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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 109 records · Page 6

Direct quantification of ion composition and mobility in organic mixed ionic-electronic conductors

Ion transport in organic mixed ionic-electronic conductors (OMIECs) is crucial due to its direct impact on device response time and operating mechanisms but is often assessed indirectly or necessitates extra assumptions. Operando x-ray fluorescence (XRF) is a powerful, direct probe for elemental characterization of bulk OMIECs and was used to directly quantify ion composition and mobility in a model OMIEC, poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS), during device operation. The first cycle revealed slow electrowetting and cation-proton exchange. Subsequent cycles showed rapid response with minor cation fluctuation (~5%). Comparison with optical-tracked electrochromic fronts revealed mesoscale structure–dependent proton transport. The calculated effective ion mobility demonstrated thickness-dependent behavior, emphasizing an interfacial ion transport pathway with a higher mobile ion density. The decoupling of interfacial effects on bulk ion mobility and the decoupling of cation and proton migration elucidate ion transport in conventional and emerging OMIEC-based devices and has broader implications for other ionic conductors writ large.

42 ENGINEERING↗

Resolution-enhanced X-ray fluorescence microscopy via deep residual networks

Abstract Multimodal hard X-ray scanning probe microscopy has been extensively used to study functional materials providing multiple contrast mechanisms. For instance, combining ptychography with X-ray fluorescence (XRF) microscopy reveals structural and chemical properties simultaneously. While ptychography can achieve diffraction-limited spatial resolution, the resolution of XRF is limited by the X-ray probe size. Here, we develop a machine learning (ML) model to overcome this problem by decoupling the impact of the X-ray probe from the XRF signal. The enhanced spatial resolution was observed for both simulated and experimental XRF data, showing superior performance over the state-of-the-art scanning XRF method with different nano-sized X-ray probes. Enhanced spatial resolutions were also observed for the accompanying XRF tomography reconstructions. Using this probe profile deconvolution with the proposed ML solution to enhance the spatial resolution of XRF microscopy will be broadly applicable across both functional materials and biological imaging with XRF and other related application areas.

36 MATERIALS SCIENCE↗

A multi-material platform for imaging of single cell-cell junctions under tensile load fabricated with two-photon polymerization

We previously reported a single-cell adhesion micro tensile tester (SCAμTT) fabricated from IP-S photoresin with two-photon polymerization (TPP) for investigating the mechanics of a single cell-cell junction under defined tensile loading. A major limitation of the platform is the autofluorescence of IP-S, the photoresin for TPP fabrication, which significantly increases background signal and makes fluorescent imaging of stretched cells difficult. In this study, we report the design and fabrication of a new SCAμTT platform that mitigates autofluorescence and demonstrate its capability in imaging a single cell pair as its mutual junction is stretched. By employing a two-material design using IP-S and IP-Visio, a photoresin with reduced autofluorescence, we show a significant reduction in autofluorescence of the platform. Further, by integrating apertures onto the substrate with a gold coating, the influence of autofluorescence on imaging is almost completely mitigated. With this new platform, we demonstrate the ability to image a pair of epithelial cells as they are stretched up to 250% strain, allowing us to observe junction rupture and F-actin retraction while simultaneously recording the accumulation of over 800 kPa of stress in the junction. In conclusion, the platform and methodology presented here can potentially enable detailed investigation of the mechanics of and mechanotransduction in cell-cell junctions and improve the design of other TPP platforms in mechanobiology applications.

Autofluorescence↗

Peptoid-Based Programmable 2D Nanomaterial Sensor for Selective and Sensitive Detection of H 2 S in Live Cells

During the past decades, a variety of two-dimensional (2D) nanosheets have been developed through supramolecular self-assembly. Among them, those assembled from sequence-defined molecules have received particularly attention because they enable a precise displaying of functional groups, including fluorescent dyes, within nanosheet surfaces. On the other hand, due to the fluorescence self-quenching, synthesis of organic 2D nanosheets exhibiting high fluorescence quantum yields is a significant challenge. Herein, we report the utilization of H 2 S-responsive probes as peptoid sidechains to design and synthesize crystalline 2D nanomembranes (2DNMs) as selective and sensitive H 2 S sensors. These 2DNM sensors exhibit a high quantum yield as a result of high crystallinity and tunable probe density. Compared with amorphous state of peptoid assembly and pre-assembled peptoid-probe conjugates, these crystalline 2DNM sensors exhibit a significantly strong fluorescence intensity and a high sensitivity (~ 0.36 nM). By sonication-cutting these 2DNM sensors into a colloidal form in aqueous solution, we further demonstrated the use of colloidal 2DNMs for detecting both exogenous and endogenous H 2 S inside cells or targeted cell organelles. As far as we know, this is the first example of using sequence-defined 2D nanomaterials for selective and sensitive detection of H 2 S. Because peptoids are biocompatible and peptoid-based 2DNMs are highly programmable, we expect that this new class of 2DNM sensors offer great potentials for detecting H 2 S and for biological applications.

2D nanomaterials↗

Optical diagnostics of laser-produced plasmas

Laser-produced plasmas (LPPs) engulf exotic and complex conditions ranging in temperature, density, pressure, magnetic and electric fields, charge states, charged particle kinetics, and gas-phase reactions, based on the irradiation conditions, target geometries, and the background cover gas. The application potential of the LPP is so diverse that it generates considerable interest for both basic and applied research areas. The fundamental research on LPPs can be traced back to the early 1960s, immediately after the invention of the laser. In the 1970s, the laser was identified as a tool to pursue inertial confinement fusion, and since then, several other technologies emerged out of LPPs. These applications prompted the development and adaptation of innovative diagnostic tools for understanding the fundamental nature and spatiotemporal properties of these complex systems. Although most of the traditional characterization techniques developed for other plasma sources can be used to characterize the LPPs, care must be taken to interpret the results because of their small size, transient nature, and inhomogeneities. The existence of the large spatiotemporal density and temperature gradients often necessitates non-uniform weighted averaging over distance and time. Among the various plasma characterization tools, optical-based diagnostic tools play a key role in the accurate measurements of LPP parameters. The optical toolbox contains optical spectroscopy (emission, absorption, and fluorescence), passive and active imaging and optical probing methods (shadowgraphy, Schlieren, interferometry, Thomson scattering, deflectometry, and velocimetry). Each technique is useful for measuring a specific property, and its use is limited to a certain time span during the LPP evolution because of the sensitivity issues related to the selected measuring tool. Therefore, multiple diagnostic tools are essential for a comprehensive insight into the entire plasma behavior. In recent times, the improvements in performance in the lasers and detector systems expanded the capability of the aforementioned passive and active diagnostics tools. Furthermore, this review provides an overview of optical diagnostic tools frequently employed for the characterization of the LPPs and emphasizes techniques, associated assumptions, and challenges. Considering most of the industrial and other applications of the LPP belong to low to moderate laser intensities (10 8 – 10 15 Wcm –2 ), this review focuses on diagnostic tools pertaining to this regime.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Microstructural and chemical characterization of a purple pigment from a Faiyum mummy portrait

Results are presented from analyses that were conducted to explain the presence of chromium, detected noninvasively using energy dispersive X-ray fluorescence (XRF), in the unusually large (2-3mm diameter) rough gem-like purple pigment particles in the paint used for a Faiyum mummy portrait. An approximately 50 µm diameter particle of the chromium-containing purple pigment was extracted from the Portrait of a Bearded Man, dated to Roman Imperial Egypt in the second century, circa 170-180 CE, accession #32.6 in the Walters Art Museum collection. The particle was characterized using energy dispersive X-ray fluorescence analysis, electron microscopy, diffraction, and atom probe tomography. It is demonstrated that the purple pigment particle is a heterogeneous organic pigment, specifically, a lake pigment likely derived from either plant or insect matter, which contains minor percentages of both transition metals and alkali / alkali earth metals, with nanometer-scale crystallites of lead carbonates and sulfates. The analyses revealed for the first time the nanoscale microstructure and stratigraphy in an ancient lake pigment. Results suggest that similarities with respect to time-period and place of production may be developed among unprovenienced Faiyum mummy portraits to help localize workshops or artists, using analyses focused on lake pigments to characterize specifically metal-based mordants.

36 MATERIALS SCIENCE↗

Spectroscopic investigation of cation effects in U(VI)-NO3- complexation in aqueous solutions

Understanding and manipulating uranyl speciation in aqueous solutions is critical for advancing chemical separation, sensing, and understanding environmental transport of uranyl. We report on the significant enhancement in the complexation of uranyl with nitrate in aqueous solutions containing quaternary ammonium cations leading to the formation of anionic complexes. We base this on the comparative study of the effect of monovalent cations (Na+, Li+, NH4+, and N(CH3)4+) on the complexation equilibria of uranyl-nitrate in solutions, probed by time-resolved laser induced fluorescence spectroscopy (TRLFS). Lifetime-corrected spectra, obtained by extrapolating the time-resolved spectra to t = 0, were used to study speciation to mitigate the effects of variations in the fluorescence lifetimes that depend on extraneous factors such as dynamic quenching. We demonstrate that the lifetime-corrected spectra can be used to determine uranyl speciation in aqueous solutions where the mono-nitrate complex forms, and in acetonitrile with N(CH3)4NO3 where di-nitrate and tris-nitrato species are formed. Aqueous solutions containing N(CH3)4+ are shown to promote the formation of higher complexes of uranyl compared to other inorganic nitrate salts based on the higher redshift in the spectra, poor fits to the two-component model, and the higher apparent formation constants. Comparing the trends in uranyl speciation in the presence of N(CH3)4+ in aqueous and acetonitrile solutions, it is proposed that the quaternary ammonium cations (quats) promote the formation of anionic complexes of uranyl by the ion-association mechanism. These results provide a basis for designing quat-assisted separation systems that target anionic actinide species in aqueous solutions.

Nayak, Srikanth (ORCID:0000000302135796)↗

Probe-Enabled Approaches for Function-Dependent Cell Sorting and Characterization of Microbiome Subpopulations

Understanding the roles that individual species or communities play within a microbiome is a significant challenge. The complexity and heterogeneity of microbiomes presents a challenge to researchers looking to unravel the function that microbiomes serve within larger environments. While identification of the species and proteins present in a microbiome can be accomplished through genomics approaches, strategies that report on enzyme activity are limited. In this chapter, we describe the application of small molecule chemical probes in the isolation and subsequent characterization of microbiome subpopulations based on enzymatic function. We will cover protocols for labeling microbes with appropriate probes, microbiome sample preparation, and using fluorescence-activated cell sorting to isolate subpopulations based on function. We hope that the strategies outlined here will serve as a resource for researchers studying the functional role that microbiomes play in the gut and soil.

Steiger, Andrea K.↗

Protein Spherical Nucleic Acids for Live-Cell Chemical Analysis

We report the development of a new strategy for the chemical analysis of live cells based on protein spherical nucleic acids (ProSNAs). The ProSNA architecture enables analyte detection via the highly programmable nucleic acid shell or a functional protein core. As a proof-of-concept, we use an i-motif as the nucleic acid recognition element to probe pH in living cells. By interfacing the i-motif with a forced-intercalation readout, we introduce a quencher-free approach that is resistant to false-positive signals, overcoming limitations associated with conventional fluorophore/quencher-based gold NanoFlares. Using glucose oxidase as a functional protein core, we show activity-based, amplified sensing of glucose. This enzymatic system affords greater than 100-fold fluorescence turn on in buffer, is selective for glucose in the presence of close analogs (i.e., glucose-6-phosphate), and can detect glucose above a threshold concentration of ~5 μM, which enables the study of relative changes in intracellular glucose concentrations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reversible Reactions, Mesh Size, and Segmental Dynamics Control Penetrant Diffusion in Ethylene Vitrimers

The diffusion of two aromatic dyes with nearly identical sizes was measured in ethylene vitrimers with precise linker lengths and borate ester cross-links using fluorescence recovery after photobleaching (FRAP). One dye possessed a reactive hydroxyl group, while the second was inert. The reaction of the hydroxyl group with the network is slow relative to the hopping times of the dye, resulting in a large slowdown by a factor of 50 for a reactive probe molecule. A kinetic model was fit to the fluorescence intensity data to determine rate constants for the reversible reaction of the dye from the network, which confirms the role of slow reaction kinetics. A second network cross-linker was also investigated with a substituted boronic ester showing ∼10,000 times faster exchange kinetics. In this system, the two dyes show the same diffusion coefficient, as the reaction is no longer the rate-limiting step. The role of dense meshes on small and large dyes is also discussed in the context of the existing theories. Finally, these results highlight the potential of dynamic networks to control penetrant transport through synergistic effects of the mesh size, dynamic bond kinetics, and penetrant–network interactions.

confinement↗

Characterizing leaf-scale fluorescence with spectral invariants

Sun-induced chlorophyll fluorescence (SIF) is increasingly recognized as a non-destructive probe for tracking terrestrial photosynthesis. Emerging developments in spectral invariants theory provide an innovative and efficient approach for representing SIF radiative transfer processes at the canopy scale. However, modeling leaf-scale fluorescence based on the spectral invariants properties (SIP) remains underexplored. In this study, the spectral invariants theory is employed for the first time to model the leaf-scale total, backward and forward fluorescence (leaf-SIP SIF). The leaf-SIP SIF model separates the leaf-scale radiative transfer process into two distinct components: the wavelength-dependent one associated with leaf biochemical properties, and the wavelength-independent component linked to leaf structural characteristics. The leaf structure-related effects are characterized by two spectrally invariant parameters: the photon recollision probability (p) and the scattering asymmetry parameter (q), which are parameterized using the directly measurable leaf dry matter. Evaluation against field measurements shows that the proposed leaf-SIP SIF model has a good performance, with coefficient of determination (R 2 ) of 0.89, 0.89, 0.90 and root mean squared errors (RMSE) of 1.28, 0.69, 0.74 Wm -2 µm -1 sr -1 , respectively for the total, backward, and forward fluorescence (660–800 nm). The leaf-SIP SIF model with a more concise formulation demonstrates comparable performance with the widely used Fluspect model. Further, the leaf-SIP SIF model provides a simple and efficient approach for simulating leaf-scale fluorescence, with the potential to be integrated into a unified SIP-based model framework for simulating the radiative transfer processes across the soil-leaf-canopy-atmosphere continuum.

59 BASIC BIOLOGICAL SCIENCES↗

Energy shift of Fe-K fluorescence lines due to low ionization demonstrated with XRISM in Centaurus X-3

The Fe K$\alpha$ fluorescence line at 6.4 keV is a powerful probe of cold matter surrounding X-ray sources and has been widely used in various astrophysical contexts. The X-ray microcalorimeter spectrometer onboard XRISM can measure line shifts with unprecedented precision of ${\sim }$0.2 eV, equivalent to a line-of-sight velocity of ${\sim }$10 km s$^{-1}$. At this level of accuracy, however, several factors that influence the line energy must be carefully considered prior to astrophysical interpretation. One such important factor is the ionization degree, Fe$^{q+}$. The K$\alpha$ line shifts redward by ${\sim }$4 eV as q increases from 0 (neutral) to 8 (Ar-like). Additionally, the accompanying Fe K$\beta$ line at 7.06 keV shifts blueward by ${\sim }$30 eV from $q=0$ to 8. We demonstrate that this effect is actually observable in the XRISM data of the high-mass X-ray binary Centaurus X-3 (Cen X-3). We advocate that the differential energy shift between the K$\alpha$ and K$\beta$ line provides a robust estimate of q by decoupling from other effects that shift the two lines in the same direction. We derived $q \sim 5$ (Sc-like) for the fluorescing matter by comparing the observation with atomic structure calculations of our own and in the literature. By accounting for the derived charge state and the corresponding shift in the rest-frame line energy, we made corrections for this effect and reached a consistent residual shift among the K$\alpha$, K$\beta$, and the optical measurement attributable to the systemic velocity of the system. Consequently, we obtained a new constraint on the location of the cold matter. This ionization effect needs to be assessed in all use cases of the Fe K$\alpha$ line shift beyond Cen X-3, and the proposed metric is generally applicable to all of them.

Astronomy and AstroPhysics↗

Wavelength modulation laser-induced fluorescence for plasma characterization

Laser-Induced Fluorescence (LIF) spectroscopy is an essential tool for probing ion and atom velocity distribution functions (VDFs) in complex plasmas. VDFs carry information about the kinetic properties of species that is critical for plasma characterization. Accurate interpretation of these functions is challenging due to factors such as multicomponent distributions, broadening effects, and background emissions. Our research investigates the use of Wavelength Modulation (WM) LIF to enhance the sensitivity of VDF measurements. Unlike standard Amplitude Modulation (AM) methods, WM–LIF measures the derivative of the LIF signal. This approach makes variations in VDF shape more pronounced. VDF measurements with WM–LIF were investigated with both numerical modeling and experimental measurements. The developed model enables the generation of both WM and AM signals, facilitating comparative analysis of fitting outcomes. Experiments were conducted in a weakly collisional argon plasma with magnetized electrons and non-magnetized ions. Measurements of the argon ion VDFs employed a narrow-band tunable diode laser, which scanned the 4p 4 D 7/2 –3d 4 F 9/2 transition centered at 664.553 nm in vacuum. A lock-in amplifier detected the second harmonic WM signal, which was generated by modulating the laser wavelength with an externally controlled piezo-driven mirror of the diode laser. Finally, our findings indicate that the WM–LIF signal is more sensitive to fitting parameters, allowing for better identification of VDF parameters such as the number of distribution components, their temperatures, and velocities. In addition, WM–LIF can serve as an independent method to verify AM measurements and is particularly beneficial in environments with substantial light noise or background emissions, such as those involving thermionic cathodes and reflective surfaces.

47 OTHER INSTRUMENTATION↗

Non-Blind Deblurring for Fluorescence: A Deformable Latent Space Approach with Kernel Parameterization

We report N\non-blind deblurring (NBD) is a modeling method of the image deblurring problem in computer vision, where the blurring kernel is known or can be externally estimated. In this paper, we attempt to solve a parametric NBD problem, inspired by the simultaneous acquisition of ptychography and fluorescent imaging (FI). Ptychography is an imaging method that favors larger probes, i.e. convolutional kernels, while FI relies on a small probe for high resolution. Also, the kernel can be solved during ptychographic reconstruction. With Ptycho-FI using the same larger kernel, we can perform NBD on the blurred fluorescent images to achieve high-resolution FI, and thus speed up the experiments. To this end, we design a deep latent space deformation network that is directly parameterized by the kernel. The network consists of three components: encoder, deformer, and decoder, where the deformer is specifically meant to rectify the latent space representations of blurred images to a standard latent space, regardless of the kernel. The deformation network is trained with a two-stage training scheme. We conduct extensive experiments to confirm that our parametric model can adapt to drastically different blurring kernels and perform robust deblurring.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Impact of Electrolyte Additives on the Lifetime of High Voltage NMC Lithium-Ion Pouch Cells

This work involves improving the lifetime of lithium-ion cells during high voltage cycling using electrolyte additives. Three generations of electrolyte additives were investigated and screened in NMC442/graphite pouch cells using a 24 h voltage-hold protocol at 40 degrees C to accelerate oxidative reactions occurring at 4.4 V. Once promising additives and combinations were identified, they were then tested in cobalt-free NMC640/graphite cells for long-term cycling to upper cutoff voltages of 4.3, 4.4, and 4.5 V at temperatures of 20, 40, and 55 degrees C. Degradation mechanisms were probed using dV/dQ analysis, micro-X-ray fluorescence spectroscopy, and electrochemical impedance spectroscopy. The primary failure mode of cells held at high voltages is due to increase in cell impedance, which is correlated to the dissolution of transition metals, specifically manganese, originating from the positive electrode. We believe this dissolution is presumably due to the formation of a high impedance rock salt surface layer on the NMC positive electrode particles. Such deleterious outcomes can be limited by selecting an appropriate electrolyte additive package. It is hoped that this paper can provide a starting point for developing NMC Li-ion cells that can operate to voltages as high as 4.4 V and still display long lifetimes.

Azam, Saad↗

Multicellular magnetotactic bacteria are genetically heterogeneous consortia with metabolically differentiated cells

Consortia of multicellular magnetotactic bacteria (MMB) are currently the only known example of bacteria without a unicellular stage in their life cycle. Because of their recalcitrance to cultivation, most previous studies of MMB have been limited to microscopic observations. To study the biology of these unique organisms in more detail, we use multiple culture-independent approaches to analyze the genomics and physiology of MMB consortia at single-cell resolution. We separately sequenced the metagenomes of 22 individual MMB consortia, representing 8 new species, and quantified the genetic diversity within each MMB consortium. This revealed that, counter to conventional views, cells within MMB consortia are not clonal. Single consortia metagenomes were then used to reconstruct the species-specific metabolic potential and infer the physiological capabilities of MMB. To validate genomic predictions, we performed stable isotope probing (SIP) experiments and interrogated MMB consortia using fluorescence in situ hybridization (FISH) combined with nanoscale secondary ion mass spectrometry (NanoSIMS). By coupling FISH with bioorthogonal noncanonical amino acid tagging (BONCAT), we explored their in situ activity as well as variation of protein synthesis within cells. We demonstrate that MMB consortia are mixotrophic sulfate reducers and that they exhibit metabolic differentiation between individual cells, suggesting that MMB consortia are more complex than previously thought. These findings expand our understanding of MMB diversity, ecology, genomics, and physiology, as well as offer insights into the mechanisms underpinning the multicellular nature of their unique lifestyle.

59 BASIC BIOLOGICAL SCIENCES↗

Engineering spin coherence in core-shell diamond nanocrystals

Fluorescent diamond nanocrystals can host spin qubit sensors capable of probing the physical properties of biological systems with nanoscale spatial resolution. Sub-100 nm diamond nanosensors can readily be delivered into intact cells and even living organisms. However, applications beyond current proof-of-principle experiments require a substantial increase in sensitivity, which is limited by surface induced charge instability and electron-spin dephasing. In this work, we utilize engineered core-shell structures to achieve a drastic increase in qubit coherence times (T 2 ) from 1.1 to 35 μs in bare nanodiamonds to upward of 52 to 87 μs. We use electron-paramagnetic-resonance results to present a band bending model and connect silica encapsulation to the removal of deleterious mid-gap surface states that are negatively affecting the qubit’s spin properties. Combined with a 1.9-fold increase in particle luminescence these advances correspond to up to two-order-of-magnitude reduction in integration time. Probing qubit dynamics at a single particle level further reveals that the noise characteristics fundamentally change from a bath with spins that rearrange their spatial configuration during the course of an experiment to a more dilute static bath. The observed results shed light on the underlying mechanisms governing fluorescence and spin properties in diamond nanocrystals and offer an effective noise mitigation strategy based on engineered core-shell structures.

core-shell↗

Hyperdimensional Imaging Contrast Using an Optical Fiber

Fluorescence properties of a molecule can be used to study the structural and functional nature of biological processes. Physical properties, including fluorescence lifetime, emission spectrum, emission polarization, and others, help researchers probe a molecule, produce desired effects, and infer causes and consequences. Correlative imaging techniques such as hyperdimensional imaging microscopy (HDIM) combine the physical properties and biochemical states of a fluorophore. Here we present a fiber-based imaging system that can generate hyper-dimensional contrast by combining multiple fluorescence properties into a single fluorescence lifetime decay curve. Fluorescence lifetime imaging microscopy (FLIM) with controlled excitation polarization and temporally dispersed emission can generate a spectrally coded, polarization-filtered lifetime distribution for a pixel. This HDIM scheme generates a better contrast between different molecules than that from individual techniques. This setup uses only a single detector and is simpler to implement, modular, cost-efficient, and adaptable to any existing FLIM microscope. We present higher contrast data from Arabidopsis thaliana epidermal cells based on intrinsic anthocyanin emission properties under multiphoton excitation. This work lays the foundation for an alternative hyperdimensional imaging system and demonstrates that contrast-based imaging is useful to study cellular heterogeneity in biological samples.

47 OTHER INSTRUMENTATION↗