Advanced Materials for Energy-Water Systems: The Central Role of Water/Solid Interfaces in Adsorption, Reactivity, and Transport.

The structure, chemistry, and charge of interfaces between materials and aqueous fluids play a central role in determining properties and performance of numerous water systems. Sensors, membranes, sorbents, and heterogeneous catalysts almost uniformly rely on specific interactions between their surfaces and components dissolved or suspended in the water-and often the water molecules themselves-to detect and mitigate contaminants. Deleterious processes in these systems such as fouling, scaling (inorganic deposits), and corrosion are also governed by interfacial phenomena. Despite the importance of these interfaces, much remains to be learned about their multiscale interactions. Developing a deeper understanding of the molecular- and mesoscale phenomena at water/solid interfaces will be essential to driving innovation to address grand challenges in supplying sufficient fit-for-purpose water in the future. In this Review, we examine the current state of knowledge surrounding adsorption, reactivity, and transport in several key classes of water/solid interfaces, drawing on a synergistic combination of theory, simulation, and experiments, and provide an outlook for prioritizing strategic research directions.

In situoff-axis electron holography of real-time dopant diffusion in GaAs nanowires.

Off-axis electron holography was used to reveal remote doping in GaAs nanowires occurring duringin situannealing in a transmission electron microscope. Dynamic changes to the electrostatic potential caused by carbon dopant diffusion upon annealing were measured across GaAs nanowires with radial p-p+ core-shell junctions. Electrostatic potential profiles were extracted from holographic phase maps and built-in potentials (Vbi) and depletion layer widths (DLWs) were estimated as function of temperature over 300-873 K. Simulations in absence of remote doping predict a significant increase ofVbiand DLWs with temperature. In contrast, we measured experimentally a nearly constantVbiand a weak increase of DLWs. Moreover, we observed the appearance of a depression in the potential profile of the core upon annealing. We attribute these deviations from the predicted behavior to carbon diffusion from the shell to the core through the nanowire sidewalls, i.e. to remote doping, becoming significant at 673 K. The DLW in the p and p+ regions are in the 10-30 nm range.

Spatial Image Resolution Assessment by Fourier Analysis (SIRAF).

Determining spatial resolution from images is crucial when optimizing focus, determining smallest resolvable object, and assessing size measurement uncertainties. However, no standard algorithm exists to measure resolution from electron microscopy (EM) images, though several have been proposed, where most require user decisions. We present the Spatial Image Resolution Assessment by Fourier analysis (SIRAF) algorithm that uses fast Fourier transform analysis to estimate resolution directly from a single image without user inputs. The method is derived from the underlying assumption that objects display intensity transitions, resembling a step function blurred by a Gaussian point spread function. This hypothesis is tested and verified on simulated EM images with known resolution. To identify potential pitfalls, the algorithm is also tested on simulated images with a variety of settings, and on real SEM images acquired at different magnification and defocus settings. Finally, the versatility of the method is investigated by assessing resolution in images from several microscopy techniques. It is concluded that the algorithm can assess resolution from a large selection of image types, thereby providing a measure of this fundamental image parameter. It may also improve autofocus methods and guide the optimization of magnification settings when balancing spatial resolution and field of view.

Unhindered Brownian Motion of Individual Nanoparticles in Liquid-Phase Scanning Transmission Electron Microscopy.

Liquid-phase transmission electron microscopy (LPTEM) offers label-free imaging of nanoparticle (NP) processes in liquid with sub-nanometer spatial and millisecond temporal resolution. However, LPTEM studies have reported only on NPs moving orders of magnitude slower than expected from bulk aqueous liquid conditions, likely due to strong interactions with the LPTEM liquid-enclosing membranes. We demonstrate how scanning transmission electron microscope (STEM) imaging can be used to measure the motion of individual NPs and agglomerates, which are not hindered by such interactions. Only at low electron flux do we find that individual NPs exhibit Brownian motion consistent with optical control experiments and theoretical predictions for unhindered passive diffusive motion in bulk liquids. For increasing electron flux, we find increasingly faster than passive motion that still appears effectively Brownian. We discuss the possible origins of this beam-sample interaction. This establishes conditions for the use of STEM as a reliable tool for imaging nanoscale hydrodynamics in situ TEM.

Mean Inner Potential of Liquid Water.

Improving our experimental and theoretical knowledge of electric potentials at liquid-solid boundaries is essential to achieve a deeper understanding of the driving forces behind interfacial processes. Electron holography has proved successful in probing solid-solid interfaces but requires knowledge of the materials' mean inner potential (MIP, V_{0}), which is a fundamental bulk material property. Combining off-axis electron holography with liquid phase transmission electron microscopy (LPTEM), we provide the first quantitative MIP determination of liquid water V_{0}=+4.48±0.19 V. This value is larger than most theoretical predictions, and to explain the disagreement we assess the dominant factors needed in quantum simulations of liquid water. A precise MIP lays the foundations for nanoscale holographic potential measurements in liquids, and provides a benchmark to improve quantum mechanical descriptions of aqueous systems and their interfaces in, e.g., electrochemistry, solvation processes, and spectroscopy.

In situ TEM modification of individual silicon nanowires and their charge transport mechanisms.

Correlating the structure and composition of nanowires grown by the vapour-liquid-solid (VLS) mechanism with their electrical properties is essential for designing nanowire devices. In situ transmission electron microscopy (TEM) that can image while simultaneously measuring the current-voltage (I-V) characteristics of individual isolated nanowires is a unique tool for linking changes in structure with electronic transport. Here we grow and electrically connect silicon nanowires inside a TEM to perform in situ electrical measurements on individual nanowires both at high temperature and upon surface oxidation, as well as under ambient conditions. As-grown, the oxide-free nanowires have nonlinear I-V characteristics. We analyse the I-V measurements in terms of both bulk and injection limited transport models, finding Joule heating effects, bulk-limiting effects for thin nanowires and an injection-limiting effect for thick wires when high voltages are applied. When the nanowire surface is modified by in situ oxidation, drastic changes occur in the electronic properties. We investigate the relation between the observed geometry, changes in the surface structure and changes in electronic transport, obtaining information for individual nanowires that is inaccessible to other measuring techniques.

Analysis of Electron Transparent Beam-Sensitive Samples Using Scanning Electron Microscopy Coupled With Energy-Dispersive X-ray Spectroscopy.

Scanning electron microscopy, coupled with energy-dispersive X-ray spectroscopy (EDS), is a powerful tool used in many scientific fields. It can provide nanoscale images, allowing size and morphology measurements, as well as provide information on the spatial distribution of elements in a sample. This study compares the capabilities of a traditional EDS detector with a recently developed annular EDS detector when analyzing electron transparent and beam-sensitive NaCl particles on a TEM grid. The optimal settings for single particle analysis are identified in order to minimize beam damage and optimize sample throughput via the choice of acceleration voltage, EDS acquisition time, and quantification model. Here, a linear combination of two models is used to bridge results for particle sizes, which are neither bulk nor sufficiently thin to assume electron transparent. Additionally, we show that the increased count rate obtainable with the annular detector enables mapping as a viable analysis strategy compared with feature detection methods, which only scan segmented regions. Finally, we discuss advantages and disadvantages of the two analysis strategies.

Methods for Calibration of Specimen Temperature During In Situ Transmission Electron Microscopy Experiments.

One of the biggest challenges for in situ heating transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) is the ability to measure the local temperature of the specimen accurately. Despite technological improvements in the construction of TEM/STEM heating holders, the problem of being able to measure the real sample temperature is still the subject of considerable discussion. In this study, we review the present literature on methodologies for temperature calibration. We analyze calibration methods that require the use of a thermometric material in addition to the specimen under study, as well as methods that can be performed directly on the specimen of interest without the need for a previous calibration. Finally, an overview of the most important characteristics of all the treated techniques, including temperature ranges and uncertainties, is provided in order to provide an accessory database to consult before an in situ TEM/STEM temperature calibration experiment.

Differential proteome and cellular adhesion analyses of the probiotic bacterium Lactobacillus acidophilus NCFM grown on raffinose - an emerging prebiotic.

Whole cell and surface proteomes were analyzed together with adhesive properties of the probiotic bacterium Lactobacillus acidophilus NCFM (NCFM) grown on the emerging prebiotic raffinose, exemplifying a synbiotic. Adhesion of NCFM to mucin and intestinal HT-29 cells increased three-fold after culture with raffinose versus glucose, as also visualized by scanning electron microscopy. Comparative proteomics using 2D-DIGE showed 43 unique proteins to change in relative abundance in whole cell lysates from NCFM grown on raffinose compared to glucose. Furthermore, 14 unique proteins in 18 spots of the surface subproteome underwent changes identified by differential 2DE, including elongation factor G, thermostable pullulanase, and phosphate starvation inducible stress-related protein increasing in a range of +2.1 - +4.7 fold. By contrast five known moonlighting proteins decreased in relative abundance by up to -2.4 fold. Enzymes involved in raffinose catabolism were elevated in the whole cell proteome; α-galactosidase (+13.9 fold); sucrose phosphorylase (+5.4 fold) together with metabolic enzymes from the Leloir pathway for galactose utilization and the glycolysis; ß-galactosidase (+5.7 fold); galactose (+2.9/+3.1 fold) and fructose (+2.8 fold) kinases. The insights at the molecular and cellular levels contributed to the understanding of the interplay of a synbiotic composed of NCFM and raffinose with the host.

Synthesis, Characterizations of Superparamagnetic Fe3O4-Ag Hybrid Nanoparticles and Their Application for Highly Effective Bacteria Inactivation.

In recent years, outbreaks of infectious diseases caused by pathogenic micro-organisms pose a serious threat to public health. In this work, Fe3O4-Ag hybrid nanoparticles were synthesized by simple chemistry method and these prepared nanoparticles were used to investigate their antibacterial properties and mechanism against methicilline-resistant Staphylococcus aureus (MRSA) pathogen. The formation of dimer-like nanostructure of Fe3O4-Ag hybrid NPs was confirmed by X-ray diffraction and High-resolution Transmission Electron Microscopy. Our biological analysis revealed that the Fe3O4-Ag hybrid NPs showed more noticeable bactericidal activity than that of plain Fe3O4 NPs and Ag-NPs. We suggest that the enhancement in bactericidal activity of Fe3O4-Ag hybrid NPs might be likely from main factors such as: (i) enhanced surface area property of hybrid nanoparticles; (ii) the high catalytic activity of Ag-NPs with good dispersion and aggregation stability due to the iron oxide magnetic carrier, and (iii) large direct physical contacts between the bacterial cell membrane and the hybrid nanoparticles. The superparamagnetic hybrid nanoparticles of iron oxide magnetic nanoparticles decorated with silver nanoparticles can be a potential candidate to effectively treat infectious MRSA pathogen with recyclable capability, targeted bactericidal delivery and minimum release into environment.

Creating New VLS Silicon Nanowire Contact Geometries by Controlling Catalyst Migration.

The formation of self-assembled contacts between vapor-liquid-solid grown silicon nanowires and flat silicon surfaces was imaged in situ using electron microscopy. By measuring the structural evolution of the contact formation process, we demonstrate how different contact geometries are created by adjusting the balance between silicon deposition and Au migration. We show that electromigration provides an efficient way of controlling the contact. The results point to novel device geometries achieved by direct nanowire growth on devices.

MWCNTs of different physicochemical properties cause similar inflammatory responses, but differences in transcriptional and histological markers of fibrosis in mouse lungs.

Multi-walled carbon nanotubes (MWCNTs) are an inhomogeneous group of nanomaterials that vary in lengths, shapes and types of metal contamination, which makes hazard evaluation difficult. Here we present a toxicogenomic analysis of female C57BL/6 mouse lungs following a single intratracheal instillation of 0, 18, 54 or 162 µg/mouse of a small, curled (CNT(Small), 0.8 ± 0.1 µm in length) or large, thick MWCNT (CNT(Large), 4 ± 0.4 µm in length). The two MWCNTs were extensively characterized by SEM and TEM imaging, thermogravimetric analysis, and Brunauer-Emmett-Teller surface area analysis. Lung tissues were harvested 24h, 3 days and 28 days post-exposure. DNA microarrays were used to analyze gene expression, in parallel with analysis of bronchoalveolar lavage fluid, lung histology, DNA damage (comet assay) and the presence of reactive oxygen species (dichlorodihydrofluorescein assay), to profile and characterize related pulmonary endpoints. Overall changes in global transcription following exposure to CNT(Small) or CNT(Large) were similar. Both MWCNTs elicited strong acute phase and inflammatory responses that peaked at day 3, persisted up to 28 days, and were characterized by increased cellular influx in bronchoalveolar lavage fluid, interstitial pneumonia and gene expression changes. However, CNT(Large) elicited an earlier onset of inflammation and DNA damage, and induced more fibrosis and a unique fibrotic gene expression signature at day 28, compared to CNT(Small). The results indicate that the extent of change at the molecular level during early response phases following an acute exposure is greater in mice exposed to CNT(Large), which may eventually lead to the different responses observed at day 28.

A uniform measurement expression for cross method comparison of nanoparticle aggregate size distributions.

Available measurement methods for nanomaterials are based on very different measurement principles and hence produce different values when used on aggregated nanoparticle dispersions. This paper provides a solution for relating measurements of nanomaterials comprised of nanoparticle aggregates determined by different techniques using a uniform expression of a mass equivalent diameter (MED). The obtained solution is used to transform into MED the size distributions of the same sample of synthetic amorphous silica (nanomaterial comprising aggregated nanoparticles) measured by six different techniques: scanning electron microscopy in both high vacuum (SEM) and liquid cell setup (Wet-SEM); gas-phase electrophoretic mobility molecular analyzer (GEMMA); centrifugal liquid sedimentation (CLS); nanoparticle tracking analysis (NTA); and asymmetric flow field flow fractionation with inductively coupled plasma mass spectrometry detection (AF4-ICP-MS). Transformed size distributions are then compared between the methods and conclusions drawn on methods' measurement accuracy, limits of detection and quantification related to the synthetic amorphous silca's size. Two out of the six tested methods (GEMMA and AF4-ICP-MS) cross validate the MED distributions between each other, providing a true measurement. The measurement accuracy of other four techniques is shown to be compromised either by the high limit of detection and quantification (CLS, NTA, Wet-SEM) or the sample preparation that is biased by increased retention of smaller nanomaterials (SEM). This study thereby presents a successful and conclusive cross-method comparison of size distribution measurements of aggregated nanomaterials. The authors recommend the uniform MED size expression for application in nanomaterial risk assessment studies and clarifications in current regulations and definitions concerning nanomaterials.

FIB-SEM imaging of carbon nanotubes in mouse lung tissue.

Ultrastructural characterisation is important for understanding carbon nanotube (CNT) toxicity and how the CNTs interact with cells and tissues. The standard method for this involves using transmission electron microscopy (TEM). However, in particular, the sample preparation, using a microtome to cut thin sample sections for TEM, can be challenging for investigation of regions with agglomerations of large and stiff CNTs because the CNTs cut with difficulty. As a consequence, the sectioning diamond knife may be damaged and the uncut CNTs are left protruding from the embedded block surface excluding them from TEM analysis. To provide an alternative to ultramicrotomy and subsequent TEM imaging, we studied focused ion beam scanning electron microscopy (FIB-SEM) of CNTs in the lungs of mice, and we evaluated the applicability of the method compared to TEM. FIB-SEM can provide serial section volume imaging not easily obtained with TEM, but it is time-consuming to locate CNTs in the tissue. We demonstrate that protruding CNTs after ultramicrotomy can be used to locate the region of interest, and we present FIB-SEM images of CNTs in lung tissue. FIB-SEM imaging was applied to lung tissue from mice which had been intratracheally instilled with two different multiwalled CNTs; one being short and thin, and the other longer and thicker. FIB-SEM was found to be most suitable for detection of the large CNTs (Ø ca. 70 nm), and to be well suited for studying CNT agglomerates in biological samples which is challenging using standard TEM techniques.

Monolithic chip system with a microfluidic channel for in situ electron microscopy of liquids.

Electron microscopy of enclosed liquid samples requires the thinnest possible membranes as enclosing windows as well as nanoscale liquid sample thickness to achieve the best possible resolution. Today liquid sample systems for transmission electron microscopy (TEM) are typically made from two sandwiched microchips with thin membranes. We report on a new microfabricated chip system based on a monolithic design that enables membrane geometry on the scale of a few micrometers. The design is intended to reduce membrane deflection when the system is under pressure, a microfluidic channel for improved flow geometry, and a better space angle for auxiliary detectors such as energy-dispersive X-ray spectroscopy. We explain the system design and fabrication and show the first successful TEM images of liquid samples in the chips.

Experimental Requirements for High-Temperature Solid-State Electrochemical TEM Experiments.

The ability to perform both electrochemical and structural/elemental characterization in the same experiment and at the nanoscale allows to directly link electrochemical performance to the material properties and their evolution over time and operating conditions. Such experiments can be important for the further development of solid oxide cells, solid-state batteries, thermal electrical devices, and other solid-state electrochemical devices. The experimental requirements for conducting solid-state electrochemical TEM experiments in general, including sample preparation, electrochemical measurements, failure factors, and possibilities for optimization, are presented and discussed. Particularly, the methodology of performing reliable electrochemical impedance spectroscopy measurements in reactive gases and at elevated temperatures for both single materials and solid oxide cells is described. The presented results include impedance measurements of electronic conductors, an ionic conductor, and a mixed ionic and electronic conductor, all materials typically applied in solid oxide fuel and electrolysis cells. It is shown that how TEM and impedance spectroscopy can be synergically integrated to measure the transport and surface exchange properties of materials with nanoscale dimensions and to visualize their structural and elemental evolution via TEM/STEM imaging and spectroscopy.

Fibroblasts cultured on nanowires exhibit low motility, impaired cell division, and DNA damage.

Nanowires are commonly used as tools for interfacing living cells, acting as biomolecule-delivery vectors or electrodes. It is generally assumed that the small size of the nanowires ensures a minimal cellular perturbation, yet the effects of nanowires on cell migration and proliferation remain largely unknown. Fibroblast behaviour on vertical nanowire arrays is investigated, and it is shown that cell motility and proliferation rate are reduced on nanowires. Fibroblasts cultured on long nanowires exhibit failed cell division, DNA damage, increased ROS content and respiration. Using focused ion beam milling and scanning electron microscopy, highly curved but intact nuclear membranes are observed, showing no direct contact between the nanowires and the DNA. The nanowires possibly induce cellular stress and high respiration rates, which trigger the formation of ROS, which in turn results in DNA damage. These results are important guidelines to the design and interpretation of experiments involving nanowire-based transfection and electrical characterization of living cells.