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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3

In situ and operando force-based atomic force microscopy for probing local functionality in energy storage materials

Electrochemical energy storage is the key enabling component of electric vehicles and solar-/wind-based energy technologies. The enhancement of energy stored requires the detailed understanding of charge storage mechanisms and local electrochemical and electromechanical phenomena over a variety of length scales from atoms to full cells. Classical electrochemical techniques, such as voltammetry, represent the macroscopic electrochemical properties, and consequently do not allow to extract important information about local electrochemical reactions, ions adsorption, intercalations, and transport. Understanding, controlling, and tuning the local electrochemical functionalities in functional energy materials require in situ/operando techniques which limit the use of structural and functional characterization techniques that provide local information. Here, force-based atomic force microscopies (AFMs) have provided novel insights into locally probing electrochemical mechanisms on tens of nanometer and even molecular length scales and provide a viable pathway to probe electrochemical processes in situ/operando. In this review, we highlight the contributions in the development and application of force-based AFM methods to elucidate the local charge storage mechanism in a variety of energy-related materials. We will focus in particular on methods or AFM modalities in a liquid electrolyte environment.

25 ENERGY STORAGE↗

Atomic Force Microscopy to Characterize Antimicrobial Peptide-Induced Defects in Model Supported Lipid Bilayers

Antimicrobial peptides (AMPs) interact with bacterial cell membranes through a variety of mechanisms, causing changes extending from nanopore formation to microscale membrane lysis, eventually leading to cell death. Several AMPs also disrupt mammalian cell membranes, despite their significantly different lipid composition and such collateral hemolytic damage hinders the potential therapeutic applicability of the AMP as an anti-microbial. Elucidating the mechanisms underlying the AMP–membrane interactions is challenging due to the variations in the chemical and structural features of the AMPs, the complex compositional variations of cell membranes and the inadequacy of any single experimental technique to comprehensively probe them. (1) Background: Atomic Force Microscopy (AFM) imaging can be used in combination with other techniques to help understand how AMPs alter the orientation and structural organization of the molecules within cell membranes exposed to AMPs. The structure, size, net charge, hydrophobicity and amphipathicity of the AMPs affect how they interact with cell membranes of differing lipid compositions. (2) Methods: Our study examined two different types of AMPs, a 20-amino acid, neutral, α-helical (amphipathic) peptide, alamethicin, and a 13-amino acid, non-α-helical cationic peptide, indolicidin (which intramolecularly folds, creating a hydrophobic core), for their interactions with supported lipid bilayers (SLBs). Robust SLB model membranes on quartz supports, incorporating predominantly anionic lipids representative of bacterial cells, are currently not available and remain to be developed. Therefore, the SLBs of zwitterionic egg phosphatidylcholine (PC), which represents the composition of a mammalian cell membrane, was utilized as the model membrane. This also allows for a comparison with the results obtained from the Quartz Crystal Microbalance with Dissipation (QCM-D) experiments conducted for these peptides interacting with the same zwitterionic SLBs. Further, in the case of alamethicin, because of its neutrality, the lipid charge may be less relevant for understanding its membrane interactions. (3) Results: Using AFM imaging and roughness analysis, we found that alamethicin produced large, unstable defects in the membrane at 5 µM concentrations, and completely removed the bilayer at 10 µM. Indolicidin produced smaller holes in the bilayer at 5 and 10 µM, although they were able to fill in over time. The root-mean-square (RMS) roughness values for the images showed that the surface roughness caused by visible defects peaked after peptide injection and gradually decreased over time. (4) Conclusions: AFM is useful for helping to uncover the dynamic interactions between different AMPs and cell membranes, which can facilitate the selection and design of more efficient AMPs for use in therapeutics and antimicrobial applications.

Swana, Kathleen W.↗

Understanding the Selective Deposition of Li Metal on Nonuniform Electrode Surfaces Using Atomic Force Microscopy

The use of lithium metal in secondary batteries has been impeded by its tendency to form dendrites: branching conductive structures of metal that can lead to capacity loss and, ultimately, internal shorts in the battery. Patterned electrodes, in addition to artificially increasing the current density of cells by increasing the surface area available for reaction, also generate a nonuniform electric field in the vicinity of the electrode surface. This nonuniform electric field, though rapidly screened by the electrolyte, can promote inhomogeneous deposition and Solid Electrolyte Interphase formation. As the consequence of these effects is not theoretically apparent since Solid Electrolyte Interphase volume and conductivity changes can, in principle, offset variations in local current density, we have performed experiments to examine the deposition of Li on nonuniform electrode surfaces using Atomic Force Microscopy. In this work, we measure the local variations in topography, SEI thickness, and composition, and discuss their implications for the formation of dendrites in Li metal.

25 ENERGY STORAGE↗

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. Overall, our novel rad-AFM opens doors into understanding the dynamics of radiolytically-driven mass transfer and surface alteration at the nanoscale in real-time.

47 OTHER INSTRUMENTATION↗

Mechanistic Pathways for the Molecular Step Growth of Calcium Oxalate Monohydrate Crystal Revealed by In Situ Liquid-Phase Atomic Force Microscopy

Calcium oxalate monohydrate (COM) crystal is the most common crystalline component of human kidney stones. The molecular-scale inhibitory mechanisms of COM crystal growth by urinary biomolecules such as citrate and osteopontin adsorbed onto the crystal surface are now well understood. However, the pathways by which dissolved calcium and oxalate ions are incorporated into the molecular step of the COM crystal surface, leading to COM crystal growth—a prerequisite to be elucidated for developing effective therapeutics to inhibit COM stones—remain unknown. Here, using in situ liquid-phase atomic microscopy along with a step kinetic model, we reveal the pathways of the calcium and oxalate ions into the COM molecular step via the growth speed analysis of the molecular steps with respect to their step width at the nanoscale. Our results show that, primarily, the ions are adsorbed onto the terrace of the crystal surface from the solution—the rate-controlling stage for the molecular step growth, i.e., COM crystal growth—and then diffuse over it and are eventually incorporated into the steps. This primary pathway of the ions is unaffected by the model peptide D-Asp6 adsorbed on the COM crystal surface, suggesting that urinary biomolecules will not alter the pathway. These new findings rendering an essential understanding of the fundamental growth mechanism of COM crystal at the nanoscale provide crucial insights beneficial to the development of effective therapeutics for COM kidney stones.

59 BASIC BIOLOGICAL SCIENCES↗

Truncated Nonlinear Interferometry for Quantum-Enhanced Atomic Force Microscopy

Nonlinear interferometers that replace beam splitters in Mach-Zehnder interferometers with nonlinear amplifiers for quantum-enhanced phase measurements have drawn increasing interest in recent years, but practical quantum sensors based on nonlinear interferometry remain an outstanding challenge. Here, we demonstrate the first practical application of nonlinear interferometry by measuring the displacement of an atomic force microscope microcantilever with quantum noise reduction of up to 3 dB below the standard quantum limit, corresponding to a quantum-enhanced measurement of beam displacement of 1.7 fm/√Hz. Further, we minimize photon backaction noise while taking advantage of quantum noise reduction by transducing the cantilever displacement signal with a weak squeezed state while using dual homodyne detection with a higher power local oscillator. This approach may enable quantum-enhanced broadband, high-speed scanning probe microscopy.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Atomic Force Microscopy and Infrared Nanospectroscopy of COVID-19 Spike Protein for the Quantification of Adhesion to Common Surfaces

The COVID-19 pandemic has claimed millions of lives worldwide, sickened many more, and has resulted in severe socio-economic consequences. As society returns to normal, understanding the spread and persistence of SARS CoV-2 on commonplace surfaces can help to mitigate future outbreaks of coronaviruses and other pathogens. We hypothesize that such an understanding can be aided from studying the binding and interaction of viral proteins with non-biological surfaces. Here, we propose a methodology for investigating the adhesion of the SARS CoV-2 spike glycoprotein on common inorganic surfaces such as aluminum-, copper-, iron-, silica-, and ceria-oxides as well as metallic gold. Quantitative adhesion was obtained from the analysis of measured forces at the nanoscale using an atomic force microscope operated under ambient conditions. Without imposing further constraints on the measurement conditions, our preliminary findings suggest that spike glycoproteins interact with similar adhesion forces across the majority of the metal oxides tested with the exception to gold, for which attraction forces ~10 times stronger than all other materials studied were observed. Ferritin, which was used as a reference protein, was found to exhibit similar adhesion forces as SARS CoV-2 spike protein. Further, this study results show that glycoprotein adhesion forces for similar ambient humidity, tip shape, and contact surface are non-specific to the properties of metal oxide surfaces, which are expected to be covered by a thin water film. The findings suggest that at ambient conditions glycoprotein adhesion to metal oxides is primarily controlled by the water capillary forces and they depend on the surface tension of the liquid (water). We discuss further strategies warranted to decipher the intricate nanoscale forces for improved quantification of the adhesion.

59 BASIC BIOLOGICAL SCIENCES↗

Exploring Domain-Wall Pinning in Ferroelectrics via Automated High-Throughput Atomic Force Microscopy

Domain-wall dynamics in ferroelectric materials are strongly position-dependent, since each polar interface is locked into a unique local microstructure. This necessitates spatially resolved studies of wall pinning using scanning-probe microscopy techniques. The pinning centers and pre-existing domain walls are usually sparse within the image plane, precluding the use of dense hyperspectral imaging modes and requiring time-consuming human experimentation. Here, a large-area epitaxial PbTiO 3 film on cubic KTaO 3 was investigated to quantify the electric-field-driven dynamics of the polar–strain domain structures using ML-controlled automated piezoresponse force microscopy. Analysis of 1500 switching events reveals that domain-wall displacement depends not only on field parameters but also on the local ferroelectric–ferroelastic configuration. For example, twin boundaries in polydomains regions, like a 1 – /c+ ∥ a 2 – /c – , stay pinned up to a certain level of bias magnitude and change only marginally as the bias increases from 20 to 30 V, whereas single-variant boundaries, like the a 2 + /c + ∥ a 2 – /c – stack, are already activated at 20 V. These statistics on the possible ferroelectric and ferroelastic wall orientations, together with the automated high-throughput AFM workflow, can be distilled into a predictive map that links domain configurations to pulse parameters. Here, this microstructure-specific rule set forms the foundation for the design of ferroelectric memories.

automated scanning probe microscopy↗