ACS Nanoscience Au最新文献

Surface chemistry of materials that host quantum bits such as diamond is an important avenue of exploration as quantum computation and quantum sensing platforms mature. Interfacing diamond in general and nanoscale diamond (ND) in particular with silica is a potential route to integrate room temperature quantum bits into photonic devices, fiber optics, cells, or tissues with flexible functionalization chemistry. While silica growth on ND cores has been used successfully for quantum sensing and biolabeling, the surface mechanism to initiate growth was unknown. This report describes the surface chemistry responsible for silica bond formation on diamond and uses X-ray absorption spectroscopy (XAS) to probe the diamond surface chemistry and its electronic structure with increasing silica thickness. A modified Stöber (Cigler) method was used to synthesize 2–35 nm thick shells of SiO₂ onto carboxylic acid-rich ND cores. The diamond morphology, surface, and electronic structure were characterized by overlapping techniques including electron microscopy. Importantly, we discovered that SiO₂ growth on carboxylated NDs eliminates the presence of carboxylic acids and that basic ethanolic solutions convert the ND surface to an alcohol-rich surface prior to silica growth. The data supports a mechanism that alcohols on the ND surface generate silyl–ether (ND–O–Si–(OH)₃) bonds due to rehydroxylation by ammonium hydroxide in ethanol. The suppression of the diamond electronic structure as a function of SiO₂ thickness was observed for the first time, and a maximum probing depth of ∼14 nm was calculated. XAS spectra based on the Auger electron escape depth was modeled using the NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to support our experimental results. Additionally, resonant inelastic X-ray scattering (RIXS) maps produced by the transition edge sensor reinforces the chemical analysis provided by XAS. Researchers using diamond or high-pressure high temperature (HPHT) NDs and other exotic materials (e.g., silicon carbide or cubic-boron nitride) for quantum sensing applications may exploit these results to design new layered or core–shell quantum sensors by forming covalent bonds via surface alcohol groups.

In this work, we demonstrate a photoluminescence-based method to monitor the kinetics of an organohalide reaction by way of detecting released bromide ions at cesium lead halide nanoparticles. Small aliquots of the reaction are added to an assay with known concentrations of CsPbI₃, and the resulting Br-to-I halide exchange (HE) results in rapid and sensitive wavelength blueshifts (Δλ) due to CsPbBr_xI_3–x intermediate concentrations, the wavelengths of which are proportional to concentrations. An assay response factor, C, relates Δλ to Br^– concentration as a function of CsPbI₃ concentration. The observed kinetics, as well as calculated rate constants, equilibrium, and activation energy of the solvolysis reaction tested correspond closely to synthetic literature values, validating the assay. Factors that influence the sensitivity and performance of the assay, such as CsPbI₃ size, morphology, and concentration, are discussed.

This paper describes coinage-metal-doped InP quantum dots (QDs) as a platform for enhanced electron transfer to molecular acceptors relative to undoped QDs. A synthetic strategy is developed to prepare doped InP/ZnSe QDs. First-principles DFT calculations show that Ag⁺ and Cu⁺ dopants localize photoexcited holes while leaving electrons delocalized. This charge carrier wave function modulation is leveraged to enhance electron transfer to molecular acceptors by up to an order of magnitude. Examination of photoluminescence quenching data suggests that larger electron acceptors, such as anthraquinone and methyl viologen, bind to the QD surface in two ways: by direct adsorption to the surface and by adsorption following displacement of a weakly bound surface cation-ligand complex. Reactions with larger acceptors show the greatest increases in electron transfer between doped and undoped quantum dots, while smaller acceptors show smaller enhancements. Specifically, benzoquinone shows the smallest, followed by naphthoquinone and then methyl viologen and anthraquinone. These results demonstrate the benefits of dopant-induced excited-state carrier localization on photoinduced charge transfer and highlight design principles for improved implementation of quantum dots in photoredox catalysis.

There is much concern about per- and polyfluoroalkyl substances (PFAS) based on their environmental persistence and toxicity, resulting in an urgent need for remediation technologies. This study focused on determining if nanoscale polymeric carbon dots are a viable sorbent material for PFAS and developing fluorine nuclear magnetic resonance spectroscopy (¹⁹F NMR) methods to probe interactions between carbon dots and PFAS at the molecular scale. Positively charged carbon dots (PEI-CDs) were synthesized using branched polyethyleneimine to target anionic PFAS by promoting electrostatic interactions. PEI-CDs were exposed to perfluorooctanoic acid (PFOA) to assess their potential as a PFAS sorbent material. After exposure to PFOA, the average size of the PEI-CDs increased (1.6 ± 0.5 to 7.8 ± 1.8 nm) and the surface charge decreased (+38.6 ± 1.1 to +26.4 ± 0.8 mV), both of which are consistent with contaminant sorption. ¹⁹F NMR methods were developed to gain further insight into PEI-CD affinity toward PFAS without any complex sample preparation. Changes in PFOA peak intensity and chemical shift were monitored at various PEI-CD concentrations to establish binding curves and determine the chemical exchange regime. ¹⁹F NMR spectral analysis indicates slow-intermediate chemical exchange between PFOA and CDs, demonstrating a high-affinity interaction. The α-fluorine had the greatest change in chemical shift and highest affinity, suggesting electrostatic interactions are the dominant sorption mechanism. PEI-CDs demonstrated affinity for a wide range of analytes when exposed to a mixture of 24-PFAS, with a slight preference toward perfluoroalkyl sulfonates. Overall, this study shows that PEI-CDs are an effective PFAS sorbent material and establishes ¹⁹F NMR as a suitable method to screen for novel sorbent materials and elucidate interaction mechanisms.

Chemical synthesis is a compelling alternative to top-down fabrication for controlling the size, shape, and composition of two-dimensional (2D) crystals. Precision tuning of the 2D crystal structure has broad implications for the discovery of new phenomena and the reliable implementation of these materials in optoelectronic, photovoltaic, and quantum devices. However, precise and predictable manipulation of the edge structure in 2D crystals through gas-phase synthesis is still a formidable challenge. Here, we demonstrate a salt-assisted low-pressure chemical vapor deposition method that enables tuning W metal flux during growth of 2D WSe₂ monolayers and, thereby, direct control of their edge structure and optical properties. The degree of structural disorder in 2D WSe₂ is a direct function of the W metal flux, which is controlled by adjusting the mass ratio of WO₃ to NaCl. This edge disorder then couples to excitonic disorder, which manifests as broadened and spatially varying emission profiles. Our work links synthetic parameters with analyses of material morphology and optical properties to provide a unified understanding of intrinsic limits and opportunities in synthetic 2D materials.

Metal–organic frameworks (MOFs) have emerged as attractive chemical sensing materials due to their exceptionally high porosity and chemical diversity. Nevertheless, the utilization of MOFs in chemiresistive type sensors has been hindered by their inherent limitation in electrical conductivity. The recent emergence of two-dimensional conductive MOFs (2D c-MOFs) has addressed this limitation by offering enhanced electrical conductivity, while still retaining the advantageous properties of MOFs. In particular, c-MOFs have shown promising advantages for the fabrication of sensors capable of operating at room temperature. Thus, active research on gas sensors utilizing c-MOFs is currently underway, focusing on enhancing sensitivity and selectivity. To comprehend the potential of MOFs as chemiresistive sensors for future applications, it is crucial to understand not only the fundamental properties of conductive MOFs but also the state-of-the-art works that contribute to improving their performance. This comprehensive review delves into the distinctive characteristics of 2D c-MOFs as a new class of chemiresistors, providing in-depth insights into their unique sensing properties. Furthermore, we discuss the proposed sensing mechanisms associated with 2D c-MOFs and provide a concise summary of the strategies employed to enhance the sensing performance of 2D c-MOFs. These strategies encompass a range of approaches, including the design of metal nodes and linkers, morphology control, and the synergistic use of composite materials. In addition, the review thoroughly explores the prospects of 2D c-MOFs as chemiresistors and elucidates their remarkable potential for further advancements. The insights presented in this review shed light on future directions and offer valuable opportunities in the chemical sensing research field.

This work presents the development and implementation of a deep learning-based workflow for autonomous image analysis in nanoscience. A versatile, agnostic, and configurable tool was developed to generate instance-segmented imaging datasets of nanoparticles. The synthetic generator tool employs domain randomization to expand the image/mask pairs dataset for training supervised deep learning models. The approach eliminates tedious manual annotation and allows training of high-performance models for microscopy image analysis based on convolutional neural networks. We demonstrate how the expanded training set can significantly improve the performance of the classification and instance segmentation models for a variety of nanoparticle shapes, ranging from spherical-, cubic-, to rod-shaped nanoparticles. Finally, the trained models were deployed in a cloud-based analytics platform for the autonomous particle analysis of microscopy images.

We have investigated the effects of high-energy electron irradiation on the oxidation of copper nanoparticles in environmental scanning transmission electron microscopy (ESTEM). The hemispherically shaped particles were oxidized in 3 mbar of O₂ in a temperature range 100–200 °C. The evolution of the particles was recorded with sub-nanometer spatial resolution in situ in ESTEM. The oxidation encompasses the formation of outer and inner oxide shells on the nanoparticles, arising from the concurrent diffusion of copper and oxygen out of and into the nanoparticles, respectively. Our results reveal that the electron beam actively influences the reaction and overall accelerates the oxidation of the nanoparticles when compared to particles oxidized without exposure to the electron beam. However, the extent of this electron beam-assisted acceleration of oxidation diminishes at higher temperatures. Moreover, we observe that while oxidation through the outward diffusion of Cu⁺ cations is enhanced, the electron beam appears to hinder oxidation through the inward diffusion of O^2– anions. Our results suggest that the impact of the high-energy electrons in ESTEM oxidation of Cu nanoparticles is mostly related to kinetic energy transfer, charging, and ionization of the gas environment, and the beam can both enhance and suppress reaction rates.

Lack of standardization is a systematic problem that impacts nanomedicine by challenging data comparison from different studies. Translation from preclinical to clinical stages indeed requires reproducible data that can be easily accessed and compared. In this work, we propose a series of experimental standards for in vitro plasmonic photothermal therapy (PPTT). This best practice guide covers the five main aspects of PPTT studies in vitro: nanomaterials, biological samples, pre-, during, and postirradiation characterization. We are confident that such standardization of experimental protocols and reported data will benefit the development of PPTT as a transversal therapy.