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At least 487 records · Page 27

In situ molecular imaging of adsorbed protein films in water indicating hydrophobicity and hydrophilicity

Abstract In situ molecular imaging of protein films adsorbed on a solid surface in water was realized by using a vacuum compatible microfluidic interface and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Amino acid fragments from such hydrated protein films are observed and identified in the positive ion mode and the results are in agreement with reported works on dry protein films. Moreover, water clusters from the hydrated protein films have been observed and identified in both the positive and negative ion mode for a series protein films. Thus, the detailed composition of amino acids and water molecules in the hydrated protein films can be characterized, and the protein water microstructures can be revealed by the distinct three-dimensional spatial distribution reconstructed from in situ liquid ToF-SIMS molecular imaging. Furthermore, spectral principal component analysis of amino acid fragment peaks and water cluster peaks provides unique insights into the water cluster distribution, hydrophilicity, and hydrophobicity of hydrated adsorbed protein films in water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unsupervised learning-enabled pulsed infrared thermographic microscopy of subsurface defects in stainless steel

Metallic structures produced with laser powder bed fusion (LPBF) additive manufacturing method (AM) frequently contain microscopic porosity defects, with typical approximate size distribution from one to 100 microns. Presence of such defects could lead to premature failure of the structure. In principle, structural integrity assessment of LPBF metals can be accomplished with nondestructive evaluation (NDE). Pulsed infrared thermography (PIT) is a non-contact, one-sided NDE method that allows for imaging of internal defects in arbitrary size and shape metallic structures using heat transfer. PIT imaging is performed using compact instrumentation consisting of a flash lamp for deposition of a heat pulse, and a fast frame infrared (IR) camera for measuring surface temperature transients. However, limitations of imaging resolution with PIT include blurring due to heat diffusion, sensitivity limit of the IR camera. We demonstrate enhancement of PIT imaging capability with unsupervised learning (UL), which enables PIT microscopy of subsurface defects in high strength corrosion resistant stainless steel 316 alloy. PIT images were processed with UL spatial–temporal separation-based clustering segmentation (STSCS) algorithm, refined by morphology image processing methods to enhance visibility of defects. The STSCS algorithm starts with wavelet decomposition to spatially de-noise thermograms, followed by UL principal component analysis (PCA), fine-tuning optimization, and neural learning-based independent component analysis (ICA) algorithms to temporally compress de-noised thermograms. The compressed thermograms were further processed with UL-based graph thresholding K-means clustering algorithm for defects segmentation. The STSCS algorithm also includes online learning feature for efficient re-training of the model with new data. For this study, metallic specimens with calibrated microscopic flat bottom hole defects, with diameters in the range from 203 to 76 µm, were produced using electro discharge machining (EDM) drilling. While the raw thermograms do not show any material defects, using STSCS algorithm to process PIT images reveals defects as small as 101 µm in diameter. To the best of our knowledge, this is the smallest reported size of a sub-surface defect in a metal imaged with PIT, which demonstrates the PIT capability of detecting defects in the size range relevant to quality control requirements of LPBF-printed high-strength metals.

36 MATERIALS SCIENCE↗

Reductive catalytic fractionation of agricultural residue and energy crop lignin and application of lignin oil as antimicrobials

Cheap and abundant waste from bioethanol and agricultural processing industries are an alluring alternative feedstock for biorefineries. In this work, we employ reductive catalytic fractionation (RCF) to depolymerize, over Ru/C powder and Ru/Al 2 O 3 pellets, five herbaceous biomass feedstocks, namely corn stover, miscanthus, switchgrass, sugarcane bagasse, and wheat straw into phenolic monomers with high yields (~40 wt.% based on total (Klason + acid soluble) lignin and > 50 wt.% when stabilized using aldehydes), leaving behind a carbohydrate pulp residue. Interestingly, a polar solvent is sufficient to solubilize and fragment the lignin polymer into monomers without any catalyst. Here, contrary to woody biomass, where the monomer yields are positively correlated with the S-content of lignin, principal component analysis indicates that the monomer yields from herbaceous biomass depend on the content of lignin crosslinker – ferulate. Using NMR, we further identify α – 6 C-C linked oligomers formed from condensation reactions, explaining the unexpected low monomer yields of high β-O-4 herbaceous biomass. Recyclability experiments indicate that catalyst deactivation occurs through sintering, leaching, and fouling. Lignin oil from herbaceous biomass exhibits bacteriostatic effects against Staphylococcus aureus, highlighting a potential application in functional food development and as food or feed preservative.

09 BIOMASS FUELS↗

Comparison of machine learning techniques to optimize the analysis of plutonium surrogate material via a portable LIBS device

The utilization of machine learning techniques has become commonplace in the analysis of optical emission spectra. These methods are often limited to variants of principal components analysis (PCA), partial-least squares (PLS), and artificial neural networks (ANNs). A plethora of other techniques exist and are well established in the world of data science, yet are seldom investigated for their use in spectroscopic problems. In this study, machine learning techniques were used to analyze optical emission spectra of laser-induced plasma from ceria pellets doped with silicon in order to predict silicon content. Additionally, a boosted regression ensemble model was created, and its predictive accuracy was compared to that of traditional PCA, PLS, and ANN regression models. Boosted regression tree ensembles yielded fits with R-squared (R2) values as high as 0.964 and mean-squared errors of prediction (MSEPs) as low as 0.074, providing the most accurate predictive model. Neural networks performed with slightly lower R2 values and higher MSEPs compared to the ensemble methods, thus indicating susceptibility to overfitting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Combined Plasmonic Au-nanoparticle and Conducting Metal Oxide High-temperature Optical Sensing with LSTO

<span style="color: rgba(0, 0, 0, 0.79); font-family: &quot;Source Sans Pro&quot;, source-sans-pro, museo_sans300, museo-sans, Arial, sans-serif; font-size: 16px; background-color: rgb(255, 255, 255);">Fiber optic sensor technology offers several advantages for harsh-environment applications. However, the development of optical gas sensing layers that are stable under harsh environmental conditions is an ongoing research challenge. In this work, electronically conducting metal oxide lanthanum-doped strontium titanate (LSTO) films embedded with gold nanoparticles are examined as a sensing layer for application in reducing gas flows at high temperature (600–800 °C). A strong localized surface plasmon resonance (LSPR) based response to hydrogen is demonstrated in the visible region of the spectrum, while a Drude free electron-based response is observed in the near-IR. Characteristics of these responses are studied both on planar glass substrates and on silica fibers. Charge transfer between the oxide film and the gold nanoparticles is explored as a possible mechanism governing the Au LSPR response and is considered in terms of the corresponding properties of the conducting metal oxide-based matrix phase. Principal component analysis is applied to the combined plasmonic and free-carrier based response over a range of temperatures and hydrogen concentrations. It is demonstrated that the combined visible and near-IR response of these films provides improved versatility for multiwavelength interrogation, as well as improved discrimination of important process parameters (concentration and temperature) through application of multivariate analysis techniques.</span>

Wuenschell, Jeffrey K.↗

Active Learning-driven Quantitative Synthesis-Structure-Property Relations for Improving Performance and Revealing Active Sites of Nitrogen-Doped Carbon for the Hydrogen Evolution Reaction

While quantitative structure-properties relations (QSPRs) have been developed successfully in multiple fields, catalyst synthesis affects structure and in turn performance, making simple QSPRs inadequate. Furthermore, catalysts often have multiple active sites preventing one from obtaining insights into structure-property relations. Here, we develop a data-driven quantitative synthesis-structure-property relation (QS2PRs) methodology to elucidate correlations between catalyst synthesis conditions, structural properties as well as observed performance and to provide fundamental insights into active sites and a systematic way to optimize practical catalysts. Here, we demonstrate the approach to the synthesis of nitrogen-doped catalysts (NDC) made via pyrolysis for the performance of the electrochemical hydrogen evolution reaction (HER), quantified by the onset potential and the current density. We determine crystallinity, nitrogen species type and fraction, surface area, and pore structure of the NDC’s using XRD, XPS, and BET characterization. We demonstrated that an active learning-based optimization combined with various elementary machine learning tools (regression, principal component analysis, partial least squares) can efficiently identify optimum pyrolysis conditions to tune structural characteristics and performance with concomitant savings in materials and experimental time. Unlike previous reports on the importance of pyridinic or graphitic nitrogen, we discover that the electrochemical performance is not driven by a single catalyst property; rather, it arises from a multivariate influence of nitrogen dopants, pore structure and disorder in the NDC materials. Identification of active sites can help mechanistic understanding and further catalyst improvement.

42 ENGINEERING↗

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 with-in plant tissues, however the mechanism(s) by which plants associate with PGPR to elicit such beneficial effects needs further study. Here, we present high mass resolution 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::GFP (P.) and Gram-positive Arthrobacter chlorophenolicus A6::GFP (A.). Delayed image extraction was used to image PGPB-treated seed sections to reveal morphological changes. ToF-SIMS spectral compari-son, 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 prod-ucts and biomarkers, such as flavonoids, phenolic com-pounds, fatty acids, and indole-3-acetic acid (IAA), were ob-served on the PGPR-treated seed surfaces. These compounds had different distributions on the Brachypodium seed surface for the two PGPR, indicating that the different bacteria elicited distinct responses from the host. Our results illustrate that ToF-SIMS is an effective tool to study plant-microbe interac-tions and to provide insightful information with submicrome-ter lateral resolution of the chemical distributions associated with morphological features, potentially offering a new way to study the mechanisms underlying beneficial roles of PGPR.

PGPR, Brachypodium distachyon, ToF-SIMS, metabolit↗

Rapid quantitative analysis of trace elements in plutonium alloys using a handheld laser-induced breakdown spectroscopy (LIBS) device coupled with chemometrics and machine learning

Here, we present the first reported quantification of trace elements in plutonium via a portable laser-induced breakdown spectroscopy (LIBS) device and demonstrate the use of chemometric analysis to enhance the handheld device's sensitivity and precision. Quantification of trace elements such as iron and nickel in plutonium metal via LIBS is a challenging problem due to the complex nature of the plutonium optical emission spectra. While rapid analysis of plutonium alloys has been demonstrated using portable LIBS devices, such as the SciAps Z300, their detection limits for trace elements are severely constrained by their achievable pulse power and length, light collection optics, and detectors. In this paper, analytical methods are evaluated as a means to circumvent the detection constraints. Three chemometric methods often used in analytical spectroscopy are evaluated; principal component regression, partial least-squares regression, and artificial neural networks. These models are evaluated based on goodness-of-fit metrics, root mean-squared error, and their achievable limits of detection (LoDs). Partial least squares proved superior for determining content of iron and nickel in plutonium metal, yielding LoDs of 15 and 20 ppm, respectively. These results of identifying the undesirable trace elements in plutonium components are critical for applications such as fabricating radioisotope thermoelectric generators or nuclear fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Unsupervised machine learning for unbiased chemical classification in X-ray absorption spectroscopy and X-ray emission spectroscopy

Here we report a comprehensive computational study of unsupervised machine learning for extraction of chemically relevant information in X-ray absorption near edge structure (XANES) and in valence-to-core X-ray emission spectra (VtC-XES) for classification of a broad ensemble of sulphorganic molecules. By progressively decreasing the constraining assumptions of the unsupervised machine learning algorithm, moving from principal component analysis (PCA) to a variational autoencoder (VAE) to t-distributed stochastic neighbour embedding (t-SNE), we find improved sensitivity to steadily more refined chemical information. Surprisingly, when embedding the ensemble of spectra in merely two dimensions, t-SNE distinguishes not just oxidation state and general sulphur bonding environment but also the aromaticity of the bonding radical group with 87% accuracy as well as identifying even finer details in electronic structure within aromatic or aliphatic sub-classes. We find that the chemical information in XANES and VtC-XES is very similar in character and content, although they unexpectedly have different sensitivity within a given molecular class. We also discuss likely benefits from further effort with unsupervised machine learning and from the interplay between supervised and unsupervised machine learning for X-ray spectroscopies. Our overall results, i.e., the ability to reliably classify without user bias and to discover unexpected chemical signatures for XANES and VtC-XES, likely generalize to other systems as well as to other one-dimensional chemical spectroscopies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solving the structure of “single-atom” catalysts using machine learning – assisted XANES analysis

We show that "single-atom” catalysts (SACs) have demonstrated excellent activity and selectivity in challenging chemical transformations such as photocatalytic CO 2 reduction. For heterogeneous photocatalytic SAC systems, it is essential to obtain sufficient information of their structure at the atomic level in order to understand reaction mechanisms. In this work, a SAC was prepared by grafting a molecular cobalt catalyst on a light-absorbing carbon nitride surface. Due to the sensitivity of the X-ray absorption near edge structure (XANES) spectra to subtle variances in the Co SAC structure in reaction conditions, different machine learning (ML) methods, including principal component analysis, K-means clustering, and neural network (NN), were utilized for in situ Co XANES data analysis. As a result, we obtained quantitative structural information of the SAC nearest atomic environment thereby extending the NN-XANES approach previously demonstrated for nanoparticles and size-selective clusters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Seeking regularity from irregularity: unveiling the synthesis–nanomorphology relationships of heterogeneous nanomaterials using unsupervised machine learning

Nanoscale morphology of functional materials determines their chemical and physical properties. However, despite increasing use of transmission electron microscopy (TEM) to directly image nanomorphology, it remains challenging to quantify the information embedded in TEM data sets, and to use nanomorphology to link synthesis and processing conditions to properties. We develop an automated, descriptor-free analysis workflow for TEM data that utilizes convolutional neural networks and unsupervised learning to quantify and classify nanomorphology, and thereby reveal synthesis–nanomorphology relationships in three different systems. While TEM records nanomorphology readily in two-dimensional (2D) images or three-dimensional (3D) tomograms, we advance the analysis of these images by identifying and applying a universal shape fingerprint function to characterize nanomorphology. After dimensionality reduction through principal component analysis, this function then serves as the input for morphology grouping through unsupervised learning. We demonstrate the wide applicability of our workflow to both 2D and 3D TEM data sets, and to both inorganic and organic nanomaterials, including tetrahedral gold nanoparticles mixed with irregularly shaped impurities, hybrid polymer-patched gold nanoprisms, and polyamide membranes with irregular and heterogeneous 3D crumple structures. In each of these systems, unsupervised nanomorphology grouping identifies both the diversity and the similarity of the nanomaterial across different synthesis conditions, revealing how synthetic parameters guide nanomorphology development. Our work opens possibilities for enhancing synthesis of nanomaterials through artificial intelligence and for understanding and controlling complex nanomorphology, both for 2D systems and in the far less explored case of 3D structures, such as those with embedded voids or hidden interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Manganese-based A-site high-entropy perovskite oxide for solar thermochemical hydrogen production

Non-stoichiometric perovskite oxides have been studied as a new family of redox oxides for solar thermochemical hydrogen (STCH) production owing to their favourable thermodynamic properties. However, conventional perovskite oxides suffer from limited phase stability and kinetic properties, and poor cyclability. Here, we report a strategy of introducing A-site multi-principal-component mixing to develop a high-entropy perovskite oxide, (La 1/6 Pr 1/6 Nd 1/6 Gd 1/6 Sr 1/6 Ba 1/6 )MnO 3 (LPNGSB_Mn), which shows desirable thermodynamic and kinetics properties as well as excellent phase stability and cycling durability. LPNGSB_Mn exhibits enhanced hydrogen production (~77.5 mmol mol oxide -1 ) compared to (La 2/3 Sr 1/3 )MnO 3 (~53.5 mmol mol oxide -1 ) in a short 1 hour redox duration and high STCH and phase stability for 50 cycles. LPNGSB_Mn possesses a moderate enthalpy of reduction (252.51–296.32 kJ (mol O) -1 ), a high entropy of reduction (126.95–168.85 J (mol O) -1 K -1 ), and fast surface oxygen exchange kinetics. All A-site cations do not show observable valence changes during the reduction and oxidation processes. In conclusion, this research preliminarily explores the use of one A-site high-entropy perovskite oxide for STCH.

08 HYDROGEN↗

Systematic characterization of selenium speciation in coal fly ash

Millions of tons of coal fly ashes (CFAs) are produced annually during coal combustion in the U.S., which are commonly beneficially used in the concrete industry or disposed of in ash ponds. CFAs contain trace amounts of a range of toxic heavy metals including selenium (Se). Because the toxicity of Se is dependent on its speciation, investigating Se speciation in CFAs as affected by coal source and combustion conditions can help understand the related environmental and human health impacts during disposal or beneficial reuse. In this study, a set of representative CFA samples were characterized for Se speciation using synchrotron X-ray absorption spectroscopy (XAS) and micro-X-ray fluorescence spectromicroscopy (μ-XRF/XAS). Se-containing particles were highly heterogeneous, and individual particles might contain multiple oxidation states including Se(0), Se(IV), and Se(VI). Principal component analysis was performed for sample characteristics including Al 2 O 3 , SiO 2 , CaO, FeO, loss on ignition, average particle size, Se concentration, and Se oxidation state. Selective catalytic reduction (SCR), which is used to limit nitrogen oxide (NO x ) emissions during coal combustion, was found to be associated with the presence of reduced Se oxidation states, with up to 90% Se(0) observed in samples with SCR. Alongside SCR, FeO content may also influence Se speciation.

01 COAL, LIGNITE, AND PEAT↗

TOFHunter—unlocking rapid untargeted screening of inductively coupled plasma–time-of-flight–mass spectrometry data

This study provides an overview of a newly developed open source program written in Python, TOFHunter, which permits the rapid and untargeted screening of inductively coupled plasma (ICP)-time-of-flight (TOF)-mass spectrometry (MS) datasets. ICP-TOF-MS is an analytical tool capable of providing quasi simultaneous detection of all nuclides from Li to Pu. This capability has triggered an increase in studies investigating single-particle analysis in which the TOF-MS provides correlated elemental/isotopic signatures on a particle basis in time. Similarly, laser ablation mapping has seen rapid growth owing to ICP-TOF-MS's capacity to handle fast washout times (<10 ms) while providing a broad nuclide coverage. The caveat to this broad mass coverage and high time resolution comes in the form of large, overwhelming datasets. With datasets typically on the scale of gigabytes, it is easy for a user to only focus on very targeted analytes; however, this focus diminishes the opportunity offered by the TOF-MS detector. TOFHunter applies chemometric methods, principal component analysis (PCA), and interesting features finder (IFF) on ICP-TOF-MS data, allowing for investigation of correlations, major and minor variance sources, and sample screening. The unique spectra identified by the (IFF) are used to generate a list of mass peaks, which are then matched with both nuclides and potential interferences before being exported for the user to investigate. Several case studies are discussed herein, demonstrating TOFHunter's ability to screen aqueous injections, single-particle/single-cell analysis, and probe laser ablation mapping files for unique regions of interest.

47 OTHER INSTRUMENTATION↗

Machine learning inversion from small-angle scattering for charged polymers

We develop Monte Carlo simulations for uniformly charged polymers and a machine learning algorithm to interpret the intra-polymer structure factor of the charged polymer system, which can be obtained from small-angle scattering experiments. The polymer is modeled as a chain of fixed-length bonds, where the connected bonds are subject to bending energy, and there is also a screened Coulomb potential for charge interaction between all joints. The bending energy is determined by the intrinsic bending stiffness, and the charge interaction depends on the interaction strength and screening length. All three contribute to the stiffness of the polymer chain and lead to longer and larger polymer conformations. The screening length also introduces a second length scale for the polymer besides the bending persistence length. To obtain the inverse mapping from the structure factor to these polymer conformation and energy-related parameters, we generate a large data set of structure factors by running simulations for a wide range of polymer energy parameters. We use principal component analysis to investigate the intra-polymer structure factors and determine the feasibility of the inversion using the nearest neighbor distance. We employ Gaussian process regression to achieve the inverse mapping and extract the characteristic parameters of polymers from the structure factor with low relative error.

36 MATERIALS SCIENCE↗

Remote sensing of Pu in uranyl nitrate crystals using reflectance spectroscopy and chemometrics

Remote quantification of Pu(VI) (0–5 mol%) co-crystallized with U in uranyl nitrate hexahydrate (UNH) crystals was achieved in a glove box using reflectance spectroscopy coupled with chemometric modeling. Reflectance spectra were also acquired for Pu(IV) and Np(VI) (0–5 mol%) crystallized with UNH; revealing spectral features consistent with their solution-phase analogs. Principal component analysis revealed Pu(IV/VI) and Np(VI) concentrations as the primary source of variation in the data, informing the development of a supervised partial least squares regression model for Pu(VI). The resulting calibration demonstrated robust performance, with replicate root mean square errors near 10% and quantifiable limits near 0.2 mol% Pu(VI) relative to U. The Pu(VI) remained stable in the crystalline UNH matrix for at least one week with minimal reduction to Pu(IV). Notably, Pu(VI) and Np(VI) incorporation in UNH quenched U(VI) fluorescence while Pu(IV) did not. This study presents a noninvasive, spectroscopic approach for solid-state Pu quantification, with direct implications for material accountability and nuclear nonproliferation monitoring.

Sadergaski, Luke R. [Oak Ridge National Laboratory↗

Erratum: Planck 2018 results: VI. Cosmological parameters

In the original version, the bounds given in Eqs. (87a) and (87b) on the contribution to the early-time optical depth, (15,30), contained a numerical error in deriving the 95th percentile from the Monte Carlo samples. The corrected 95% upper bounds are: τ(15,30) < 0:018 (lowE, flat τ(15, 30), FlexKnot), (1) τ(15, 30) < 0:023 (lowE, flat knot, FlexKnot): (2) These bounds are a factor of 3 larger than the originally reported results. Consequently, the new bounds do not significantly improve upon previous results from Planck data presented in Millea & Bouchet (2018) as was stated, but are instead comparable. Equations (1) and (2) give results that are now similar to those of Heinrich & Hu (2021), who used the same Planck 2018 data to derive a 95% upper bound of 0.020 using the principal component analysis (PCA) model and uniform priors on the PCA mode amplitudes.

79 ASTRONOMY AND ASTROPHYSICS↗

SUGAR: An improved empirical model of Type Ia supernovae based on spectral features

Type Ia supernovae (SNe Ia) are widely used to measure the expansion of the Universe. Improving distance measurements of SNe Ia is one technique to better constrain the acceleration of expansion and determine its physical nature. This document develops a new SNe Ia spectral energy distribution (SED) model, called the SUpernova Generator And Reconstructor (SUGAR), which improves the spectral description of SNe Ia, and consequently could improve the distance measurements. This model was constructed from SNe Ia spectral properties and spectrophotometric data from the Nearby Supernova Factory collaboration. In a first step, a principal component analysis-like method was used on spectral features measured at maximum light, which allowed us to extract the intrinsic properties of SNe Ia. Next, the intrinsic properties were used to extract the average extinction curve. Third, an interpolation using Gaussian processes facilitated using data taken at different epochs during the lifetime of an SN Ia and then projecting the data on a fixed time grid. Finally, the three steps were combined to build the SED model as a function of time and wavelength. This is the SUGAR model. Results. The main advancement in SUGAR is the addition of two additional parameters to characterize SNe Ia variability. The first is tied to the properties of SNe Ia ejecta velocity and the second correlates with their calcium lines. The addition of these parameters, as well as the high quality of the Nearby Supernova Factory data, makes SUGAR an accurate and efficient model for describing the spectra of normal SNe Ia as they brighten and fade. The performance of this model makes it an excellent SED model for experiments like the Zwicky Transient Facility, the Large Synoptic Survey Telescope, or the Wide Field Infrared Survey Telescope.

79 ASTRONOMY AND ASTROPHYSICS↗