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At least 127 records · Page 7

Accumulation of Large Ion Populations with High Ion Densities and Effects Due to Space Charge in Traveling Wave-Based Structures for Lossless Ion Manipulations (SLIM) IMS-MS

The accumulation of very large ion populations in traveling wave (TW)-based Structures for Lossless ion Manipulations (SLIM) has been studied to better understand aspects of ‘in-SLIM’ ion accumulation, and particularly its use in conjunction with ion mobility spectrometry (IMS). A linear SLIM ion path was implemented that had a ‘gate’ for blocking and accumulating ions for arbitrary time periods. Removing the gate potential caused ions to exit and the spatial distributions of accumulated ions were examined. The ion populations for a set of peptides were observed to increase with increased accumulation times until space change effects became significant, after which the peptide precursor ion populations decreased due to growing space charge-related ion activation, reactions, and losses. Ions closest to the gate were preferentially activated, and increasingly so with added storage times, TW amplitude, and the size of the total ion population. For analytical applications, we found that relatively weak TWs in the accumulation/storage region should be utilized to prevent or minimize ion losses and/or ion heating effects that can also lead to fragmentation. Our results further indicate that an accumulation region close to the SLIM entrance is advantageous for both speeding accumulation, minimizing ion heating, and avoiding ion population profiles that result in IMS peak tailing. Importantly, space charge-driven separations were observed for large populations of accumulated species and attributed to the opposing effects of space charge and the TW. In these separations, ion species form distributions or peaks, sometimes moving against the TW, and ordered in the SLIM based on their mobilities. Such separations may offer utility for ion pre-fractionation of ions and increasing the dynamic range measurements, increasing the resolving power of IMS separations by decreasing peak widths for accumulated ion populations, and other purposes benefitting from separations of extremely large ion populations.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Local Chemical Enhancement and Gating of Organic Coordinated Ionic-Electronic Transport

Superior properties in organic mixed ionic-electronic conductors (OMIECs) over inorganic counterparts have inspired intense interest in biosensing, soft-robotics, neuromorphic computing, and smart medicine. However, slow ion transport relative to charge transport in these materials is a limiting factor. Here, it is demonstrated that hydrophilic molecules local to an interfacial OMIEC nanochannel can accelerate ion transport with ion mobilities surpassing electrophoretic transport by more than an order of magnitude. Furthermore, ion access to this interfacial channel can be gated through local surface energy. This mechanism is applied in a novel sensing device, which electronically detects and characterizes chemical reaction dynamics local to the buried channel. The ability to enhance ion transport at the nanoscale in OMIECs as well as govern ion transport through local chemical signaling enables new functionalities for printable, stretchable, and biocompatible mixed conduction devices.

36 MATERIALS SCIENCE↗

Mechanical and Ionic Characterization for Organic Semiconductor–Incorporated Perovskites for Stable 2D/3D Heterostructure Perovskite Solar Cells

Hybrid metal halide perovskite (MHP) materials, while being promising for photovoltaic technology, also encounter challenges related to material stability. Combining 2D MHPs with 3D MHPs offers a viable solution, yet there is a gap in the understanding of the stability among various 2D materials. The mechanical, ionic, and environmental stability of various 2D MHP ligands are reported, and an improvement with the use of a quater-thiophene-based organic cation (4TmI) that forms an organic-semiconductor incorporated MHP structure is demonstrated. It is shown that the best balance of mechanical robustness, environmental stability, ion activation energy, and reduced mobile ion concentration under accelerated aging is achieved with the usage of 4TmI. It is believed that by addressing mechanical and ion-based degradation modes using this built-in barrier concept with a material system that also shows improvements in charge extraction and device performance, MHP solar devices can be designed for both reliability and efficiency.

14 SOLAR ENERGY↗

Origins of Lithium/Sodium Reverse Permeability Selectivity in 12-Crown-4-Functionalized Polymer Membranes

Direct lithium extraction via membrane separations has been fundamentally limited by lack of monovalent ion selectivity exhibited by conventional polymeric membranes, particularly between sodium and lithium ions. Recently, a 12- Crown-4-functionalized polynorbornene membrane was shown to have the largest lithium/sodium permeability selectivity observed in a fully aqueous system to date. Using atomistic molecular dynamics simulations, we reveal that this selectivity is due to strong interactions between sodium ions and 12-Crown-4 moieties, which reduce sodium ion diffusivity while leaving lithium ion mobility relatively unaffected. Furthermore, the ion diffusivities in the membrane, when scaled by their respective solution diffusivities and free ion fractions, can be collapsed to an almost universal relationship depending on solvent volume fraction.

36 MATERIALS SCIENCE↗

Role of Intradomain Heterogeneity on Ion and Polymer Dynamics in Block Polymer Electrolytes: Investigating Interfacial Mobility and Ion-Specific Dynamics and Transport

Block polymers show promise as solid-state battery electrolytes due to the optimization of conductive and mechanical properties enabled via tuning of block chemistry and length. We investigate a polystyrene-block-poly(oligo-oxyethylene methacrylate) (PS-b-POEM) electrolyte doped with various lithium salts to investigate the role of molecular structure on ion transport properties and on local ion dynamics and associations. Anion charge becomes more delocalized with increasing size, reducing the coupling between salt ions while increasing coupling between ion and polymer chain motions and creating a more mobile overall environment. We observe support for this ion-polymer coupling via 1 H, 7 Li and 19 F NMR spectroscopy, from which we obtain ion-specific mobility transition temperatures that differ from the polymer glass transition temperature. We also note faster transport and weaker local energetic interactions with anion size using temperature-dependent NMR diffusometry. 1 H NMR spectroscopy further elucidates polymer chain dynamics and enables quantification of the temperature-dependent fraction of the conducting block that is immobile near the PS-POEM domain interface. As a result, NMR thus represents a species-specific and timescale-specific platform to quantify phase and interface behavior, and to correlate ion-specific transport with polymer chain dynamics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

LipidOz enables automated elucidation of lipid carbon–carbon double bond positions from ozone-induced dissociation mass spectrometry data

Lipids play essential roles in many biological processes and disease pathology, but unambiguous identification of lipids is complicated by the presence of multiple isomeric species differing by fatty acyl chain length, stereospecifically numbered (sn) position, and position/stereochemistry of double bonds. Conventional liquid chromatography-mass spectrometry (LC-MS/MS) analyses enable the determination of fatty acyl chain lengths (and in some cases sn position) and number of double bonds, but not carbon-carbon double bond positions. Ozone-induced dissociation (OzID) is a gas-phase oxidation reaction that produces characteristic fragments from lipids containing double bonds. OzID can be incorporated into ion mobility spectrometry (IMS)-MS instruments for the structural characterization of lipids, including additional isomer separation and confident assignment of double bond positions. The complexity and repetitive nature of OzID data analysis and lack of software tool support have limited the application of OzID for routine lipidomics studies. Here, we present an open-source Python tool, LipidOz, for the automated determination of lipid double bond positions from OzID-IMS-MS data, which employs a combination of traditional automation and deep learning approaches. Our results demonstrate the ability of LipidOz to robustly assign double bond positions for lipid standard mixtures and complex lipid extracts, enabling practical application of OzID for future lipidomics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Beyond Ion Migration in Metal Halide Perovskites: Toward a Broader Photoelectrochemistry Perspective

Ion migration is a broad term used to account for the degradation of halide perovskite materials and devices. However, ion mobility is only one piece of the full picture-mobile ions/defects are first created, then transported, and eventually annihilated or immobilized. In this Perspective, we summarize emerging work that shows how tractable photochemical and Faradaic reactions provide a continuous source of ions to migrate. Furthermore, we discuss strategies to fundamentally manipulate ion migration by targeting specific electrochemical and reduction/oxidation mechanisms. This highlights the important role of defect photoelectrochemistry, as well as the soft nature of the perovskite lattice, in ion migration and self-healing. We conclude that distinguishing more detailed processes involved in “ion migration”, with an emerging focus on the reactions that form mobile ionic defects, is necessary to greatly improve the stability of devices and open up more technological applications.

defects↗

Entropy-Tailored Fast-Charging Sodium Layered Cathodes

O3-type layered transition metal (TM) oxides are widely used as cathode materials for Na-ion batteries due to their high energy density potential, enabled by the state of charge (SoC)-dependent transition from octahedral (O-type) to prismatic (P-type) structures during Na-ion (de)sodiation. However, the O–P transition is often criticized for compromising the Na-ion mobility and limiting the cycle life. Herein, we reveal the intrinsic correlation between O–P transitions, oxygen behaviors, and Na-ion kinetics. We demonstrate that a compositionally versatile, entropy-tailored approach can promote preferred transitions (characterized by large lattice parameter deviations in the O-type region and rapid O–P biphasic reactions), enhancing Na-ion migration, as revealed by in situ high-energy synchrotron X-ray diffraction (HEXRD). Additionally, irreversible oxygen loss at high SoC is effectively mitigated, while TM migration and surface reconstruction are greatly suppressed, further accelerating Na-ion transport and stabilizing the structure, as confirmed by X-ray absorption spectroscopy (XAS) and theoretical analyses. The result is an exceptionally high rate capability of 88.7 mAh g –1 at 20 C (2.4 A g –1 ) with a superior normalized retention of 72.6%, accompanied by a prolonged lifetime with 74.3% retention after 1000 cycles. In conclusion, this work advances the understanding of the chemistry–property relationships in O3-type layered cathodes and broadens the prospects for fabricating high-power-density electrodes.

36 MATERIALS SCIENCE↗

Field reversal in low pressure, unmagnetized radio frequency capacitively coupled argon plasma discharges

In general, the radio frequency (rf) electric field within a sheath points toward the metal electrode in low pressure, unmagnetized rf electropositive capacitively coupled plasma (CCP) glow discharges. This is due to the large ratio of electron to ion mobility and the formation of an ion sheath. In this work, we studied, using fully kinetic particle-in-cell simulations, a reversed electric field induced by the strong secondary electron emission during the phase of sheath collapse in a high-voltage rf-driven low pressure CCP glow discharge. We explored the transition behavior of the formation of field reversal as a function of driving voltage amplitude and found that field reversal starts to form at around 750 V, for a discharge with an electrode spacing of 4 cm at 10 mTorr argon pressure driven at 13.56 MHz. Accordingly, the energy distribution function of electrons incident on the electrode shows peaks from around 3 to 10 eV while varying the driving voltage from 150 to 2000 V, showing potentially beneficial effects in plasma material processing where relatively directional electrons are preferred to solely thermal diffusion electrons.

Physics↗

Reducing ion diffusion at atmospheric pressure through intermingled positive and negative ions

Increasing ion molecule reaction times for ambient ionization techniques can increase sensitivity of detection. Longer reaction times result in an increase in analyte signal relative to the reactant ion signal, however with a subsequent decrease in the total ion intensity. This loss in the total number of ions reaching the detector limits the extent to which increased reaction time can improve detection in practical applications. In this study ion loss was measured using either electric fields or gas flow to control ion transit time. Ion transit times ranged from 40 ms to 8s, which resulted in ion densities ranging from 5 x 10 6 to 2 x 10 4 ions/cm 3 , respectively. These results provide insights into practical reaction time limitations or experimental boundaries when exploring sensitivity enhancements in ambient ionization. When exploring longer reaction times with an atmospheric flow tube coupled to a mass spectrometer (AFT-MS), an additional corona discharge ionization source of the same polarity was added in an attempt to increase total ion signal, but no improvement in signal was observed. This observation suggested that there was a maximum ion density being reached by the corona discharge that could not be increased by adding more of the same polarity ions. A hypothesis was that intermingling both polarities of ions would reduce ion loss and increase the measured ion signal. When two corona discharge sources—one each of positive and negative polarity—were used simultaneously in an AFT-MS, the total ion signal of either polarity measured by the MS was approximately double the current from a single corona discharge source. An increase in the negative ion signal was also observed when ~10 parts-per-trillion vapor levels of an explosive (RDX) were introduced. In this case both the nitrate reactant ions and the RDX signal more than doubled with the addition of a corona discharge source producing positive ions. When intermingling positive and negative ions, an increase in ion current was also observed when the AFT was coupled directly to a Faraday detector or to an ion mobility spectrometer. This was the first demonstration of interfacing the AFT to an IMS. The observations and developments from this work will help in creating more portable instruments with improved sensitivity for detection of chemicals.

47 OTHER INSTRUMENTATION↗

Synthetic Accessibility and Sodium Ion Conductivity of the Na8–x A x P2O9 (NAP) High-Temperature Sodium Superionic Conductor Framework

Advancement of solid-state electrolytes (SSEs) for all solid-state batteries typically focuses on modification of a known structural framework to improve conductivity, e.g., cation substitution for an immobile ion or varying the concentration of the mobile ions. Novel frameworks can be disruptive by enabling fast ion conduction aided by different structure and diffusion mechanisms, thereby unlocking optimal conductors with different properties. Herein, we perform a high-throughput survey of a structural framework for sodium ion conduction, Na8–x A x P2O9 (NAP), to understand the family’s thermodynamic stability, synthesizability, and ionic conduction. We show that the parent phase Na4TiP2O9 (NTP) undergoes a structural distortion (with accompanying conductivity transition) due to unstable phonons arising from pseudo-Jahn–Teller mode in the 1D titanium chains. Screening compounds in which Ti is substituted by other metals computationally reveal a number of candidates that are predicted to be low in formation energy and have high predicted ionic conductivities. High-throughput experimental and subsequent methodology optimization trials deliver one new compound, Na4SnP2O9 (NSP). X-ray diffraction (XRD), microscopy, and spectroscopy characterization indicate that the room-temperature structure of NSP is similar to the high-temperature, orthorhombic NTP phase but with some small unresolved structural differences. These uncharacterized structural details are speculated to limit the ion conductivity. Temperature-dependent XRD and electrochemical impedance spectroscopy indicate multiple coupled conductivity–structure transitions at a high temperature. We demonstrate the challenges with synthesis development and a priori identification of promising SSE phases as a major bottleneck in new (energy) materials development.

Chemical reactions↗

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↗