ACS Nanoscience Au最新文献

Understanding the polydispersity of nanoparticles is crucial for establishing the efficacy and safety of their role as drug delivery carriers in biomedical applications. Detonation nanodiamonds (DNDs), 3–5 nm diamond nanoparticles synthesized through detonation process, have attracted great interest for drug delivery due to their colloidal stability in water and their biocompatibility. More recent studies have challenged the consensus that DNDs are monodispersed after their fabrication, with their aggregate formation poorly understood. Here, we present a novel characterization method of combining machine learning with direct cryo-transmission electron microscopy imaging to characterize the unique colloidal behavior of DNDs. Together with small-angle X-ray scattering and mesoscale simulations we show and explain the clear differences in the aggregation behavior between positively and negatively charged DNDs. Our new method can be applied to other complex particle systems, which builds essential knowledge for the safe implementation of nanoparticles in drug delivery.

Corticosteroids are widely used as an anti-inflammatory treatment for eye inflammation, but the current methods used in clinical practice for delivery are in the form of eye drops which is usually complicated for patients or ineffective. This results in an increase in the risk of detrimental side effects. In this study, we demonstrated proof-of-concept research for the development of a contact lens-based delivery system. The sandwich hydrogel contact lens consists of a polymer microchamber film made via soft lithography with an encapsulated corticosteroid, in this case, dexamethasone, located inside the contact lens. The developed delivery system showed sustained and controlled release of the drug. The central visual part of the lenses was cleared from the polylactic acid microchamber in order to maintain a clean central aperture similar to the cosmetic-colored hydrogel contact lenses.

The success of mRNA vaccines during the COVID-19 pandemic has greatly accelerated the development of mRNA therapy. mRNA is a negatively charged nucleic acid that serves as a template for protein synthesis in the ribosome. Despite its utility, the instability of mRNA requires suitable carriers for in vivo delivery. Lipid nanoparticles (LNPs) are employed to protect mRNA from degradation and enhance its intracellular delivery. To further optimize the therapeutic efficacy of mRNA, site-specific LNPs have been developed. Through local or systemic administration, these site-specific LNPs can accumulate in specific organs, tissues, or cells, allowing for the intracellular delivery of mRNA to specific cells and enabling the exertion of local or systemic therapeutic effects. This not only improves the efficiency of mRNA therapy but also reduces off-target adverse effects. In this review, we summarize recent site-specific mRNA delivery strategies, including different organ- or tissue-specific LNP after local injection, and organ-specific or cell-specific LNP after intravenous injection. We also provide an outlook on the prospects of mRNA therapy.

Organic–inorganic halide perovskites are interesting candidates for solar cell and optoelectronic applications owing to their advantageous properties such as a tunable band gap, low material cost, and high charge carrier mobilities. Despite making significant progress, concerns about material stability continue to impede the commercialization of perovskite-based technology. In this article, we investigate the impact of environmental parameters on the alteration of structural properties of MAPbI₃ (CH₃NH₃PbI₃) thin films using microscopy techniques. These characterizations are performed on MAPbI₃ thin films exposed to air, nitrogen, and vacuum environments, the latter being possible by using dedicated air-free transfer setups, after their fabrication into a nitrogen-filled glovebox. We observed that even less than 3 min of air exposure increases the sensitivity to electron beam deterioration and modifies the structural transformation pathway as compared to MAPbI₃ thin films which are not exposed to air. Similarly, the time evolution of the optical responses and the defect formation of both air-exposed and non-air-exposed MAPbI₃ thin films are measured by time-resolved photoluminescence. The formation of defects in the air-exposed MAPbI₃ thin films is first observed by optical techniques at longer timescales, while structural modifications are observed by transmission electron microscopy (TEM) measurements and supported by X-ray photoelectron spectroscopy (XPS) measurements. Based on the complementarity of TEM, XPS, and time-resolved optical measurements, we propose two different degradation mechanism pathways for air-exposed and non-air-exposed MAPbI₃ thin films. We find that when exposed to air, the crystalline structure of MAPbI₃ shows gradual evolution from its initial tetragonal MAPbI₃ structure to PbI₂ through three different stages. No significant structural changes over time from the initial structure are observed for the MAPbI₃ thin films which are not exposed to air.

Herein, we designed and synthesized a hybrid material comprising polystyrene submicrobeads coated with silver nanospheres. This material provides a dense collection of electromagnetic hot spots upon illumination with visible light. The subsequent coating with a metal-framework and the adsorption of bathocuproine on it yield an optical sensor for SERS that can specifically detect Cu(II) in a variety of aqueous samples at the ultratrace level. Detection limits with this method are superior to those of induced coupled plasma or atomic absorption and comparable with those obtained with induced coupled plasma coupled with a mass detector.

The electronic properties of electrode materials play a crucial role in defining their electrochemical behavior in energy conversion and storage devices. The assembly of van der Waals heterostructures and fabrication into mesoscopic devices enable the dependence of an electrochemical response on electronic properties to be systematically interrogated. Here, we evaluate the effect of charge carrier concentration on heterogeneous electron transfer at few-layer MoS₂ electrodes by combining spatially resolved electrochemical measurements with field-effect electrostatic manipulation of band alignment. Steady-state cyclic voltammograms and finite-element simulations reveal a strong modulation of the measured electrochemical response for outer-sphere charge transfer at the electrostatic gate voltage. In addition, spatially resolved voltammetric responses, obtained at a series of locations at the surface of few-layer MoS₂, reveal the governing role of in-plane charge transport on the electrochemical behavior of 2D electrodes, especially under conditions of low carrier densities.

Thienothiophene thienoisoindigo (ttTII)-based covalent organic frameworks (COFs) have been shown to offer low band gaps and intriguing optical and electrochromic properties. So far, only one tetragonal thienothiophene thienoisoindigo-based COF has been reported showing stable and fast electrochromism and good coloration efficiencies. We have developed two novel COFs using this versatile and nearly linear ttTII building block in a tetragonal and a hexagonal framework geometry to demonstrate their attractive features for optoelectronic applications of thienoisoindigo-based COFs. Both COFs exhibit good electrical conductivities, show promising optical absorption features, are redox-active, and exhibit a strong electrochromic behavior when applying an external electrical stimulus, shifting the optical absorption even farther into the NIR region of the electromagnetic spectrum and achieving absorbance changes of up to 2.5 OD. Cycle-stable cyclic voltammograms with distinct oxidation and reduction waves reveal excellent reversibility and electrochromic switching over 200 cycles and confirm the high stability of the frameworks. Furthermore, high coloration efficiencies in the NIR region and fast switching speeds for coloration/decoloration as fast as 0.75 s/0.37 s for the Cz-ttTII COF and 0.61 s/0.29 s for the TAPB-ttTII COF at 550 nm excitation were observed, outperforming many known electrochromic materials, and offering options for a great variety of applications, such as stimuli-responsive coatings, optical information processing, or thermal control.

Current approaches to carbon nanotube (CNT) synthesis are limited in their ability to control the placement of atoms on the surface of nanotubes. Some of this limitation stems from a lack of understanding of the chemical bond-building mechanisms at play in CNT growth. Here, we provide experimental evidence that supports an alkyne polymerization pathway in which short-chained alkynes directly incorporate into the CNT lattice during growth, partially retaining their side groups and influencing CNT morphology. Using acetylene, methyl acetylene, and vinyl acetylene as feedstock gases, unique morphological differences were observed. Interwall spacing, a highly conserved value in natural graphitic materials, varied to accommodate side groups, increasing systematically from acetylene to methyl acetylene to vinyl acetylene. Furthermore, attenuated total reflectance Fourier-transfer infrared spectroscopy (ATR-FTIR) illustrated the existence of intact methyl groups in the multiwalled CNTs derived from methyl acetylene. Finally, the nanoscale alignment of the CNTs grown in vertically aligned forests differed systematically. Methyl acetylene induced the most tortuous growth while CNTs from acetylene and vinyl-acetylene were more aligned, presumably due to the presence of polymerizable unsaturated bonds in the structure. These results demonstrate that feedstock hydrocarbons can alter the atomic-scale structure of CNTs, which in turn can affect properties on larger scales. This information could be leveraged to create more chemically and structurally complex CNT structures, enable more sustainable chemical pathways by avoiding the need for solvents and postreaction modifications, and potentially unlock experimental routes to a host of higher-order carbonaceous nanomaterials.

Sonophotocatalysis is described as a combination of two individual processes of photocatalysis and sonocatalysis. It has proven to be highly promising in degrading dissolved contaminants in wastewaters as well as bacteria disinfection applications. It eliminates some of the main disadvantages observed in each individual technique such as high costs, sluggish activity, and prolonged reaction times. The review has accomplished a critical analysis of sonophotocatalytic reaction mechanisms and the effect of the nanostructured catalyst and process modification techniques on the sonophotocatalytic performance. The synergistic effect between the mentioned processes, reactor design, and the electrical energy consumption has been discussed due to their importance when implementing this novel technology in practical applications, such as real industrial or municipal wastewater treatment plants. The utilization of sonophotocatalysis in disinfection and inactivation of bacteria has also been reviewed. In addition, we further suggest improvements to promote this technology from the lab-scale to large-scale applications. We hope this up-to-date review will advance future research in this field and push this technology toward widespread adoption and commercialization.

The marriage between nanoscience and heterogeneous catalysis has introduced transformative opportunities for accessing better nanocatalysts. However, the structural heterogeneity of nanoscale solids stemming from distinct atomic configurations makes it challenging to realize atomic-level engineering of nanocatalysts in the way that is attained for homogeneous catalysis. Here, we discuss recent efforts in unveiling and exploiting the structural heterogeneity of nanomaterials for enhanced catalysis. Size and facet control of nanoscale domains produce well-defined nanostructures that facilitate mechanistic studies. Differentiation of surface and bulk characteristics for ceria-based nanocatalysts guides new thoughts toward lattice oxygen activation. Manipulating the compositional and species heterogeneity between local and average structures allows regulation of catalytically active sites via the ensemble effect. Studies on catalyst restructurings further highlight the necessity to assess the reactivity and stability of nanocatalysts under reaction conditions. These advances promote the development of novel nanocatalysts with expanded functionalities and bring atomistic insights into heterogeneous catalysis.