallic atoms to ensure the homogeneous dispersion of SACs in the resulting metalized COFs. In the photocatalytic CO₂ reduction, the Co/TpPa-1 composite exhibits significantly enhanced performance compared to the TpPa-1 COFs. The CO yield of 0.05 mM Co/TpPa-1 composite is approximately 414.5 μmol g^–1 h^–1, representing a two-order-of-magnitude improvement over the TpPa-1 COF catalyst (approximately 4.15 μmol g^–1 h^–1). Moreover, the 0.05 mM Co/TpPa-1 composite shows 99.45% selectivity for CO and good stability, maintaining a over 97% CO₂ reduction rate after four cycles. The reason lies in the fact that the interaction between monatomic Co and TpPa-1 COFs enhances visible light absorption and extends the lifetime of the photogenerated carriers by promoting electron transfer through the loaded monatomic Co. This work provides a new idea for the catalyst synthesis with high performance and high selectivity.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"5 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866419","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Co-Assembly-Driven Chiral Induction of Well-Defined Polyfluorene-block-Poly(phenyl isocyanide) and Its Enhanced Circularly Polarized Luminescence Performance","authors":"Hui Zou, Shuyang Zhao, Chaofan Han, Menghao Hu, Li Zhou, Benfa Chu","doi":"10.1021/acsami.5c04689","DOIUrl":"https://doi.org/10.1021/acsami.5c04689","url":null,"abstract":"Chiral induction of polyfluorene (PF)-containing block copolymers plays a crucial role in the development of advanced functional materials; however, research in this area remains scarce. In this contribution, PFO-<i>b</i>-PPI diblock copolymers comprising blocks of poly(9,9-dioctylfluorene) (PFO) and poly(phenyl isocyanide) (PPI) were readily synthesized in one pot by combining chain-growth Suzuki cross-coupling polymerization of a modified 9,9-dioctylfluorene monomer with Pd(II)-catalyzed polymerization of a phenyl isocyanide monomer bearing a pentafluorophenyl ester substitute. The obtained PFO-<i>b</i>-PPI possessed a controlled molar mass (<i>M</i>_n) and narrow dispersity (<i>M</i>_w/<i>M</i>_n, <i>Đ</i>). Meanwhile, optically active supramolecular assemblies could be formed via coassembly of PFO-<i>b</i>-PPI with a chiral binaphthyl-based inducer in the film state after thermal annealing treatment, and the chirality of the supramolecular assemblies was influenced by the temperature of thermal annealing treatment, the weight ratio of the PFO-<i>b</i>-PPI copolymer to the chiral inducer, and the thickness of the film. Further investigations revealed that optically active supramolecular assemblies exhibited the morphology of single-handed helical nanofibers, and the helical sense of the nanofibers depended on the configuration of the binaphthyl-based inducer. Moreover, the supramolecular assemblies of helical nanofibers possessed excellent circularly polarized luminescence (CPL) performance with a <i>g</i>_lum as high as 0.11.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"31 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866422","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Metabolite Co-Delivery Strategy to Improve mRNA Lipid Nanoparticle Delivery","authors":"Yutian Ma, Vincent Fung, Rachel VanKeulen-Miller, Palas B. Tiwade, Eshan A. Narasipura, Nicole A. Gill, Owen S. Fenton","doi":"10.1021/acsami.4c22969","DOIUrl":"https://doi.org/10.1021/acsami.4c22969","url":null,"abstract":"Lipid nanoparticles (LNPs) effectively protect mRNA and facilitate its entry into target cells for protein synthesis. Despite these successes, cellular entry alone may not be enough for optimal protein expression, as mRNA translation also depends on the availability of essential metabolites, including metabolic energy sources, coenzymes, and amino acids. Without adequate metabolites, mRNA translation may be less efficient, potentially leading to higher dosing requirements or poorer therapeutic outcomes for LNP therapies. To address this, we develop a metabolite co-delivery strategy by encapsulating essential metabolites within mRNA LNPs, hypothesizing that our approach can uniformly improve mRNA delivery. Instead of adding a fifth component to the organic phase, our strategy involves mixing the metabolite with the mRNA payload in the aqueous phase, while maintaining the molar ratio of the components in the organic phase during LNP formulation. We verify our approach <i>in vitro</i> and <i>in vivo</i>, highlighting the broad applicability of our strategy through mechanism and efficacy studies across multiple cell lines, and physiological conditions, such as normoxia (i.e., 21% oxygen), hypoxia (i.e., 1% oxygen), and in mice. Taken collectively, we anticipate that our metabolite co-delivery strategy may serve as a generalizable strategy to enhance <i>in vitro</i> and <i>in vivo</i> protein expression using mRNA LNPs, potentially offering broad applicability for the study and treatment of disease.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"3 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143875974","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Saponin Gallate-Loaded Gd-Doped Zinc–Gallium Layered Double Hydroxides (Zn/Ga@Gd-LDH) Nanocarrier for Attenuating NF-κB-Mediated Inflammation","authors":"Momna Aslam, Batool Fatima, Rafia Batool, Muhammad Imran, Dilshad Hussain, Muhammad Najam-ul-Haq, Rubaida Mehmood","doi":"10.1021/acsami.5c00453","DOIUrl":"https://doi.org/10.1021/acsami.5c00453","url":null,"abstract":"This work describes a drug delivery system (DDS) based on the therapeutic anti-inflammatory efficacy of saponin gallate (SG), a combination of gallic acid and saponin, chemically conjugated via an ester linkage. This formulation was loaded onto a biocompatible gadolinium-doped zinc–gallium-layered double hydroxide (Zn/Ga@Gd-LDH) nanocarrier. FT-IR, XRD, SEM, and HPLC were used to characterize the synthesized materials. UV–visible spectroscopy was employed to investigate the drug release from SG-Zn/Ga@Gd-LDH at an optimized temperature (45 °C) and pH (5). The kinetic release behavior of SG-Zn/Ga@Gd-LDH nanoparticles suggested that the first-order kinetic model was the most appropriate for the release profile. The regression value (<i>R</i>²) of 0.96614 indicated an optimal and controlled release for therapeutic effectiveness and minimal adverse effects over 54 h. The <i>in vitro</i> and <i>in vivo</i> models confirmed that drug-loaded nanocarriers exhibited antioxidant, anti-inflammatory, and anticancer properties. Western blotting analysis suggested that SG-Zn/Ga@Gd-LDH abrogates the anti-inflammatory properties by halting the phosphorylation of pro-inflammatory proteins p-p65 and decreasing CRP levels involved in the NF-κB pathway. SG-Zn/Ga@Gd-LDH exhibited an anti-inflammatory effect by reducing the secretion of proinflammatory cytokines. SG-Zn/Ga@Gd-LDH treatment against an acute CCl4-induced liver injury model showed anti-inflammatory potential in histological parameters’ study. Radiolabeling of the drug saponin gallate with ^99mTc was carried out to determine its <i>in vivo</i> biodistribution. The chromatographic results indicated promising radiolabeling of up to 90% percentages. SPECT-CT imaging and <i>ex vivo</i> gamma counting in Wistar rats revealed different clearance rates of nanoparticles, aiding in the evaluation of the drug delivery nanosystem. The designed system also demonstrated antioxidant potential due to the SG compound having IC₅₀ 127.45 μg/mL free radical scavenging activity. Ga@Gd-LDH showed a tumor-suppressing ability of 79.89 ± 3.91% for viable cells against breast cancer MCF-7 cells. The developed formulation could thus be a conducive strategy against inflammatory diseases.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"42 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866580","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nitrogen-Functionalized p-Type Graphene Window and Silicon Nanowire Heterostructure with High-Performing NIR Light Detection","authors":"Dipayan Roy, S. Najes Riaz, Anibrata Banerjee, Souvik Bhattacharjee, Sourav Sarkar, Kalyan Kumar Chattopadhyay","doi":"10.1021/acsami.5c03700","DOIUrl":"https://doi.org/10.1021/acsami.5c03700","url":null,"abstract":"In recent development, the type of dopants, strain, vacancies, and band alignment in reduced graphene oxide, namely, graphene window, can be a promising candidate to exhibit high near-infrared light detection. In this work, we delineate structural effects, in-plane hopping defects, and vacancies that enhance p-type behavior of nitrogen/oxygen functionalized reduced graphene oxide (NORG). The NORG-6/30 has been prepared from pyrazole at different time intervals (6–30 h). A combined spectroscopic approach and ab initio calculation imply pyrazole-based 4-pyrrole unit complex macrocyclic unit formation, i.e., in-plane hopping defect and vacancies are maximum for NORG-30. Thus, the structural effect in NORG-30 opens the band gap and work function, shifts the Fermi level position toward the valence band, and increases the hole doping concentrations. The suitable band alignment between different layered NORG-30 and Silicon nanowire substrate shows remarkable NIR-based photodetector devices having maximum responsivity and detectivity as high as 50 mA W ^–1 and 2.2 × 10¹¹ Jones at −2 V. The temperature-dependent Thermionic and Cheung’s models are introduced to estimate the Schottky barrier height of 0.98 eV and the diode ideality factor of 2.92, which are well corroborated with UPS analysis. The high photocurrent from photoexcited high charge carrier formation of the NORG-30/SiNW device is 2 orders higher in magnitude than other NORG/SiNW and ORG/SiNW (without using any nitrogen precursors) devices. Finally, the hybrid NORG-30/SiNW device rapidly quantifies the alcohol content and has excellent potential for application in the food industry.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"22 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866421","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bioinspired Nanoporous MOF-Modified Basalt Fiber Fabrics for Efficient and Multifunctional Oil–Water Separation","authors":"Liang Wu, Xue Yao, Ze Luo, Lan Li, Haibo Huang, Hua Tang","doi":"10.1021/acsami.5c00237","DOIUrl":"https://doi.org/10.1021/acsami.5c00237","url":null,"abstract":"Oily wastewater pollution is increasing globally. Conventional treatment methods often fail due to inefficiency and secondary contamination. Therefore, developing advanced membrane separation technologies is crucial. While membrane separation technology holds promise as a solution, its widespread applicability necessitates overcoming significant obstacles related to corrosion resistance, alkali resistance, and the prevention of membrane fouling. This study presents a novel and highly efficient approach for oil–water separation, employing bioinspired, nanoporous metal–organic framework-modified basalt fiber fabrics (BFF). The integration of UiO-66-NH₂, renowned for its high porosity and tunable functionalities, with a chitosan-dopamine (CS-DA) layer on BFFs creates a multifunctional membrane with enhanced hydrophilicity and underwater superoleophobicity. This bioinspired design (refers to engineering solutions that mimic natural structures or mechanisms to improve performance and efficiency), drawing inspiration from the structure and function of natural materials, results in superior oil–water separation performance, demonstrating excellent flux and oil rejection rates. The UiO-66-NH₂ effectively captures oil droplets due to its high porosity, while the CS-DA layer facilitates water permeability and promotes surface stability. Furthermore, the composite membrane exhibits exceptional stability and reusability, positioning it as a promising candidate for efficient and sustainable oil–water separation applications. This research showcases the potential of bioinspired design principles for developing innovative solutions to pressing environmental challenges.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"15 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143875973","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sensing of Organic Vapors with Plasmonic Distributed Bragg Reflectors","authors":"Zdeněk Krtouš, Oleksandr Polonskyi, Pavel Pleskunov, Miroslav Cieslar, Bill Baloukas, Ludvik Martinu, Jaroslav Kousal","doi":"10.1021/acsami.5c02058","DOIUrl":"https://doi.org/10.1021/acsami.5c02058","url":null,"abstract":"In recent years, advancements in air quality monitoring have been driven by the development of various sensor technologies, each with distinct advantages and limitations. Among these, polymer-based Distributed Bragg Reflectors (DBRs) have garnered significant interest for use in cost-effective, portable colorimetric sensors for detecting volatile organic compounds (VOCs). However, a key challenge in the fabrication of polymer-based DBRs lies in achieving an adequate refractive index contrast between the individual polymer layers. In this work, we fabricate plasmonic DBR sensors by a combination of low-temperature plasma-based techniques with reduced environmental footprint, investigate their potential as VOC sensors, and propose an optical model that links the sensors’ optical properties and microstructure. Plasmonic nanoparticles of silver (Ag) are synthesized by gas aggregation and embedded into thermally evaporated poly(lactic acid) (PLA) layers to create nanocomposites with an enhanced refractive index (∼2.0). A 6-bilayer plasmonic DBR sensor is then produced by alternating depositions of plain PLA and nanocomposite layers as low and high refractive index materials, respectively. The resulting DBR achieves a 77% reflectance at 570 nm. The potential use-case of such a DBR as a VOC sensor is highlighted by its optical response upon exposure to ethanol (a model VOC) vapors as well as other VOCs (water, propanol, acetone, hexane). In an ethanol atmosphere, swelling of the polymer layers occurs, resulting in a red-shift of the reflection peak to 640 nm and a change in the DBR color. We take advantage of a generalized Maxwell-Garnett approach to create an advanced model that accurately reproduces the DBR spectra and captures swelling and degradation by accounting for structural changes and the behavior of isolated and coalesced Ag NPs within individual layers. Despite a decrease in the sensing performance with the number of swelling cycles, these plasmonic DBRs offer a promising solution for low-cost real-time VOC sensing.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"42 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866590","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Perovskite AMoO3 (A = Ca, Sr, Ba): A New Ambient-Stable and Water-Soluble Sacrificial Layer Family for Single-Crystal Self-Supporting Oxide Membrane Fabrication","authors":"Moussa Mebarki, Bruno Bérini, Vincent Polewczyk, Arnaud Fouchet, Valérie Demange, Yves Dumont","doi":"10.1021/acsami.5c01621","DOIUrl":"https://doi.org/10.1021/acsami.5c01621","url":null,"abstract":"Development of self-supporting oxide membrane fabrication using a sacrificial layer method has attracted great attention over the past decade, specifically for their promising integration as devices on silicon and flexible substrates due to their large panel of properties such as ferroelectricity, ferromagnetism, superconductivity, and metal/insulator transition. Known sacrificial layer materials with a perovskite-related structure, such as La_<i>x</i>Sr_1–<i>x</i>MnO₃ and YBa₂Cu₃O₇, are dissolved in acidic or basic solutions. To prevent oxide membranes from being attacked by the sacrificial layer dissolution solution, it is important to find perovskite water-soluble sacrificial buffers. In this work, we evidence the perovskite molybdates AMoO₃ (A = Ca, Sr, Ba) as a new ambient-stable and efficient water-soluble sacrificial layer family for the fabrication of oxide membranes. We first show the stability in an ambient environment of CaMoO₃, SrMoO₃, and BaMoO₃ epitaxial films deposited on (001)SrTiO₃ substrates and their water dissolution kinetics with membrane release times longer than the SrVO₃ material and the well-known Sr₃Al₂O₆ sacrificial layer material. We analyze the etching kinetics via operando optical monitoring of the remaining sacrificial layer surface still attached to the initial template substrate. We found for the molybdate family a first-order reaction kinetics with a main exponential decay, with constants, respectively, of around 11 h, 14 h, and 19 h for CaMoO₃, SrMoO₃, and BaMoO₃. We use this molybdate family to release an 80 nm-thick SrTiO₃ membrane on a polydimethylsiloxane support with a smooth morphology observed by atomic force microscopy and a monocrystalline quality observed by high-resolution X-ray diffraction. These results open a range of pseudocubic lattice parameters of the ambient-stable and water-soluble sacrificial buffers with pseudocubic lattice parameters from 3.90 to 4.04 Å for self-supporting perovskite oxide monocrystalline membrane fabrication.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"108 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866586","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An Expansion-Mitigant Binder for Stable Cycling of High-Loading Lithium–Sulfur Batteries","authors":"Avinash Raulo, Saheed A. Lateef, Golareh Jalilvand","doi":"10.1021/acsami.5c01464","DOIUrl":"https://doi.org/10.1021/acsami.5c01464","url":null,"abstract":"Lithium–sulfur batteries with high sulfur content and mass loading are promising energy storage technologies due to sulfur’s exceptional theoretical energy density. However, in practice, their actual capacity drastically decays when the sulfur cathode is loaded to the commercially required levels of 4 mg_sulfur cm^–2 and above, significantly reducing the energy density. This reduction is due to the excessive formation of polysulfides during sulfur lithiation, which not only deteriorates battery performance through their detrimental shuttling but also results in substantial stress buildup due to their significantly larger volume compared to sulfur. To address these challenges, we have developed an approach to suppress lithium polysulfide shuttling by limiting the space for sulfur expansion while improving the Li⁺ ion diffusion. This was achieved through a straightforward but effective method to cross-link the organic binder used in sulfur electrodes. Specifically, PVDF, one of the most common binder materials for battery electrodes, was studied. The chemical, mechanical, and structural properties of the cross-linked PVDF binder were thoroughly investigated, compared with standard PVDF, and correlated to the achieved electrochemical performance of sulfur electrodes. As a result, sulfur cathodes with cross-linked PVDF binder exhibited prolonged cycle life compared to their standard counterparts. Moreover, using this expansion-mitigant binder, cathodes with areal sulfur loading of 4 mg cm^–2 showed exceptional stability for more than 200 cycles and a Coulombic efficiency above 97%. This approach offers a promising avenue to alleviate the major roadblocks of lithium–sulfur battery commercialization while allowing the utilization of the commonly accessible and well-studied binder chemistries.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"7 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866428","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nanoscale Investigation of Elasticity Changes and Augmented Rigidity of Block Copolymer Micelles Induced by Reversible Core-Cross-Linking","authors":"Xinyue Wang, Andreas Stihl, Christiane Höppener, Jürgen Vitz, Felix H. Schacher, Volker Deckert","doi":"10.1021/acsami.5c04826","DOIUrl":"https://doi.org/10.1021/acsami.5c04826","url":null,"abstract":"Drug-delivery systems have attracted considerable attention due to their potential to increase the bioavailability of certain drugs and mitigate side effects by enabling targeted drug release. Reversibly core-cross-linked block copolymer micelles providing a hydrophilic and potentially nonimmunogenic shell and a hydrophobic core suitable for the uptake of hydrophobic drugs are frequently considered because of their high stability against environmental changes and dilution. Ultimately, triggering core-de-cross-linking enables the implementation of strategies for targeted drug release, which requests insights into the impact of varying nanomechanical properties on the stability of individual micelles. Here, atomic force microscopy nanoindentation in aqueous media is applied to intact α-allyl-PEG₈₀-<i>b</i>-P(<i>t</i>BGE₅₂-<i>co</i>-FGE₁₂) micelles to quantify changes in their nanomechanical properties induced by dithiobismaleimidoethane (DTME)-mediated Diels–Alder cross-linking of furfuryl moieties and sequential de-cross-linking by reduction of its disulfide bond by tris(2-carboxyethyl)phosphine. As a result of crosslinking by DTME, the apparent Young’s modulus of the micelles roughly doubles to 1.18 GPa. Changes to the Young’s modulus can be largely reversed by de-cross-linking. Cross-linked and de-cross-linked micelles maintain their structural integrity even in diluted aqueous media below the critical micelle concentration, in contrast to the micelles prior to crosslinking. Understanding the structure–property relationships associated with the observed augmented mechanical stability in native environments is crucial for improving the efficiency of drug encapsulation and introducing refined temporal and spatially controlled drug-release mechanisms.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":"17 1","pages":""},"PeriodicalIF":9.5,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866478","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}