An operando electrochemical stage for the transmission electron microscope has been configured to form a "Li battery" that is used to quantify the electrochemical processes that occur at the anode during charge/discharge cycling. Of particular importance for these observations is the identification of an image contrast reversal that originates from solid Li being less dense than the surrounding liquid electrolyte and electrode surface. This contrast allows Li to be identified from Li-containing compounds that make up the solid-electrolyte interphase (SEI) layer. By correlating images showing the sequence of Li electrodeposition and the evolution of the SEI layer with simultaneously acquired and calibrated cyclic voltammograms, electrodeposition, and electrolyte breakdown processes can be quantified directly on the nanoscale. This approach opens up intriguing new possibilities to rapidly visualize and test the electrochemical performance of a wide range of electrode/electrolyte combinations for next generation battery systems.
Global quantification of protein abundances in single cells could provide direct information on cellular phenotypes and complement transcriptomics measurements. However, single-cell proteomics is still immature and confronts many technical challenges. Herein we describe a nested nanoPOTS (N2) chip to improve protein recovery, operation robustness, and processing throughput for isobaric-labeling-based scProteomics workflow. The N2 chip reduces reaction volume to <30 nL and increases capacity to >240 single cells on a single microchip. The tandem mass tag (TMT) pooling step is simplified by adding a microliter droplet on the nested nanowells to combine labeled single-cell samples. In the analysis of ~100 individual cells from three different cell lines, we demonstrate that the N2 chip-based scProteomics platform can robustly quantify ~1500 proteins and reveal membrane protein markers. Our analyses also reveal low protein abundance variations, suggesting the single-cell proteome profiles are highly stable for the cells cultured under identical conditions.
New nanofluidic LC-TEM devices enable controlling and understanding electron irradiation history effects on liquid samples.
Operando MAS NMR studies provide unique insights into the details of chemical reactions; comprehensive information about temperature-and time-dependent changes in chemical species is accompanied by similarly rich information about changes in phase and chemical environment. Here we describe a new MAS NMR rotor (the WHiMS rotor) capable of achieving internal pressures up to 400 bar at 20 °C or 225 bar at 250 °C, a range that includes many reactions of interest. The MAS NMR spectroscopy enabled by these rotors is ideal for studying the behavior of mixed-phase systems, such as reactions involving solid catalysts and volatile liquids, with the potential to add gases at high pressure. The versatile operation of the new rotors is demonstrated by collecting operando 1 H and 13 C spectra during the hydrogenolysis of benzyl phenyl ether, catalyzed by Ni/γ-Al 2 O 3 at ca. 250 °C, both with and without H 2 (g) supplied to the rotor. The 2-propanol solvent, which exists in the supercritical phase under these reaction conditions, serves as an internal source of H 2 . The NMR spectra provide detailed kinetic profiles for the formation of the primary products toluene and phenol as well as secondary hydrogenation and etherification products.
Global quantification of protein abundances in single cells would provide more direct information on cellular function phenotypes and complement transcriptomics measurements. However, single-cell proteomics (scProteomics) is still immature and confronts technical challenges, including limited proteome coverage, poor reproducibility, as well as low throughput. Here we describe a nested nanowell (N2) chip to dramatically improve protein recovery, operation robustness, and processing throughput for isobaric-labeling-based scProteomics workflow. The N2 chip allows reducing cell digestion volume to <30 nL and increasing processing capacity to > 240 single cells in one microchip. In the analysis of ~100 individual cells from three different cell lines, we demonstrate the N2 chip-based scProteomics platform can robustly quantify ~1500 proteins and reveal functional differences. Our analysis also reveals low protein abundance variations (median CVs < 16.3%), highlighting the utility of such measurements, and also suggesting the single-cell proteome is highly stable for the cells cultured under identical conditions.
A longstanding limitation of high-resolution NMR spectroscopy is the requirement for samples to have macroscopic dimensions. Commercial probes, for example, are designed for volumes of at least 5 μL, in spite of decades of work directed toward the goal of miniaturization. Progress in miniaturizing inductive detectors has been limited by a perceived need to meet two technical requirements: (1) minimal separation between the sample and the detector, which is essential for sensitivity, and (2) near-perfect magnetic-field homogeneity at the sample, which is typically needed for spectral resolution. The first of these requirements is real, but the second can be relaxed, as we demonstrate here. By using pulse sequences that yield high-resolution spectra in an inhomogeneous field, we eliminate the need for near-perfect field homogeneity and the accompanying requirement for susceptibility matching of microfabricated detector components. With this requirement removed, typical imperfections in microfabricated components can be tolerated, and detector dimensions can be matched to those of the sample, even for samples of volume ≪5 μL. Pulse sequences that are robust to field inhomogeneity thus enable small-volume detection with optimal sensitivity. We illustrate the potential of this approach to miniaturization by presenting spectra acquired with a flat-wire detector that can easily be scaled to subnanoliter volumes. In particular, we report high-resolution NMR spectroscopy of an alanine sample of volume 500 pL.
In geologic carbon sequestration, CO2 is injected into geologic reservoirs as a supercritical fluid (scCO2). The carbonation of divalent silicates exposed to humidified scCO2 occurs in angstroms to nanometers thick adsorbed H2O films. A threshold H2O film thickness is required for carbonate precipitation, but a mechanistic understanding is lacking. In this study, we investigated carbonation of forsterite (Mg2SiO4) in humidified scCO2 (50 °C and 90 bar), which serves as a model system for understanding subsurface divalent silicate carbonation reactivity. Attenuated total reflection infrared spectroscopy pinpointed that magnesium carbonate precipitation begins at 1.5 monolayers of adsorbed H2O. At about this same H2O coverage, transmission infrared spectroscopy showed that forsterite dissolution begins and electrical impedance spectroscopy demonstrated that diffusive transport accelerates. Molecular dynamics simulations indicated that the onset of diffusion is due to an abrupt decrease in the free-energy barriers for lateral mobility of outer-spherically adsorbed Mg2+. The dissolution and mass transport controls on divalent silicate reactivity in wet scCO2 could be advantageous for maximizing permeability near the wellbore and minimize leakage through the caprock.
Subsampled image acquisition followed by image inpainting in a scanning transmission electron microscope is a novel approach to control dose and increase the image frame rate during experiments, thereby allowing independent control of the spatial and temporal dose envelope during image acquisition. Here, subsampled imaging is shown to permit precise in situ observations of the fundamental kinetic processes behind nucleation and growth of silver (Ag) nanoparticles from an aqueous solution. At high sampling-levels, nanoparticles can be observed with morphologies that are consistent with strong interface interactions, i.e., rafts and pillars, whereas at low sampling-levels, the particles exhibit regular spherical morphologies. The relative numbers of rafts/pillars and regular nanoparticles, their sizes, and their incubation times can be attributed to local changes in the molar concentration of the Ag ions in the aqueous solution; higher sampling-levels significantly increase the reactants in the vicinity of the window, leading to rapid supersaturation and the precipitation on the window surface. These precisely controlled kinetics highlight subsampled imaging as a method by which the driving force for nucleation and growth (i.e., the electron beam) can be disentangled from the spatial/temporal resolution of the observation in all in situ experiments, providing a pathway to identify and quantify the importance of individual kinetic factors behind nucleation and growth in a wide variety of complex materials systems and architectures.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.