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At least 127 records · Page 7

Evaluating Ion Accumulation and Storage in Traveling Wave Based Structures for Lossless Ion Manipulations

Structures for lossless ion manipulations (SLIM) technology has demonstrated high resolving power ion mobility separation and flexibility to integrate complex ion manipulations into a single experimental platform. To enable IMS separations, trapping/accumulating ions inside SLIM (or in-SLIM) prior to injection of a packet for separations provides ease of operation and reduces the need for dedicated ion traps external to SLIM. To fully characterize the ion accumulation process, we have evaluated the effect of TW amplitudes, ion collection times, and storage times on the “in-SLIM” accumulation process. The study utilized a SLIM module comprising 5 distinct tracks, each with a specific ion accumulation configuration. The effect of the TW conditions on the accumulation process was investigated for a 3-peptide mixture: kemptide, angiotensin II, and neurotensin at a TW speed of 106 m/s. The effect of ion accumulation time/collection time and storage time was investigated, in addition to TW amplitude. Overall, the signal of the analyte ions increased when the ion collection time increased from 49 to 163 ms but decreased when the ion collection time increased further to 652 ms due to the space charge effects. Ion losses were observed at high TW amplitudes (e.g., 15 V p–p and 20 V p–p ). In addition, under space charge conditions (e.g., collection times of 163 and 652 ms), the signal of the analyte ions decreased with an increase in storage times for all TW amplitudes applied to the trapping region. For ion accumulation, the data indicate that gentler TW conditions must be utilized to minimize ion losses and fragments to benefit from the “in-SLIM” accumulation process. Finally, wider SLIM tracks provided better performance than those with narrower tracks.

59 BASIC BIOLOGICAL SCIENCES↗

Exploring new frontiers in type 1 diabetes through advanced mass-spectrometry-based molecular measurements

Type 1 diabetes (T1D) is a devastating autoimmune disease for which advanced mass spectrometry (MS) methods are increasingly used to identify new biomarkers and better understand underlying mechanisms. For example, integration of MS analysis and machine learning has identified multimolecular biomarker panels. In mechanistic studies, MS has contributed to the discovery of neoepitopes, and pathways involved in disease development and identifying therapeutic targets. However, challenges remain in understanding the role of tissue microenvironments, spatial heterogeneity, and environmental factors in disease pathogenesis. Recent advancements in MS, such as ultra-fast ion-mobility separations, and single-cell and spatial omics, can play a central role in addressing these challenges. Here, in this work, we review recent advancements in MS-based molecular measurements and their role in understanding T1D.

60 APPLIED LIFE SCIENCES↗

Ambient Ion Trapping and Separations for High Throughput Structurally Selective Material Deposition

While ion mobility coupled to mass spectrometry (IMS/MS) has been increasingly adapted to biological analysis, the structural and molecular specificity offered by IMS/MS has untapped potential for creating novel materials (for energy, catalysis, biomolecular switches etc.) with rationally tailored properties by precisely controlling the chemical structure and composition of these materials. While electrochemical and catalytic properties of the bulk material are understood by mass-selective ion-soft-landing, different structures of one molecule can exhibit distinct properties from the bulk. Many biological phenomenon occur at interfaces and are highly structurally specific. IMS/MS offers means to separate molecules in a sample (which is first ionized and released to gas phase from the condensed phase) based on mass and structure. Species thus separated can potentially be deposited onto surfaces with molecular and structural specificity, to perform fundamental investigations for understanding critical interfacial phenomenon. Key performance metrics for IMS/MS analysis are resolution of separations and sensitivity. Recently developed Structures for Lossless Ion Manipulations (SLIM)4 enabled unprecedented resolution in IMS separations. In addition, high sensitivity was enabled in SLIM due to lossless confinement of ions using radio frequency fields. Thus, SLIM enabled extremely long path length separations (up to 0.1 km thus far) providing efficient separation of molecular ions never before achieved (e.g. isotopologues, D&L amino acids). While SLIM has unprecedented analytical separations power/utility, the use of SLIM platform for depositing mobility and mass selected molecular ions has two specific technological challenges: (a) Pulsed nature of IMS separations and their low duty cycle and (b) the need for a low vacuum of ~4 torr for lossless ion confinement. These limitations lead to long deposition times due to loss of ions generated from the sample. Enabling ion confinement at atmospheric pressure will be path-breaking contribution to the fundamental understanding of ion manipulations and separations and will also enable novel science currently precluded due to the inability of the present technologies to confine ions under ambient conditions. Traditionally used radio frequency fields are ineffective in confining ions at high pressures due to ion/neutral collisions. To address these, we propose to (a) develop methods for confining and manipulating ions for lossless IMS separations at atmospheric pressure enabling high sensitivity and throughput and (b) use the high specificity of IMS/MS and high throughput from ambient ion confinement to perform mobility and mass selective ion deposition at atmospheric pressure. Our goal is to enable the study of the fundamental properties of energy/catalysis materials and biomolecules. This project paves the way for high-throughput, mass and structure selective material deposition for highly specific surface creation/functionalization (discussed in Section 2 of the report). Further, the developments reported continue to push the boundaries of this process to ambient conditions (discussed in Section 3 of the report). We conclude with a list of specific intellectual property and publications which have been the outcome of this funded project.

36 MATERIALS SCIENCE↗

PeakQC: A Software Tool for Omics-Agnostic Automated Quality Control of Mass Spectrometry Data

Mass spectrometry is broadly employed to study complex molecular mechanisms in various biological and environmental fields, enabling 'omics' research such as proteomics, metabolomics, and lipidomics. As study cohorts grow larger and more complex with dozens to hundreds of samples, the need for robust quality control (QC) measures through automated software tools becomes paramount to ensure the integrity, high quality, and validity of scientific conclusions from downstream analyses and minimize the waste of resources. Since existing QC tools are mostly dedicated to proteomics, automated solutions supporting metabolomics are needed. To address this need, we developed the software PeakQC, a tool for automated QC of MS data that is independent of omics molecular types (i.e., omics-agnostic). It allows automated extraction and inspection of peak metrics of precursor ions (e.g., errors in mass, retention time, arrival time) and supports various instrumentations and acquisition types, from infusion experiments or using liquid chromatography and/or ion mobility spectrometry front-end separations and with/without fragmentation spectra from data-dependent or independent acquisition analyses. Diagnostic plots for fragmentation spectra are also generated. Here, in this paper, we describe and illustrate PeakQC’s functionalities using different representative data sets, demonstrating its utility as a valuable tool for enhancing the quality and reliability of omics mass spectrometry analyses.

47 OTHER INSTRUMENTATION↗

PeakDecoder enables machine learning-based metabolite annotation and accurate profiling in multidimensional mass spectrometry measurements

Multidimensional measurements using state-of-the-art separations and mass spectrometry provide advantages in untargeted metabolomics analyses for studying biological and environmental bio-chemical processes. However, the lack of rapid analytical methods and robust algorithms for these heterogeneous data has limited its application. Here, we develop and evaluate a sensitive and high-throughput analytical and computational workflow to enable accurate metabolite profiling. Our workflow combines liquid chromatography, ion mobility spectrometry and data-independent acquisition mass spectrometry with PeakDecoder, a machine learning-based algorithm that learns to distinguish true co-elution and co-mobility from raw data and calculates metabolite identification error rates. We apply PeakDecoder for metabolite profiling of various engineered strains of Aspergillus pseudoterreus, Aspergillus niger, Pseudomonas putida and Rhodosporidium toruloides. Results, validated manually and against selected reaction monitoring and gas-chromatography platforms, show that 2683 features could be confidently annotated and quantified across 116 microbial sample runs using a library built from 64 standards.

59 BASIC BIOLOGICAL SCIENCES↗

Apolipoprotein A-I modulates HDL particle size in the absence of apolipoprotein A-II

Human high-density lipoproteins (HDLs) are a complex mixture of structurally related nanoparticles that perform distinct physiological functions. We previously showed that human HDL containing apolipoprotein A-I (APOA1) but not apolipoprotein A-II (APOA2), designated LpA-I, is composed primarily of two discretely sized populations. Here, we isolated these particles directly from human plasma by antibody affinity chromatography, separated them by high-resolution size-exclusion chromatography and performed a deep molecular characterization of each species. The large and small LpA-I populations were spherical with mean diameters of 109 Å and 91 Å, respectively. Unexpectedly, isotope dilution MS/MS with [ 15 N]-APOA1 in concert with quantitation of particle concentration by calibrated ion mobility analysis demonstrated that the large particles contained fewer APOA1 molecules than the small particles; the stoichiometries were 3.0 and 3.7 molecules of APOA1 per particle, respectively. MS/MS experiments showed that the protein cargo of large LpA-I particles was more diverse. Human HDL and isolated particles containing both APOA1 and APOA2 exhibit a much wider range and variation of particle sizes than LpA-I, indicating that APOA2 is likely the major contributor to HDL size heterogeneity. We propose a ratchet model based on the trefoil structure of APOA1 whereby the helical cage maintaining particle structure has two “settings”—large and small—that accounts for these findings. This understanding of the determinants of HDL particle size and protein cargo distribution serves as a basis for determining the roles of HDL subpopulations in metabolism and disease states.

59 BASIC BIOLOGICAL SCIENCES↗

Strongly Correlated Ion Dynamics in Plastic Ionic Crystals and Polymerized Ionic Liquids

Understanding the mechanisms controlling ionic conductivity is critical for the development of the next generation of batteries and supercapacitors. This paper discusses the significant role played by ionic correlations in conductivity of concentrated ionic systems. Our studies of an organic ionic plastic crystal reveal that correlations in ions dynamics suppress conductivity by 25–100 times in comparison to the expected uncorrelated ionic conductivity estimated from the Nernst–Einstein relationship. Furthermore, additional analysis also demonstrates that ionic correlations suppress conductivity in polymerized ionic liquids and gel by ~10 times. Thus, ionic correlations, usually neglected in many studies, play a very important role in conductivity of concentrated ionic systems. These results cannot be explained by a diffusion of ion pairs because all these systems are essentially single ion conductors. In contrast, strongly correlated motions of mobile ions with the same charge (cation–cation or anion–anion correlations) are the major mechanism suppressing the ionic conductivity in these systems. Finally, on the basis of these results, we emphasize that charge transport rather than ion diffusion is critical for electrolyte performance and suggest the potential design of plastic crystals and polymer electrolytes with enhanced ionic conductivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Refining PeakDecoder Version 2

Novel computational tools for processing multidimensional mass spectrometry (MS) data are necessary to enable deeper and automated detection and quantification of metabolites in complex backgrounds. Multidimensional MS data includes measurements from liquid chromatography (LC) and ion mobility spectrometry (IM) separations, and precursor and fragment ion spectra collected in data-independent acquisition (DIA) mode. PeakDecoder is an artificial intelligence (AI)-based software that enables automated interpretation of this kind of data to identify and quantify individual metabolites in complex mixtures. The goal of this project was to improve and re-implement PeakDecoder in a better suited programming language to enable its commercialization.

97 MATHEMATICS AND COMPUTING↗

What is the Role of Relative Humidity on Conductivity in Polymer Electrolytes?

Ion transport properties in polymer electrolytes have been widely studied under rigorously dry and highly water-swollen conditions. However, the transition between these extremes, i.e., the low hydration regime, is still poorly understood at the molecular level and relevant to applications ranging from battery electrolytes to electrophoretic separations. Here, in this study, we apply atomistic molecular dynamics simulations to probe the role of hydration on ion mobilities and conductivities in LiTFSI-doped polyethers at low water content (less than 10% water by volume), which corresponds to 0−80% relative humidity conditions. With increasing water content, Li + ions exhibit two distinct regimes in their mobilities. At low water content, the majority of the Li + ions are weakly hydrated (two or fewer water molecules per Li + ion), maintaining strong interactions with their polymer solvation cage, and therefore exhibit only a weak increase in mobility relative to dry conditions. As water content increases, Li + ions form complete hydration shells, residing within water-rich domains that promote faster mobilities. Further, Li + mobilities increase more significantly in polymer electrolytes composed of more hydrophilic polymers and higher salt concentrations due to the formation of larger water-rich domains. In contrast, TFSI − has comparatively weak interactions with both the polymer and water, exhibiting a monotonic increase in mobility as a function of water content. Overall, these results help clarify the molecular mechanisms underlying ionic mobilities and conductivities in polymer electrolytes at low water content.

36 MATERIALS SCIENCE↗

Molecular understanding of ion transport in a zwitterionic electrolyte

Zwitterions (ZIs) are unique molecules that carry both positive and negative charges, resulting in overall charge neutrality and high dielectric constants. These distinctive properties have enabled broad applications of zwitterionic functionality, including the emerging use of ZIs in lithium-ion battery electrolytes. As a contribution to this developing field, we use all-atom molecular dynamics simulations to investigate the ion transport mechanisms in amorphous mixtures of a zwitterionic liquid containing a range of LiTFSI salt concentrations. Furthermore, the local coordination environment around the Li + ions plays a strong role in governing ionic conductivity, as well as the enhancement of Li + transport numbers with increasing salt concentration. Addition of small amounts of water leads to increased conductivity and ion mobilities due to the water coordinating with the Li + ions, which reduces direct interactions with larger charged species.

Classical molecular dynamic simulations↗

Light induced ion migration studies in perovskite solar cell using nonlinear impedance spectroscopy

Complex interactions between mobile ions and charge carriers in perovskite solar cells (PSCs) make it challenging to fully understand their dynamic interplay. Exposure to light further complicates these interactions, altering the system’s dynamics and inducing nonlinear effects that lead to changes in the J−V curve. Understanding these effects is crucial for improving the operational stability of PSCs. Impedance spectroscopy (IS) is a powerful technique for evaluating relaxation processes in the frequency domain; however, it is limited in capturing nonlinear contributions. Here, in this work, nonlinear impedance spectroscopy (NLIS) is employed to analyze the higher harmonic response to AC perturbation, both in the dark and after short-term light exposure. A shift in the low-frequency (LF) higher harmonic peak is observed after open-circuit light exposure, attributed to an altered electric field suggesting ion re-distribution, whereas closed-circuit exposure shows no LF shift, indicating minimal ion movement. Additionally, light exposure reduces higher-order admittance, more notably in open-circuit conditions, suggesting decreased recombination. Temperature-dependent analysis was conducted to characterize the activation energy of migrating species, identifying iodide as the dominant migrating ion.

14 SOLAR ENERGY↗

Characterization of Gas-Phase Native(-like) Proteins Using Structures for Lossless Ion Manipulations

High-resolution mobility-based ion separations in Structures for Lossless Ion Manipulations (SLIM) have been useful for ion mobility separations for a variety of molecular classes in the gas phase. Here, in this study, we present multipass SLIM separations for gas-phase proteins in their near-native state exhibiting charge-state-dependent arrival time distributions using carbonic anhydrase (29 kDa), alcohol dehydrogenase (148 kDa), and apo-transferrin (79 kDa). The experimental CCS values were obtained from calibration curves for the arrival times of Agilent Tune Mix ions. For multipass separations, the ATDs were converted to CCS values by deconvoluting the multipass arrival times into accurate single-pass values amenable to the single-pass calibration curves. Mass spectra of carbonic anhydrase (CA) showed three different charge states (z = 9+ to 11+). Their corresponding mobility peaks were baseline-separated by using 8-m single-pass separations. When compared to the corresponding drift tube ion mobility (DTIMS) measurements, the CCS values obtained from DTIMS and SLIM were in agreement within experimental error. Single-pass analysis of alcohol dehydrogenase (ADH) exhibits three predominant charge states (z = 23+ to 25+) with mobility overlap between adjacent charge states. The mobility peak resolution for ADH improved with multipass separations (up to 24-m path length). In addition, CCS distributions obtained for charge states z = 16+ to 18+ of apo-transferrin reveal a transition from a compact unimodal form (z = 18+ and 19+) to broader multimodal CCS distributions for z = 16+. For apo-transferrin, 40-m multipass separations were performed allowing for complete isolation of the selected mobility range corresponding to z = 17+, leading to selective isolation of a narrow arrival time window. The extended mobility separations provided minimal alterations to the structure of the proteins, and the experimentally derived CCS values showed minimal change as a function of the separation time or number of passes. Mobility-based ion separations for native-like proteins, using SLIM, open opportunities for native-IMS applications as well as other manipulations enabled by SLIM-like mobility-selective isolation and collection.

charge state distribution↗

High‐Entropy Lithium Argyrodite Solid Electrolytes Enabling Stable All‐Solid‐State Batteries

Abstract Superionic solid electrolytes (SEs) are essential for bulk‐type solid‐state battery (SSB) applications. Multicomponent SEs are recently attracting attention for their favorable charge‐transport properties, however a thorough understanding of how configurational entropy (ΔS conf ) affects ionic conductivity is lacking. Here, we successfully synthesized a series of halogen‐rich lithium argyrodites with the general formula Li 5.5 PS 4.5 Cl x Br 1.5‐x (0≤x≤1.5). Using neutron powder diffraction and 31 P magic‐angle spinning nuclear magnetic resonance spectroscopy, the S 2− /Cl − /Br − occupancy on the anion sublattice was quantitatively analyzed. We show that disorder positively affects Li‐ion dynamics, leading to a room‐temperature ionic conductivity of 22.7 mS cm −1 (9.6 mS cm −1 in cold‐pressed state) for Li 5.5 PS 4.5 Cl 0.8 Br 0.7 (ΔS conf =1.98R). To the best of our knowledge, this is the first experimental evidence that configurational entropy of the anion sublattice correlates with ion mobility. Our results indicate the possibility of improving ionic conductivity in ceramic ion conductors by tailoring the degree of compositional complexity. Moreover, the Li 5.5 PS 4.5 Cl 0.8 Br 0.7 SE allowed for stable cycling of single‐crystal LiNi 0.9 Co 0.06 Mn 0.04 O 2 (s‐NCM90) composite cathodes in SSB cells, emphasizing that dual‐substituted lithium argyrodites hold great promise in enabling high‐performance electrochemical energy storage.

Chemistry↗

Unveiling the lithium-ion transport mechanism in Li{sub 2}ZrCl{sub 6} Solid-State Electrolyte {ital via} deep learning-accelerated molecular dynamics simulations.

Lithium zirconium chlorides (LZCs) present a promising class of cost-effective solid electrolytes for next-generation all-solid-state batteries. The unique crystal structure of LZCs plays a crucial role in facilitating lithium-ion mobility, which further affects the electrochemical performance. To understand the underlying mechanism governing ion transport, we employed deep learning-accelerated molecular dynamics simulation on Li2ZrCl6 (trigonal alpha- and monoclinic beta-LZC), focusing specifically on the zirconium coordination environment. Our results reveal that disordered alpha-LZC exhibits the highest ionic conductivity, while beta-LZC demonstrates significantly lower conductivity, closely aligning with experimental findings. The study confirms that across all phases, lithium migration proceeds via the site-to-site hopping mechanism, where variations in site residence times critically impact the overall ionic conductivity. In alpha-LZCs, lithium ions prefer to anisotropically diffuse across interlayers as the result of a lower energy barrier, driven primarily by collective diffusion. In contrast, lithium ions in beta-LZC primarily isotropically diffuse within the intralayer, hindered by higher energy barriers and determined by individual diffusion. The variation in ZrCl6 2- octahedral unit softening, induced by the specific layered arrangement of zirconium atoms, emerges as a critical determinant of the energy barriers across the LZC phases. These atomic-scale insights into the transport processes provide valuable guidance for the rational design and optimization of LZCs-based electrolytes, accelerating their practical application in advanced energy storage technologies.

Guo, Hanzeng↗

Role of Decomposition Product Ions in Hysteretic Behavior of Metal Halide Perovskite

Ion migration is one of the most debated mechanisms and credited with multiple observed phenomena and performance in metal halide perovskites (MHPs) semiconductor devices. However, to date, the migration of ions and their effects on MHPs are not still fully understood, largely due to a lack of direct observations of temporal ion migration. In this work, using direct observation of ion migration in-operando, we observe the hysteretic migration behavior of intrinsic ions (i.e., CH 3 NH 3 + and I – ) as well as reveal the migration behavior of CH 3 NH 3 + decomposition ions. We find that CH 3 NH 3 + decomposition products can be affected by light and accumulate at the interfaces under bias. These MHP decomposition products are tightly related to the device performance and stability. Complementary results of time-resolved Kelvin probe force microscopy (tr-KPFM) demonstrate a correlation between dynamics of these interfacial ions and charge carriers. Overall, we find that there are a number of mobile ions including CH 3 NH 3 + decomposition products in MHPs that need to be taken into account when measuring MHP device responses (e.g., charge dynamics) and should be considered in future optimization studies of MHP semiconductor devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Theoretical Investigation of the Hydrogenation of Cyclohexene Catalyzed by Supported Single-Atom Sites on Redox Noninnocent LiMn 2 O 4 and Li 2 Mn 2 O 4 Surfaces

Here, the tuning of catalyst activity via stereoelectronic modulation of the active-site structure remains a grand challenge in heterogeneous catalysis. In homogeneous catalysis, the redox noninnocent ligands can be introduced to organometallic fragments to donate electrons to the metal center and fine-tune the catalytic activity. Analogously, lithium-ion battery materials, such as lithium manganese oxide (LMO), lithium titanium oxides (LTO), etc., can serve as redox noninnocent catalyst support to modulate the electronic structures of the active site via lithiation, hence tuning the catalytic activity of supported active sites. Experimentally, the Ni single-atom site was supported on LiMn 2 O 4 via oxidative grafting and exhibited no catalytic activity toward the hydrogenation of cyclohexene. After introducing additional Li into the catalyst support forming Li 2 Mn 2 O 4 , the Ni single-atom site becomes active, with the catalytic rates increasing as a function of the lithiation for Li/Mn ratios >0.9. In this paper, density functional theory (DFT) calculations are performed to study the Ni site structure via X-ray absorption near edge structure (XANES) simulations and investigate the electronic properties of Ni single-atom site before and after the addition of intercalated lithium in the LMO spinel structure. Furthermore, the study of the reaction mechanism is also carried out to understand the thermodynamically and kinetically favored pathways. XANES simulation suggests that the Ni single-atom site is likely to stay in the Li channel of the spinel support structure and form an octahedral structure. After Li intercalation, the Ni site becomes less positively charged, indicating the partial reduction of the Ni site. The simulated reaction energy profile over the LiMn 2 O 4 support exhibits high-energy barriers (1.07 eV) for the hydrogenation of cyclohexene; however, the Li 2 Mn 2 O 4 support is able to better stabilize low-coordinated ion sites and improve ion mobility, leading to lower overall energy barriers (0.64 eV). The reduced and low-coordinated ion site, thus, can better stabilize the reaction intermediates and promote hydrogenation reaction. Similarly, other transition metal ions (Fe, Co, and Cu) are also considered over the LiMn 2 O 4 and Li 2 Mn 2 O 4 catalyst supports for hydrogenation reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Measurement of moisture-dependent ion diffusion constants in wood cell wall layers using time-lapse micro X-ray fluorescence microscopy

Our future bioeconomy depends on increased utilization of renewable lignocellulosic biomass. Controlling the diffusion of chemicals, such as inorganic ions, within secondary plant cell walls is central to many biomass applications. However, insufficient understanding of intra-cell-wall diffusion within secondary plant cell walls is hindering the advancement of many lignocellulosic biomass applications. In this work, X-ray fluorescence microscopy was used to measure diffusion constants of K + , Cu 2+ , and Cl - diffusing through loblolly pine (Pinus taeda) cell wall layers under 70%, 75%, or 80% relative humidity (RH). Results revealed that diffusion constants increased with RH, the larger Cu 2+ diffused more slowly than the K + , and the Cl - diffusion constant was the same as that for the counter cation, indicating cations and anions diffused together to maintain charge neutrality. Comparison with electrical conductivity measurements showed that conductivity is being controlled by ion mobility over these RH. The results further support that intra-cell-wall diffusion of inorganic ions is a Fickian diffusion process occurring through rubbery amorphous polysaccharides, which contradicts previous assertions that intra-cell-wall diffusion is an aqueous process occurring through water pathways. Researchers can now utilize polymer science approaches to engineer the molecular architecture of lignocellulosic biomass to optimize properties for specific end uses.

59 BASIC BIOLOGICAL SCIENCES↗