ACS Applied Materials & Interfaces最新文献

Cell-membrane hybrid nanoparticles (NPs) are designed to improve drug delivery, thermal therapy, and immunotherapy for several diseases. Here, we report the development of distinct biomimetic magnetic nanocarriers containing magnetic nanoparticles encapsulated in vesicles and IR780 near-infrared dyes incorporated in the membranes. Distinct cell membranes are investigated, red blood cell (RBC), melanoma (B16F10), and glioblastoma (GL261). Hybrid nanocarriers containing synthetic lipids and a cell membrane are designed. The biomedical applications of several systems are compared. The inorganic nanoparticle consisted of Mn-ferrite nanoparticles with a core diameter of 15 ± 4 nm. TEM images show many multicore nanostructures (∼40 nm), which correlate with the hydrodynamic size. Ultrahigh transverse relaxivity values are reported for the magnetic NPs, 746 mM^-1s^-1, decreasing respectively to 445 mM^-1s^-1 and 278 mM^-1s^-1 for the B16F10 and GL261 hybrid vesicles. The ratio of relaxivities r₂/r₁ decreased with the higher encapsulation of NPs and increased for the biomimetic liposomes. Therapeutic temperatures are achieved by both, magnetic nanoparticle hyperthermia and photothermal therapy. Photothermal conversion efficiency ∼25-30% are reported. Cell culture revealed lower wrapping times for the biomimetic vesicles. In vivo experiments with distinct routes of nanoparticle administration were investigated. Intratumoral injection proved the nanoparticle-mediated PTT efficiency. MRI and near-infrared images showed that the nanoparticles accumulate in the tumor after intravenous or intraperitoneal administration. Both routes benefit from MRI-guided PTT and demonstrate the multimodal theranostic applications for cancer therapy.

Enhancement of the perovskite film quality and charge transfer capability is crucial for enhancing device performance. The all-inorganic CsPbCl₃ perovskite, which shows great potential as an absorber layer in ultraviolet photodetectors (UV PDs), has been hindered by poor material stability and high interface states, limiting its widespread application. In this work, the quality of the CsPbCl₃ films and the perovskite/Au electrode interface were synergistically modulated using V₂CT_x MXene. After additive (CsPbCl₃@V₂CT_x) and interface (CsPbCl₃/V₂CT_x) engineering, the optimal properties of CsPbCl₃ films and the van der Waals (vdW) bonding of V₂CT_x strengthen the charge extraction and hole transport while reducing nonradiative charge recombination caused by internal defects and interface states. Ultimately, the UV PD featuring the FTO/SnO₂/CsPbCl₃@V₂CT_x/V₂CT_x/Au structure manifests outstanding performance under the self-powered mode, attaining an extremely high responsivity of up to 1.01 × 10³ mA/W and a considerable specific detectivity of 5.46 × 10¹¹ cm Hz^1/2/W (365 nm, 0.16 mW/cm²) coupled with a swift rise/decay time of 1.54/1.50 μs. Even after 30 days under an air atmosphere, the responsivity of the device remains at 8.46 × 10² mA/W, indicating extraordinary stability. This approach offers a novel way to enhance the performance of UV PD based on the CsPbCl₃ perovskite through the dual strategy of V₂CT_x MXene modulation.

Extensive research on supercapacitor-battery hybrid devices has bridged the gap between conventional batteries and supercapacitors. However, several challenges persist, including limited capacitance in the negative potential range, restricted rate capability, and a narrow potential window (<1.23 V) in aqueous electrolytes. Drawing inspiration from the notable benefits of bottom-up synthesis, which allows tailoring of structure and functionality through the selection of molecular components, we successfully synthesized an Fe-incorporated zeolitic imidazolate framework-8 (composed of Zn nodes and 2-methylimidazole linkers). Subsequently, the metal-organic framework was hydrothermally composited with graphene oxide in the presence of urea to prepare a dual metal oxide/N-doped reduced graphene oxide (DMO-NrGO) nanocomposite. Benefiting from the high hydrogen evolution overpotential of zinc-based compounds and the promising negative potential range activity of iron-based species, the lower potential limit of the X-ray confirmed crystalline-amorphous heterophase DMO-NrGO nanocomposite extends up to -1.45 V. It exhibits a specific capacity (capacitance) of 119 mA h g^-1 (378 F g^-1) at 1.0 A g^-1 in 3.0 M KOH. Interestingly, the symmetric DMO-NrGO based superbattery device demonstrates an ultrawide voltage window of 1.95 V, with a superior specific energy of 28 W h kg^-1 and an outstanding specific power of 29 kW kg^-1 at 3.0 A g^-1. The outstanding electrochemical performance can be attributed to the heterophase structure of the nanocomposite, which accommodates more active sites, provides additional ion transport channels, reduces phase-transformation resistance, and facilitates smooth electron transfer between metal oxides and graphene. This innovative synthetic strategy opens opportunities for developing high-performance aqueous energy storage devices.

Incorporating enzymes into nanostructured supercapacitor devices represents a groundbreaking advancement in energy storage. Enzyme catalysis using nanomaterials enhances performance, efficiency, and stability by facilitating precise charge transfer, while the nanostructure provides a high surface area and improved conductivity. This synergy yields eco-friendly, high-performance energy storage solutions crucial for diverse applications, from portable electronics to renewable energy systems. In this study, we harnessed the versatility of Langmuir-Blodgett films to create meticulously organized thin films with specific enzyme properties, coupled with carbon nanotubes, to develop biosupercapacitors. Langmuir monolayers were constructed with stearic acid, carbon nanotubes, and galactose oxidase. Following comprehensive characterization using tensiometric, rheological, morphological, and spectroscopic techniques, the monolayers were transferred to solid supports, yielding Langmuir-Blodgett films. These films exhibited superior performance, with persisting enzyme activity. However, increasing film thickness did not enhance enzymatic activity values, indicating a surface-driven process. Subsequently, we explored the electrochemical properties of the films, revealing stability compatible with supercapacitor applications. The introduction of carbon nanotubes demonstrated a higher capacitance, indicating the potential viability of the films for energy storage applications.

In situ 3D printing is attractive for the direct repair of bone defects in underdeveloped countries and in emergency situations. So far, the lack of an interesting method to produce filament using FDA-approved biopolymers and nanoceramics combined with a portable strategy limits the use of in situ 3D printing. Herein, we investigated the osseointegration of new nanocomposite filaments based on polylactic acid (PLA), laponite (Lap), and hydroxyapatite (Hap) printed directly at the site of the bone defect in rats using a portable 3D printer. The filaments were produced using a single-screw extruder (L/D = 26), without the addition of solvents that can promote the toxicity of the materials. In vitro performance was evaluated in the cell differentiation process with mesenchymal stem cells (MSC) by an alkaline phosphatase activity test and visualization of mineralization nodules; a cell viability test and total protein dosage were performed to evaluate cytotoxicity. For the in vivo analysis, the PLA/Lap composite filaments with a diameter of 1.75 mm were printed directly into bone defects of Wistar rats using a commercially available portable 3D printer. Based on the in vitro and in vivo results, the in situ 3D printing technique followed by rapid cooling proved to be promising for bone tissue engineering. The absence of fibrous encapsulation and inflammatory processes became a good indicator of effectiveness in terms of biocompatibility parameters and bone tissue formation, and the use of the portable 3D printer showed a significant advantage in the application of this material by in situ printing.

This study addresses the extension of the service life of carbon-fiber reinforced epoxies by inducing thermal healing of microcracks through the use of a vitrimer as a polymeric matrix. Our aim was to explore the feasibility of using a blend of selected carboxylic acids (citric, glutaric, and sebacic acids) and commercial monomers to design a matrix specifically developed for technological implementation in composites with the ability of intrinsic repair of microcracks under moderate (even remote) heating treatments. The selection of the formulation (the acid blend, catalysts, and monomers) was the result of an exhaustive prescreening analysis of processing requisites and final properties. The glass transition temperature of the cured vitrimer composite measured by differential scanning calorimetry (DSC) is 94 °C, a value lying in the range required for several technological applications, whereas stress relaxation to (1/e) of the initial value took ∼4.7 h at 180 °C and only 1.1 h at 200 °C. Composites containing 50 vol % of carbon fibers could be successfully prepared by compression molding. Acoustic emission tests proved the formation and partial healing of microcracks during tensile tests performed until 350 MPa. Surface scratches could also be healed by remote activation using near-infrared irradiation (NIR). These first results under nonoptimized thermal cycles are a proof of concept that microcrack and scratch healing can be produced in high glass-transition temperature epoxy-based carbon-reinforced composites.

In this contribution, nanocatalysts with rather diverse architectures were designed to promote different intimacy degrees between Cu and SiO₂ and consequently tune distinct Cu-SiO₂ interactions. Previously synthesized copper nanoparticles were deposited onto SiO₂ (NPCu/SiO₂) in contrast to ordinarily prepared supported Cu/SiO₂. NPCu@SiO₂ and SiO₂@Cu core-shell nanocatalysts were also synthesized, and they were all bulk and surface characterized by XRD, TGA, TEM/HRTEM, H₂-TPR, XANES, and XPS. It was found that Cu⁰ is the main copper phase in NPCu/SiO₂ while Cu²⁺ rules the ordinary Cu/SiO₂ catalyst, and Cu⁰ and electron-deficient Cu^δ+ species coexist in the core-shell nanocatalysts as a consequence of a deeper metal-support interaction. Catalytic performance could not be associated with the physical properties of the nanocatalysts derived from their architectures but was associated with the more refined chemical characteristics tuned by their design. Cu/SiO₂ and NPCu/SiO₂ catalysts led to the formation of furfuryl alcohol, evidencing that catalysts holding weak or no metal-support interaction have no significant impact on product distribution even in the aqueous phase. The establishment of such interactions through advanced catalyst architecture, allowing the formation of electron-deficient Cu^δ+ moieties, particularly Cu²⁺ and Cu⁺ as unveiled by spectroscopic investigations, is critical to promoting the hydrogenation-ring rearrangement cascade mechanism leading to cycloketones.