Microscale Electrochemical Corrosion of Uranium Oxide Particles.

Understanding the corrosion of spent nuclear fuel is important for the development of long-term storage solutions. However, the risk of radiation contamination presents challenges for experimental analysis. Adapted from the system for analysis at the liquid-vacuum interface (SALVI), we developed a miniaturized uranium oxide (UO2)-attached working electrode (WE) to reduce contamination risk. To protect UO2 particles in a miniatured electrochemical cell, a thin layer of Nafion was formed on the surface. Atomic force microscopy (AFM) shows a dense layer of UO2 particles and indicates their participation in electrochemical reactions. Particles remain intact on the electrode surface with slight redistribution. X-ray photoelectron spectroscopy (XPS) reveals a difference in the distribution of U(IV), U(V), and U(VI) between pristine and corroded UO2 electrodes. The presence of U(V)/U(VI) on the corroded electrode surface demonstrates that electrochemically driven UO2 oxidation can be studied using these cells. Our observations of U(V) in the micro-electrode due to the selective semi-permeability of Nafion suggest that interfacial water plays a key role, potentially simulating a water-lean scenario in fuel storage conditions. This novel approach offers analytical reproducibility, design flexibility, a small footprint, and a low irradiation dose, while separating the α-effect. This approach provides a valuable microscale electrochemical platform for spent fuel corrosion studies with minimal radiological materials and the potential for diverse configurations.

A microfluidic electrochemical cell for studying the corrosion of uranium dioxide (UO2).

We have developed a specialized microfluidic electrochemical cell that enables in situ investigation of the electrochemical corrosion of microgram quantities of redox active solids. The advantage of downscaling is the reduction of hazards, waste, expense, and greatly expanding data collection for hazardous materials, including radioactive samples. Cyclic voltammetry was used to monitor the oxidation-reduction cycle of minute quantities of micron-size uraninite (UO2) particles, from the formation of hexavalent uranium (U(vi)), U3O7 and reduction to UO2+x . Reaction progress was also studied in situ with scanning electron microscopy. The electrochemical measurements matched those obtained at the bulk-scale and were consistent with ex situ characterization of the run products by X-ray photoelectron spectroscopy, scanning transmission electron microscopy, and atomic force microscopy; thus, demonstrating the utility of the microfluidic approach for studying radioactive materials.

Integrated atomic force microscopy and x-ray irradiation for in situ characterization of radiation-induced processes.

Understanding radiation-induced chemical and physical transformations at material interfaces is important across diverse fields, but experimental approaches are often limited to either ex situ observations or in situ electron microscopy or synchrotron-based methods, in which cases the radiation type and dose are inextricably tied to the imaging basis itself. In this work, we overcome this limitation by demonstrating integration of an x-ray source with an atomic force microscope to directly monitor radiolytically driven interfacial chemistry at the nanoscale. We illustrate the value of in situ observations by examining effects of radiolysis on material adhesion forces in aqueous solution as well as examining the production of alkali nitrates at the interface between an alkali halide crystal surface and air. For the examined salt-air interface, direct visualization under flexible experimental conditions greatly extends prior observations by enabling the transformation process to be followed comprehensively from source-to-sink with mass balance quantitation. Our novel rad-atomic force microscope opens doors into understanding the dynamics of radiolytically driven mass transfer and surface alteration at the nanoscale in real-time.

Studying Corrosion Using Miniaturized Particle Attached Working Electrodes and the Nafion Membrane.

We developed a new approach to attach particles onto a conductive layer as a working electrode (WE) in a microfluidic electrochemical cell with three electrodes. Nafion, an efficient proton transfer molecule, is used to form a thin protection layer to secure particle electrodes. Spin coating is used to develop a thin and even layer of Nafion membrane. The effects of Nafion (5 wt% 20 wt%) and spinning rates were evaluated using multiple sets of replicates. The electrochemical performance of various devices was demonstrated. Additionally, the electrochemical performance of the devices is used to select and optimize fabrication conditions. The results show that a higher spinning rate and a lower Nafion concentration (5 wt%) induce a better performance, using cerium oxide (CeO2) particles as a testing model. The WE surfaces were characterized using atomic force microscopy (AFM), scanning electron microscopy-focused ion beam (SEM-FIB), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and X-ray photoelectron spectroscopy (XPS). The comparison between the pristine and corroded WE surfaces shows that Nafion is redistributed after potential is applied. Our results verify that Nafion membrane offers a reliable means to secure particles onto electrodes. Furthermore, the electrochemical performance is reliable and reproducible. Thus, this approach provides a new way to study more complex and challenging particles, such as uranium oxide, in the future.

Molecular imaging of plant-microbe interactions on the Brachypodium seed surface.

Plant growth-promoting rhizobacteria (PGPR) play a crucial role in biological control and pathogenic defense on and within plant tissues, however the mechanisms by which plants associate with PGPR to elicit such beneficial effects need further study. Here, we present time-of-flight secondary ion mass spectrometry (ToF-SIMS) imaging of Brachypodium distachyon (Brachypodium) seeds with and without exposure to two model PGPR, i.e., Gram-negative Pseudomonas fluorescens SBW25 (P.) and Gram-positive Arthrobacter chlorophenolicus A6 (A.). Delayed image extraction was used to image PGPR-treated seed sections to reveal morphological changes. ToF-SIMS spectral comparison, principal component analysis (PCA), and two-dimensional (2D) imaging show that the selected PGPR have different effects on the host seed surface, resulting in changes in chemical composition and morphology. Metabolite products and biomarkers, such as flavonoids, phenolic compounds, fatty acids, and indole-3-acetic acid (IAA), were identified on the PGPR-treated seed surfaces. These compounds have different distributions on the Brachypodium seed surface for the two PGPR, indicating that the different bacteria elicit distinct responses from the host. Our results illustrate that ToF-SIMS is an effective tool to study plant-microbe interactions and to provide insightful information with submicrometer lateral resolution of the chemical distributions associated with morphological features, potentially offering a new way to study the mechanisms underlying beneficial roles of PGPR.

Stamping Nanoparticles onto the Electrode for Rapid Electrochemical Analysis in Microfluidics.

Electrochemical analysis is an efficient way to study various materials. However, nanoparticles are challenging due to the difficulty in fabricating a uniform electrode containing nanoparticles. We developed novel approaches to incorporate nanoparticles as a working electrode (WE) in a three-electrode microfluidic electrochemical cell. Specifically, conductive epoxy was used as a medium for direct application of nanoparticles onto the electrode surface. Three approaches in this work were illustrated, including sequence stamping, mix stamping, and droplet stamping. Shadow masking was used to form the conductive structure in the WE surface on a thin silicon nitride (SiN) membrane. Two types of nanomaterials, namely cerium oxide (CeO2) and graphite, were chosen as representative nanoparticles. The as-fabricated electrodes with attached particles were characterized using atomic force microscopy (AFM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Electrochemical analysis was performed to verify the feasibility of these nanoparticles as electrodes. Nanomaterials can be quickly assessed for their electrochemical properties using these new electrode fabrication methods in a microfluidic cell, offering a passport for rapid nanomaterial electrochemical analysis in the future.

Direct visualization of radiation-induced transformations at alkali halide-air interfaces.

Radiation driven reactions at mineral/air interfaces are important to the chemistry of the atmosphere, but experimental constraints (e.g. simultaneous irradiation, in situ observation, and environmental control) leave process understanding incomplete. Using a custom atomic force microscope equipped with an integrated X-ray source, transformation of potassium bromide surfaces to potassium nitrate by air radiolysis species was followed directly in situ at the nanoscale. Radiolysis initiates dynamic step edge dissolution, surface composition evolution, and ultimately nucleation and heteroepitaxial growth of potassium nitrate crystallites mediated by surface diffusion at rates controlled by adsorbed water. In contrast to in situ electron microscopy and synchrotron-based imaging techniques where high radiation doses are intrinsic, our approach illustrates the value of decoupling irradiation and the basis of observation.

Self-organizing layers from complex molecular anions.

The formation of traditional ionic materials occurs principally via joint accumulation of both anions and cations. Herein, we describe a previously unreported phenomenon by which macroscopic liquid-like thin layers with tunable self-organization properties form through accumulation of stable complex ions of one polarity on surfaces. Using a series of highly stable molecular anions we demonstrate a strong influence of the internal charge distribution of the molecular ions, which is usually shielded by counterions, on the properties of the layers. Detailed characterization reveals that the intrinsically unstable layers of anions on surfaces are stabilized by simultaneous accumulation of neutral molecules from the background environment. Different phases, self-organization mechanisms and optical properties are observed depending on the molecular properties of the deposited anions, the underlying surface and the coadsorbed neutral molecules. This demonstrates rational control of the macroscopic properties (morphology and size of the formed structures) of the newly discovered anion-based layers.

"Size-Independent" Single-Electron Tunneling.

Incorporating single-electron tunneling (SET) of metallic nanoparticles (NPs) into modern electronic devices offers great promise to enable new properties; however, it is technically very challenging due to the necessity to integrate ultrasmall (<10 nm) particles into the devices. The nanosize requirements are intrinsic for NPs to exhibit quantum or SET behaviors, for example, 10 nm or smaller, at room temperature. This work represents the first observation of SET that defies the well-known size restriction. Using polycrystalline Au NPs synthesized via our newly developed solid-state glycine matrices method, a Coulomb Blockade was observed for particles as large as tens of nanometers, and the blockade voltage exhibited little dependence on the size of the NPs. These observations are counterintuitive at first glance. Further investigations reveal that each observed SET arises from the ultrasmall single crystalline grain(s) within the polycrystal NP, which is (are) sufficiently isolated from the nearest neighbor grains. This work demonstrates the concept and feasibility to overcome orthodox spatial confinement requirements to achieve quantum effects.

High-Resolution Imaging of Polyethylene Glycol Coated Dendrimers via Combined Atomic Force and Scanning Tunneling Microscopy.

Dendrimers have shown great promise as drug delivery vehicles in recent years because they can be synthesized with designed size and functionalities for optimal transportation, targeting, and biocompatibility. One of the most well-known termini used for biocompatibility is polyethylene glycol (PEG), whose performance is affected by its actual conformation. However, the conformation of individual PEG bound to soft materials such as dendrimers has not been directly observed. Using atomic force microscopy (AFM) and scanning tunneling microscopy (STM), this work characterizes the structure adopted by PEGylated dendrimers with the highest resolution reported to date. AFM imaging enables visualization of the individual dendrimers, as well as the differentiation and characterization of the dendrimer core and PEG shell. STM provides direct imaging of the PEG extensions with high-resolution. Collectively, this investigation provides important insight into the structure of coated dendrimers, which is crucial for the design and development of better drug delivery vehicles.

High-Resolution Imaging of Dendrimers Used in Drug Delivery via Scanning Probe Microscopy.

Dendrimers and telodendrimer micelles represent two new classes of vehicles for drug delivery that have attracted much attention recently. Their structural characterization at the molecular and submolecular level remains a challenge due to the difficulties in reaching high resolution when imaging small particles in their native media. This investigation offers a new approach towards this challenge, using scanning tunneling microscopy (STM) and atomic force microscopy (AFM). By using new sample preparation protocols, this work demonstrates that (a) intramolecular features such as drug molecules and dendrimer termini can be resolved; and (b) telodendrimer micelles can be immobilized on the surface without compromising structural integrity, and as such, high resolution AFM imaging may be performed to attain 3D information. This high-resolution structural information should enhance our knowledge of the nanocarrier structure and nanocarrier-drug interaction and, therefore, facilitate design and optimization of the efficiency in drug delivery.

High-resolution imaging of the intramolecular structure of indomethacin-carrying dendrimers by scanning tunneling microscopy.

Dendrimers have shown great potential in drug delivery because of their enhancement of drug solubility in aqueous media, leading to an increase in in vivo circulation and efficacy to targets. The structure of drug-dendrimer complexes however, is not well-known owing to the difficulties associated with visualizing individual drug molecules attached to dendrimers. Scanning tunneling microscopy (STM) enables visualization of dendrimer intramolecular structures using our approach of metal ion tagging. This work extends the approach to reveal the hierarchical structure of indomethacin-loaded poly(amidoamine) hydroxyl-terminated dendrimers. STM imaging provides structural information such as their height, lateral dimensions, and volume. High-resolution STM images enable the identification and count of individual indomethacin molecules bound to the anterior of dendrimers. Removal of drug molecules by the STM tip allows the calculation of individual drug-dendrimer binding energy, which is consistent with 1-3 hydrogen bonds. These investigations provide new insight into the hierarchical structure and nature of indomethacin-dendrimer interactions and deepen our understanding of the stability and pharmacokinetic behavior of dendrimer-based drug delivery vehicles.