Search NASA⌕ Search

SEARCH · Search NASA

Results for “separability”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 1,135 records · Page 63
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Bi2WO6/ZnFe2O4 heterostructures nanofibers: Enhanced visible-light photocatalytic activity and magnetically separable property

Highlights: • Bi{sub 2}WO{sub 6} nanosheets were grown on ZnFe{sub 2}O{sub 4} nanofibers by a hydrothermal method. • The Bi{sub 2}WO{sub 6}/ZnFe{sub 2}O{sub 4} heterostructures nanofibers showed high photodegredation of RhB under visible-light. • The Bi{sub 2}WO{sub 6}/ZnFe{sub 2}O{sub 4} heterostructures nanofibers possessed magnetically separable property. - Abstract: Bi{sub 2}WO{sub 6} nanosheets were uniformly grown on electrospun ZnFe{sub 2}O{sub 4} nanofibers via a solvothermal technique. The loading amounts of Bi{sub 2}WO{sub 6} in the Bi{sub 2}WO{sub 6}/ZnFe{sub 2}O{sub 4} heterostructures nanofibers could be controlled by adjusting the precursor concentration in solvothermal process. Under visible-light irradiation, the degradation rate constant (rhodamine B) of the Bi{sub 2}WO{sub 6}/ZnFe{sub 2}O{sub 4} heterostructures was 11.6 times than that of pure ZnFe{sub 2}O{sub 4} nanofibers and 5.8 times than that of pure Bi{sub 2}WO{sub 6} nanosheets, mainly owing to the effective separation of the photogenerated electron-hole pairs in the Bi{sub 2}WO{sub 6}/ZnFe{sub 2}O{sub 4} heterostructures. Notably, the Bi{sub 2}WO{sub 6}/ZnFe{sub 2}O{sub 4} heterostructures nanofibers could be easily separated from the solution under an external magnetic field by employing the ferromagnetic behaviors of ZnFe{sub 2}O{sub 4}. After several cycles, the photocatalytic activity of the Bi{sub 2}WO{sub 6}/ZnFe{sub 2}O{sub 4} heterostructures nanofibers did not decrease significantly suggesting that the Bi{sub 2}WO{sub 6}/ZnFe{sub 2}O{sub 4} heterostructures possess stable characteristics. This kind of Bi{sub 2}WO{sub 6}/ZnFe{sub 2}O{sub 4} heterostructures nanofibers with high visible-light photocatalytic activity, excellent stability and excellent recyclability could be significance in environmental application.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Kinetics and mechanism of light-induced phase separation in a mixed-halide perovskite

Halide ion phase separation is a barrier to the application of mixed-halide perovskites, whereby the presence of large populations of photo-generated or injected carriers causes undesirable changes in the local band gap. Here, we investigate the mechanism of phase separation in CsPbI x Br 3-x perovskite single crystals driven by light. The phase separation process and its dynamics are visualized at the nanometer scale at cryogenic temperatures using in-situ scanning transmission electron microscopy and cathodoluminescence. Combined with phase field modeling that accounts for the coupling between electronic and chemical driving forces, our observations point to a spinodal decomposition mechanism in which both the amplitude of composition fluctuation and the characteristic length scale grow non-linearly with time. Our findings provide microscopic insights that can assist in further engineering mixed-halide perovskites either for stability or for intentional programming of the local halide ion composition, opening pathways to a wide range of applications.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Addition-type alkoxysilyl-substituted polynorbornenes for post-combustion carbon dioxide separations

The separation of CO 2 from N 2 using polymeric membranes has proven a particularly challenging task. One promising class of polymers for this application is alkoxysilyl-substituted vinyl-added polynorbornenes (VAPNBs), which are high T g materials that often exhibit notable CO 2 /N 2 separation performance. This performance is believed to arise from their anomalous behavior in which they display high levels of solubility selectivity, a trait more commonly encountered in rubbery polymers than high T g glassy materials. While this trait has been documented in literature, no systematic investigations have been reported that probe the relationship between alkoxysilyl-substituted VAPNB structure and their resultant gas separation behavior. Here, we describe the synthesis and evaluation of three sets of alkoxysilyl-substituted VAPNBs that are designed to probe distinct facets of their structure-transport relationship. This includes investigations into the effect that alkoxysilyl branching, chain length, and carbon linker length have on CO 2 /N 2 permeability, solubility, and diffusivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Polystyrene sulfonate (PSS) stabilized polyethylenimine (PEI) membranes fabricated by spray coating for highly effective CO 2 /N 2 separation

Greenhouse effect, largely caused by CO 2 emission, has become a major concern for global climate change. Post-combustion CO 2 capture is one of the critical strategies to mitigate this issue. Membrane technology for carbon capture has drawn significant attention because of the cost and energy efficiency and scalability. Many membranes for CO 2 capture are limited by the trade-off between CO 2 permeability and CO 2 /N 2 selectivity and the long-term stability under practical operating conditions. Facilitated transport membranes with efficient CO 2 carriers have demonstrated potential to surpass the permeability-selectivity trade-off, but these carriers are often lost under operational conditions. In this work, we designed and fabricated a polystyrene sulfonate (PSS) stabilized polyethylenimine (PEI) membrane by a facile and scalable spray-coating method. The deposited defect-free selective layer, in which the amine carriers in PEI can be stabilized electrostatically by PSS, exhibited superior CO 2 separation performance with good long-term stability under practical operating conditions. The separation performance was optimized by spray-coating cycles, CNT network loading, and PSS loading. Our membrane showed CO 2 permeance ranging from 820 to 1,770 GPU and CO 2 /N 2 selectivity varying from 395 to 460 under vacuum operation mode in the temperature range between 80 and 90 °C. Furthermore, the membrane was successfully scaled up to 200 cm 2 with good uniformity. These results might suggest a novel membrane structure and a scalable approach for fabrication of highly efficient CO 2 separation membranes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Ultrathin-film composite (uTFC) membranes based on amorphous perfluoropolymers for liquid separations

Thin-film composite membranes based on ~100nm cross-linked polyamides (PAs) are state-of-the-art membranes for liquid separations such as desalination. However, the PA layer shows poor antifouling properties and instability in chlorine solutions. Herein, we show for the first time that glassy amorphous perfluoropolymers (PFPs, such as Teflon AF and Hyflon AD) can be fabricated into ultrathin film composite (uTFC) membranes with a selective layer of <20nm for desalination. Increasing the polymer concentration in the coating solutions from 0.05 mass% to 0.3 mass% increases the selective layer thickness from 9 to 25nm. When Teflon AF2400 was fabricated into 16-nm selective layers on various porous supports, the water permeance decreases from 0.37 LMH/bar for PES10k to 0.07 LMH/bar for PES1k, and the Na 2 SO 4 rejection increases from 86.6% to 95.2%. While the water permeance is lower than the commercial PA-based NF membranes, the rejection in these PFP-based membranes is comparable. Furthr, the effect of the porous support on the water permeance can be ascribed to the geometric restriction and satisfactorily described using an empirical model. Interestingly, the membranes also exhibit good Na + /Li + separation performance and stable performance for organic solvent nanofiltration, showcasing the versatility of the PFP-based uTFC membranes for various liquid separations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Adsorptive separation of CO 2 in sulfur-doped nanoporous carbons: Selectivity and breakthrough simulation

In this research, we have synthesized two sulfur functionalized nanoporous carbons by post-synthesis modifications with sulfur bearing activating agents that simultaneously enhanced the surface area and introduced sulfur functionalities on the carbon surface. The Brunauer–Emmett–Teller (BET) surface areas of these materials were 2865 and 837 m 2 /g with total sulfur contents of 8.2 and 12.9 %, respectively. The sulfur-functionalized carbons were characterized with pore textural properties, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and electron microscopy (SEM and TEM). In both the carbons, CO 2 adsorption isotherms and kinetics were measured in three different temperatures of 298, 288 and 278 K and pressures up to 760 torr. The gravimetric CO 2 uptake followed the trend with BET surface area but the surface area-based uptake was reversed and it followed the trend of sulfur content. The heat of adsorption of CO 2 in low uptake was 60-65 kJ/mol, which is the highest for CO 2 adsorption in porous carbons. In order to investigate the adsorptive separation of CO 2 , N 2 and CH 4 adsorption isotherms were also measured at 298 K and 760 torr. The selectivity of separation for CO 2 /N 2 and CO 2 /CH 4 was calculated based on the Ideal Adsorbed Solution Theory (IAST) and all the results demonstrated the high CO 2 selectivity for the carbon with higher sulfur content. The adsorption isotherms were combined with mass balances to calculate the breakthrough behavior of the binary mixtures of CO 2 /N 2 and CO 2 /CH 4 . The simulation results demonstrated that the dimensionless breakthrough time is a decreasing function of the mole fraction of CO 2 in the feed stream. The overall results suggest that the sulfurfunctionalized carbons can be employed as potential adsorbents for CO 2 separation.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Dual-pace transient heat conduction in vertically aligned carbon nanotube arrays induced by structure separation

Vertically aligned arrays of carbon nanotubes (CNTs) are attractive for a wide range of macroscopic applications which can exploit the remarkable properties of individual nanotubes. In this work, an abnormal behavior of CNT bundles in heat conduction is discovered under the transient electro-thermal characterization. The measured voltage change over the sample shows a dual-pace thermal response (DTR), which could not be fitted using a single thermal diffusivity heat transfer model. Instead, two thermal diffusivities are determined from the DTR phenomenon. Three rounds of cryogenic experiments are conducted to investigate the physics behind DTR phenomenon. It starts to emerge when the temperature is reduced to a certain level. After two rounds of cryogenic experiments, the DTR phenomenon becomes permanent from 295 K to 10 K. The nano-scale structure separation induced by the increased thermal strain leads to macroscale structure separation, which results in two parallel heat conduction paths responsible for the DTR phenomenon. By building a new parallel heat transfer model taking both the transient and steady-state electrical and thermal response into consideration, the area ratio of separated CNTs is determined. Furthermore, this result uncovers the existence of coiled morphology and nano-structure evolution of CNTs under cryogenic state and its effect on thermal and electrical transport, especially on their transient behaviors. Knowledge of the thermal transport in these CNTs arrays is important considering the fact that transient thermal response strongly affects their mechanical, optical, and electrical behaviors.

42 ENGINEERING↗
DOE OSTI2023

Commissioning of the Advanced Rare Isotope Separator ARIS at FRIB

The Facility for Rare Isotope Beams (FRIB) at Michigan State University (MSU) consists of a newly constructed linear accelerator and fragment separator that are designed for enhanced production rates of rare isotopes for use in research and other societal applications. Recent activities through to August 2022 took place to commission the Advanced Rare Isotope Separator (ARIS) and carry out the first experiments. This followed commissioning of the newly constructed linac that is designed to provide orders of magnitude higher beam power than the previously coupled cyclotrons. This required that more advanced target, beam dump, and collimation systems of the new separator be designed and constructed to sustain unprecedented conditions by heavy ion beams. Commissioning with ~1 kW beams began recently and results from activities that began in late 2021 are reported here. Comparisons between the previous and current facilities are provided.

43 PARTICLE ACCELERATORS↗
DOE OSTI2019

The effect of Poly(Ethylene oxide) cross-linking structure on the mechanical properties and CO 2 separation performance of an ion gel membrane

Ionic liquid gels of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide plasticizing a cross-linked poly(ethylene oxide) are high performance CO 2 separation membranes. Here, the effect of polymer cross-link density on the ionic liquid stability, on the mechanical properties of the resulting films, and on the gas separation properties were studied. Cross-link density was modified by changing the chain length of ethoxylated diacrylate and triacrylate monomers, and by incorporating small amounts of short, multifunctional acrylate monomers. Without the ionic liquid acting as permanent plasticizer, higher cross-link density is associated with higher yield strength but lower strain at break, as expected. In a plasticized network, however, the loss in flexibility is not accompanied by higher yield strength, leaving ion gels made from highly cross-linked network more fragile than those having longer, more flexible chains. In conclusion, lowering cross-link density also allowed more ionic liquids to be incorporated as a phase stable gel and led to better CO 2 separation performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Sustainable recycling of cathode scraps via Cyrene-based separation

Separation of cathode materials from the current collector remains a challenging task for the recycling of both spent lithium-ion batteries and cathode scraps. Dissolving the organic binder polyvinylidene difluoride (PVDF) with an organic solvent to recover both cathode materials and Al foils is an efficient and promising method. However, the use of toxic solvents limits their practical application in recycling large amounts of cathode scraps generated during the manufacturing process. Cyrene, a bioderived green solvent, is proposed here for a solvent-based separation process. This study investigated a closed-loop recovery process to reclaim cathode materials, Al foils, and PVDF binder from cathode scraps. Furthermore, the reuse of the Cyrene solvent led to a circular recycling process. Additionally, the Cyrene-based separation process embraces a sustainable electrode recovery and reuse platform and paves the way for battery recycling.

25 ENERGY STORAGE↗
DOE OSTI2017

Active and separate secretion of fiber and penton base during the early phase of Ad2 or Ad5 infection

Fiber and penton base overproduced in adenovirus (Ad) infected cells can be secreted prior to progeny release and thereby regulate progeny spread. We aimed to investigate the mechanisms of fiber and penton base secretion in Ad2- or Ad5-infected A549 cells. Our flow cytometry analyses detected abundant surface fiber molecules, but little penton base molecules at 12 h post infection. Immunogold staining combined with transmission electron microscopic analyses revealed separate, non-co-localized release of fiber and penton base in the proximity of the plasma membrane. Depolymerization of microtubule and actin cytoskeletons, and inhibition of Rock kinase and myosin II activity together demonstrated cytoskeletal network-dependent fiber secretion. Inhibition of intracellular calcium [Ca{sup 2+}]{sub i} signaling caused diminished fiber secretion, which was associated with diminished progeny production. Thus, fiber and penton base are actively and separately secreted during the early stages of Ad2 or Ad5 infection, their secretion may play important role in Ad life cycle. - Highlights: •Excessive production of structural proteins is common to viral infection, which may regulate the host-virus equilibrium and the spreading of viruses. •The adenovirus (Ad) structural proteins, fiber and penton base, are respectively important for Ad binding to its receptor and subsequent internalization in host cells. In Ad infected cells, these two structural proteins are excessively produced. •The mechanisms underlying the release of fiber and penton base molecules at the early phase of Ad infection is yet poorly understood. •Our studies show that in Ad5 or Ad2 infected A549 cells, fiber and penton base molecules are actively and separately secreted. •Fiber secretion is dependent on cytoskeleton-mediated protein traffic. •Inhibition of myosin II motor and Ca{sup 2+} signaling activity significantly diminishes fiber secretion. •These findings could contribute to our understanding of Ad spread in human populations.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Aerosol Optical Tweezers Elucidate the Chemistry, Acidity, Phase Separations, and Morphology of Atmospheric Microdroplets

Aerosol particles represent unique chemical environments because of their high surface area-to-volume ratio that promotes the effects of interfacial chemistry in confined environments. Properties such as viscosity, diffusivity, water content, pH, and morphology—following liquid–liquid phase separation—can strongly alter how a particle interacts with condensable vapors and reactive trace gases, thus modifying its continual evolution and environmental effects. Our understanding of this chemical evolution of atmospheric particulate matter and its environmental impacts is largely limited by our ability to directly observe how these critical particle properties respond to the addition or reactive uptake of new chemical components. Aerosol optical tweezers (AOT) stably trap particles in focused laser beams, providing positional control and the retrieval of many of these critical properties required to understand and predict the chemistry of aerosolized microdroplets. The analytical power of the AOT stems from the retrieval of the cavity-enhanced Raman spectrum induced by the trapping laser. Analysis of the whispering gallery modes (WGMs) that resonate as a standing wave around the droplet’s interface, provide high accuracy measurements of the droplet’s size, refractive index (and thus a measurement of composition), and can distinguish between core–shell, partially engulfed, and homogeneous morphologies. In this study, we have advanced the ability to determine the properties of the core and shell phases in biphasic droplets, including obtaining high-accuracy pH measurements. These capabilities were applied to perform AOT physical chemistry experiments on authentic secondary organic aerosol (SOA) produced directly in the AOT chamber by ozonolysis of terpene vapors. The propensity of the SOA to phase separate as a shell from a wide range of nonpolar to polar core phases was observed, along with the discovery of a stable emulsified state of SOA particles in an aqueous salt droplet. Micron-thick SOA shells did not impede the gain or loss of water or squalane from the core to the surrounding air, indicating no significant diffusional limitations to condensational growth or partitioning even under dry conditions. These experiments formed the foundation of a new framework that predicts how the phase-separated morphology of complex aerosols containing organic carbon evolves during continual atmospheric oxidation processes. Increases in oxidation state will quickly drive conversion from a partially engulfed to core–shell morphology that has dramatically different chemical reactivity since the core phase is completely concealed by the shell. The recent advances in the experimental capabilities of the AOT technique such as presented here enable novel experimental methodologies that provide insights into the chemistry and multidimensional properties of aerosol microdroplets, and how these coevolve and respond to continual chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Using a Chromatographic Pseudophase Model To Elucidate the Mechanism of Olefin Separation by Silver(I) Ions in Ionic Liquids

Silver(I) ions undergo selective olefin complexation and have been utilized in various olefin/paraffin separation techniques such as argentation chromatography and facilitated transport membranes. Ionic liquids (ILs) are solvents known for their low vapor pressure, high thermal stability, low melting points, and ability to promote a favorable solvation environment for silver(I) ion–olefin interactions. To develop highly selective separation systems, a fundamental understanding of analyte partitioning to the stationary phase and the thermodynamic driving forces behind solvation is required. In this study, a chromatographic model treating silver(I) ions as a pseudophase is constructed and employed for the first time to investigate the olefin separation mechanism in silver(I) salt/IL mixtures. Stationary phases containing varying amounts of noncoordinated silver(I) salt ([Ag + ][NTf 2 – ]) dissolved in the 1-decyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C 10 MIM + ][NTf 2 – ]) IL are utilized to determine the partition coefficients of various analytes including alkanes, alkenes, alkynes, aromatics, aldehyde, esters, and ketones. As ligand coordination to silver(I) ions is known to lower its olefin complexation capability, this study also examines two different types of coordinated silver(I) ion pseudophases, namely, monocoordinated silver(I) salt ([Ag + (1-decyl-2-methylimidazole, DMIM)][NTf 2 – ]) and dicoordinated silver(I) salt ([Ag + (1-methylimidazole, MIM)(DMIM)][NTf 2 – ]). The extent of olefin partitioning to the coordinated silver(I) ion pseudophases over the carrier gas and IL decreased by up to two orders of magnitude. Values for enthalpy, entropy, and free energy of solvation were determined for the three silver(I) ion-containing systems. Olefin retention was observed to be enthalpically dominated, while ligand coordination to the silver(I) ion pseudophase resulted in variations for both enthalpic and entropic contributions to the free energy of solvation. Furthermore, the developed model can be used to study chemical changes that occur in silver(I) ions over time as well as identify optimal silver(I) salt/IL mixtures that yield high olefin selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

A Miniature Multilevel Structures for Lossless Ion Manipulations Ion Mobility Spectrometer with Wide Mobility Range Separation Capabilities

Here, ion mobility spectrometry employing structures for lossless ion manipulations (SLIM-IMS) is an attractive gas-phase separation technique due to its ability to achieve unprecedented effective ion path lengths (>1 km) and IMS resolving powers in a small footprint. The emergence of multilevel SLIM technology, where ions are transferred between vertically stacked SLIM electrode surfaces, has subsequently allowed for ultralong single pass path lengths (>40 m) to be achieved, enabling ultrahigh resolution IMS measurements to be performed over the entire mobility range in a single experiment. The implementation of multiple SLIM levels requires very little additional space for the SLIM system, and we developed a miniature SLIM module (miniSLIM) based on multilevel SLIM technology and report the performance here. The module is 11.1 cm x 6.7 cm x 1.4 cm (L x W x H) and consists of three SLIM levels totaling 1-meter path length. Ion trajectory simulations were used to optimize the SLIM board spacings and SLIM board thicknesses of the miniSLIM IMS system. Methods of efficiently transferring ions between SLIM levels were examined and a new approach using asymmetric traveling waves (TWs) was developed and implemented in the miniSLIM. We experimentally characterized the performance of the --meter multilevel miniSLIM IMS-MS relative to a drift tube IM--MS using an Agilent tuning mixture and tetraalkylammonium cations. The 1-meter miniSLIM achieved a resolving power of up to 131 (CCS/ΔCCS), ~1.5x higher than achievable with a 78 cm path length drift tube IMS, and successfully transmitted the entire ion mobility range in a single separation. We also demonstrated the miniSLIM’s performance as a standalone IMS system (i.e., without MS), showing baseline separation between Agilent tuning mixture cations with the full mobility range observed, and a standard peptide mixture with different charge states readily differentiated. Overall the miniSLIM provides a compact alternative to high performance IMS instruments possessing similar path lengths.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Cyclable Variable Path Length Multilevel Structures for Lossless Ion Manipulations (SLIM) Platform for Enhanced Ion Mobility Separations

Ion mobility-mass spectrometry (IMS-MS) is increasingly used to analyze complex samples and provide structural information of unknown compounds. As the complexity of samples increases, there is a need to improve the resolution of IMS-MS instruments to increase the rate of molecular identification. In this work, we evaluated a cyclable and variable-pathlength multilevel Structures for Lossless Ion Manipulations (SLIM) platform to achieve a higher resolving power than previously possible. This new multilevel SLIM platform has eight separation levels connected by ion escalators and a path length of ~88 meters (~11 meters per level). Our new multilevel SLIM can also be operated in an ‘ion cycling’ mode where a set of return ion escalators transport ions from the eighth back to the first level, allowing even longer path lengths (and higher IMS resolution). The platform has been improved to enhance the ion transmission and IMS separation quality by reducing the spacing between SLIM boards as well as board thickness, reducing the ions’ escalator residence time. Compared to the previous generation, the new multilevel SLIM demonstrated a better transmission for a set of phosphazene ions, especially for the low-mobility ions. The new multilevel SLIM achieved better resolving powers than our previous 4-level SLIM. The collision cross-section-based resolving power of the SLIM platform was tested using a pair of singly-charged reverse sequence peptides (SDGRG 1+ , GRGDS 1+ ). We achieved 1100 resolving power using 88 meters of path length (i.e., 8 levels) and 1400 following an additional pass through the eight levels (i.e., 16 levels or 173.5 m). The multilevel SLIM was further evaluated to demonstrate the enhanced separation for a positively and negatively charged brain total lipid extract sample. Finally, the new multilevel SLIM enables much higher resolving powers for a wide range of ion mobilities, improved transmission for low-mobility ions, and the ability to perform even higher resolving power for ions of interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Development of a Platform for High-Resolution Ion Mobility Separations Coupled with Messenger Tagging Infrared Spectroscopy for High-Precision Structural Characterizations

The ability to uniquely identify a compound requires highly precise and orthogonal measurements. Here we describe a newly developed analytical platform that integrates high resolution ion mobility and cryogenic vibrational ion spectroscopy for high-precision structural characterizations. This platform allows for the temporal separation of isomeric/isobaric ions and provides a highly sensitive description of the ion’s adopted geometry in the gas phase. The combination of these orthogonal structural measurements yields precise descriptors that can be used to resolve between and confidently identify highly similar ions. The unique benefits of our instrument, which integrates a structures for lossless ion manipulations ion mobility (SLIM IM) device with messenger tagging infrared spectroscopy, include the ability to perform high-resolution ion mobility separations and to record the IR spectra of all ions simultaneously. The SLIM IM device, with its 13 m separation path length, allows for multipass experiments to be performed for increased resolution as needed. It is integrated with an Agilent qTOF MS where the collision cell was replaced with a cryogenically held (30 K) TW-SLIM module. The cryo-SLIM is operated in a novel manner that allows ions to be streamed through the device and collisionally cooled to a temperature where they can form noncovalently bound N 2 complexes that are maintained as they exit the device and are detected by the TOF mass analyzer. The instrument can be operated in two modes: IMS+IR where the IR spectra for mobility-selected ions can be recorded and IR-only mode where the IR spectra for all mass-resolved ions can be recorded. In IR-only mode, IR spectra (400 cm –1 spectral range) can be recorded in as short as 2 s for high throughput measurements. Further, this work details the construction of the instrument and modes of operation. It provides initial benchmarking of CCS and IR measurements to demonstrate the utility of this instrument for targeted and untargeted approaches.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Rapid Ion Mobility Separations of Bile Acid Isomers Using Cyclodextrin Adducts and Structures for Lossless Ion Manipulations

Bile acids (BAs) constitute an important class of steroid metabolites with changes implicated in disease states and other health conditions. Current analyses for these structurally similar compounds are limited by a lack of sensitivity, and long separation times with often poor isomeric resolution. To overcome these challenges and provide rapid analyses for the BA isomers, we utilized cyclodextrin adducts and ion mobility (IM) separations in structures for lossless ion manipulations (SLIM). Cyclodextrin was found to interact with both the tauro- and glyco-conjugated BA isomers studied, forming rigid noncovalent host-guest inclusion complexes. SLIM capabilities for the accumulation of large ion populations and peak compression, enabled both the sensitive detection and high-resolution separation of all the isomers studied.

Chouinard, Christopher D.↗
DOE OSTI2019

Exploiting the Dynamic Relationship between Peptide Separation Quality and Peptide Coisolation in a Multiple-Peptide Matches-per-Spectrum Approach Offers a Strategy To Optimize Bottom-Up Proteomics Throughput and Depth

We present that peptide cofragmentation leads to chimeric MS/MS spectra that negatively impact traditional single-peptide match-per-spectrum (sPSM) search strategies in proteomics. The collection of chimeric spectra is influenced by peptide coelution and the width of precursor isolation windows. Although peptide cofragmentation can be reduced by advanced chromatography, such as UHPLC and 2D-HPLC separation schemes, and narrower isolation windows, chimeric spectra can still be as high as 30–50% of the total MS/MS spectra collected. Alternatively, cofragmented peptides in chimeric spectra and the use of wider isolation windows benefit multiple-peptide matches-per-spectrum (mPSM) algorithms, such as CharmeRT, which facilitate the identification of several cofragmented peptides. Considering recent advancements in LC and mPSM methodologies, we present a comprehensive examination of the levels of chimeric spectra collected in the analysis of a HeLa digest measured using different LC modes of separation and isolation windows and compare the depth of identifications obtained when these data are annotated using a sPSM or a mPSM approach. Our results demonstrate that MS/MS data derived from 1D-HPLC strategies under different gradient schemes and searched with CharmeRT yielded higher average numbers of PSMs (11%–49%), peptide analytes (10%–16%), and peptide sequences (3%–10%) compared to data derived from 1D-UHPLC runs but searched with a sPSM strategy. Interestingly, data from a 2D-HPLC separation strategy benefits more from the application of CharmeRT results when compared to a 50 cm 1D-UHPLC column employing a 500 min gradient. In conclusion, these results provide new insights into how to better configure LC-MS/MS measurements for improved throughput and peptide identification in complex proteomes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗