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At least 577 records · Page 32
All sourcesNASA NTRSDOE OSTI
DOE OSTI2010

EXPERIMENTAL RESULTS FOR THE ISOTOPIC EXCHANGE OF A 1600 LITER TITANIUM HYDRIDE STORAGE VESSEL

Titanium is used as a low pressure tritium storage material. The absorption/desorption rates and temperature rise during air passivation have been reported previously for a 4400 gram prototype titanium hydride storage vessel (HSV). A desorption limit of roughly 0.25 Q/M was obtained when heating to 700 C which represents a significant residual tritium process vessel inventory. To prepare an HSV for disposal, batchwise isotopic exchange has been proposed to reduce the tritium content to acceptable levels. A prototype HSV was loaded with deuterium and exchanged with protium to determine the effectiveness of a batch-wise isotopic exchange process. A total of seven exchange cycles were performed. Gas samples were taken nominally at the beginning, middle, and end of each desorption cycle. Sample analyses showed the isotopic exchange process does not follow the standard dilution model commonly reported. Samples taken at the start of the desorption process were lower in deuterium (the gas to be removed) than those taken later in the desorption cycle. The results are explained in terms of incomplete mixing of the exchange gas in the low pressure hydride.

36 MATERIALS SCIENCE↗
DOE OSTI2012

The use Na, Li, K cations for modification of ZSM-5 zewolite to control hydrocarbon cold-start emission

This paper addresses the problem of controlling hydrocarbon emissions from cold-start of engines by investigating the adsorbents which could adsorb the hydrocarbons at cold temperatures and hold them to 250-300 ?. The materials, that has been studied, are based on the modification of ZSM-5 (SiO{sub 2}/Al{sub 2}O{sub 3} = 35) zeolite with Li, K, Na cations. It has been shown that the introduction of Li, Na and K in an amount that is equivalent to the content of Al in zeolite results in occurrence of toluene temperature desorption peaks at high-temperatures. The toluene temperature desorption curves for 5%Li-ZSM-5 and 2.3%Na-ZSM-5 zeolites are identical and have peak toluene desorption rate between 200 to 400 ?. Upon analysis of toluene adsorption isotherms for 2.3%Na-ZSM-5 and 5%Li-ZSM-5, it was concluded that the toluene diffusion inside of the modified zeolites channels is extremely slow and the sorption capacity of 2.3%Na-ZSM-5 is higher than with 5%Li-ZSM-5. The 2.3%Na-ZSM-5 didn't change toluene temperature programmed desorption (TPD) rate of curve after the treatment in environment with 10% ?{sub 2}? at 750-800 ? for about 28 h. The 2.3%Na-ZSM-5 zeolite is very promising as adsorbent to control the cold-start hydrocarbon emissions.

42 ENGINEERING↗
DOE OSTI2015

Isotopic exchange on solid-phase micro extraction fiber in sediment under stagnant conditions: Implications for field application of performance reference compound calibration

An overlooked issue for field application of in situ performance reference compound (PRC) calibration methods is the validity of the assumption that both the sorption of a target compound and desorption of its corresponding PRC follow the first-order kinetics with the same rate constants under stagnant conditions. In the present study, disposable polydimethylsiloxane fibers of 2 sizes (7 and 35 µm) impregnated with 8 13 C-labeled or deuterated PRCs were statically deployed into different marine sediments, from which the kinetics for sorption of the target compounds and desorption of the PRCs were characterized. Nonsymmetrical profiles were observed for exchange of the target analytes and their corresponding PRCs in sediment under stagnant conditions. Further, the hysteretic desorption of PRCs in the kinetic regime may be ascribed to the low chemical potential between the fiber and sediment porewater, which reflects the inability of water molecules to rapidly diffuse through sediment to solvate the PRCs in the aqueous layer around the fiber surface. A moderate correlation (r = 0.77 and r = 0.57, p < 0.05 for both regressions) between the PRC-calibrated equilibrium concentrations of 1,1-dichloro-2,2-bis-(chlorophenyl) ethylene (p,p'-DDE) and polychlorinated biphenyl (PCB)-153 and the lipid normalized levels in worms (Neanthes arenaceodentata) was obtained in co-exposure tests under simulating field conditions, probably resulting from slightly overestimated bioavailability because of the hysteretic desorption of PRCs and toxic effects. Environ Toxicol Chem 2016;35:1978–1985. © 2015 SETAC

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Manipulation of mass transport rates using bead-in-a-tube method

In ultralow Pu analyses, the gold standard is thermal ionization mass spectrometry (TIMS), which requires pure sources to achieve its performance. This purity is achieved through step-wise purifications. In this work single anion-exchange beads were trapped in tubing to allow for dynamic solution cycling over the surface of the beads to improve the rates of metal complex uptake. Rates of Pu sorption on single ~900 µm SIR-1200 and ~620 µm Reillex-HPQ beads were determined for single beads trapped in a tube with syringe pump driven dynamic solution cycling over the bead, improving sorption and desorption rates. A static control was used as a comparison. Using 238Pu to enable facile activity-based measurements, rates were determined by measuring the residual Pu after contact with beads using liquid scintillation analysis (LSA) for fixed periods of time. Syringe pump driven dynamic solution cycling results in ~5 and ~15-fold improvements in the sorption rates for SIR-1200 and Reillex-HPQ. Impacts on desorption were also examined.

Bead-in-a-tube, Mass Transport Rates↗
DOE OSTI2020

D retention and depth profile behavior for single crystal tungsten with high temperature neutron irradiation

Single crystalline W (tungsten) samples irradiated at 633, 963 and 1073 K by neutrons to a damage level of 0.1 dpa were exposed to a high-flux D (deuterium) plasma at 673, 873 and 973 K, respectively, in TPE (Tritium Plasma Experiment) at INL (Idaho National Laboratory). Deuterium desorption was analyzed by TDS (Thermal Desorption Spectroscopy), and D depth profiles were determined by NRA (Nuclear Reaction Analysis) at SNL (Sandia National Laboratories). HIDT (Hydrogen Isotope Diffusion and Trapping) simulation code was applied to evaluate D behavior for neutron-damaged W at higher temperature. The D retention at depths up to 3 f.tm for the neutron-damaged sample at 673 K was two orders of magnitude larger than that for undamaged tungsten, and its D desorption spectrum had a single broad stage at around 900 K. As the neutron irradiation/plasma exposure temperature increased, D retention was largely reduced, and the desorption temperature was increased to higher temperatures above 1100 K. The D depth profiles by NRA also showed D migration toward bulk by higher temperature irradiation, compared to undamaged W. The HIDT simulation indicated that the major binding energy of D was changed from 1.43 eV to 2.07 eV at higher neutron irradiation and plasma exposure temperatures, suggesting that some vacancies and small vacancy clusters would aggregate to form larger voids, or depopulation of weak traps at high D plasma exposure temperatures. It can be said that more stable trapping sites played dominant roles in the D retention at higher neutron irradiation and plasma exposure temperature. The binding energy by HIDT simulation was almost consistent with the reported value by TMAP, but the consideration of not only total D retention measured by TDS but also D depth profile by NRA led to the more accurate D behavior in neutron-damaged W.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Quenching of electron transfer reactions through coadsorption: A study of oxygen photodesorption from TiO2(110)

Using temperature programmed desorption (TPD) and photon stimulated desorption (PSD), we show that coadsorbates of varying binding energies on the rutile TiO2(110) surface exert a commensurate inhibiting influence on the hole-mediated photodesorption of adsorbed O2. A variety of coadsorbates (Ar, Kr, Xe, N2, CO, CO2, CH4, N2O, acetone, methanol or water) were shown to quench O2 photoactivity, with the extent correlating with the coadsorbate’s gas phase basicity, which in turn determines the strength of the coadsorbate-Ti4+ bond. Coadsorbed rare gases inhibited the photodesorption of O2 by ~10-25%, whereas strongly bound species (water, methanol and acetone) nearly completely inhibited O2 PSD. We suggest that coadsorption of these molecules inhibit the arrival probability of holes to the surface. Band bending effects, which vary with the extent of charge transfer between the coadsorbate and the TiO2(110) surface, are not expected to be significant in the cases of the rare gases and physisorbed species. These results indicate that neutral coadsorbates can exert a significant influence on charge transfer events by altering the interfacial dipole in the vicinity of the target molecule. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The work was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle under Contract DE-AC05-76RL01830.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2017

Elucidation of Active Sites for the Reaction of Ethanol on TiO 2 /Au(111)

Obtaining a molecular-level understanding of the reaction of alcohols with heterogeneous model catalysts is critical for improving industrial catalytic processes, such as the production of H 2 from alcohols. Gold has been shown to be an excellent oxidation catalyst once oxygen is added to it. The use of reducible oxides provides a source of oxygen on Au(111) for the reaction of ethanol, which is easily regenerated in the presence of an oxygen background. In this work, ethanol operates as a probe molecule to investigate the role of Au(111), TiO 2 nanoparticles, and TiO 2 /Au interfacial surface sites on the catalytic properties of TiO 2 /Au(111). Ultrahigh vacuum temperature-programmed desorption (TPD) studies with ethanol/Au(111) elucidate previously unreported adsorption sites for ethanol. Ethanol molecularly adsorbs to Au terrace sites, step edges, and undercoordinated kink sites with adsorption energies of -51.7, -55.8, and -65.1 kJ/mol, respectively. In a TPD coverage study of ethanol on TiO 2 /Au(111) indicates ethanol undergoes dissociative adsorption to form H*(a) and CH 3 CH 2 O*(a) on the inverse model catalyst surface. The desorption temperature of low coverages of ethanol from TiO2/Au(111) (Tdes ≈ 235 K) is at an intermediate temperature between the desorption temperatures from bulk Au(111) and TiO 2 (110), indicating both Au and TiO 2 play a role in the adsorption of ethanol. Both low-temperature adsorption and high-temperature reactions are studied and indicate that ethanol-derived products such as acetaldehyde and ethylene desorb from TiO 2 /Au(111) at ~500 K. Here, we report the identification of catalytically active sites on TiO 2 /Au(111) as interfacial sites between the oxide and Au(111) surface through the use of temperature-programmed desorption and infrared reflection absorption spectroscopy.

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

Molecular water adsorption and reactions on (alpha)-Al2O3(0001) and (alpha)-Alumina Particles

The adsorption and reaction of water on single crystal, -Al2O3(0001) in ultrahigh vacuum, and -alumina particles in ambient conditions, was investigated using temperature programmed desorption (TPD), infrared reflection absorption spectroscopy (IRAS), diffuse reflectance infrared Fourier transform spectra (DRIFTS) and other surface science techniques. For a water coverage of 1 H2O/(surface Al3+) on -Al¬2O3(0001), no evidence for the surface hydroxyls expected from dissociative adsorption was observed in the infrared spectra, while the 2 vibration of molecular water was observed. Electron-stimulated desorption of molecular water at low coverages also indicated molecular or mixed (molecular plus dissociative) adsorption. Analysis of Kr TPD spectra showed that the water films wet the alumina substrate and suggested that the films were initially growing layer-by-layer. In contrast with the single crystal results, DRIFTS of water adsorption on alumina particles indicated the presence of surface hydroxyls that persist even after annealing to high temperatures in oxygen. For water on -Al2O3(0001) at coverages less than 0.3 H2O/(surface Al3+), water desorbed over a broad temperature range extending from ~250 K to 700 K. For larger coverages, water desorption occurred at temperatures between ~160 K and 250 K, consistent with desorption of molecular water. The results, which are consistent with at most a small amount of water dissociation on the Al-terminated (0001) surface, are difficult to reconcile with calculations suggesting that the barrier to dissociation is small. However, the results are consistent with recent vibrational sum frequency experiments showing that the hydroxylation of the Al-terminated (0001) surface takes many days even at ambient pressures and temperatures.

Petrik, Nikolay G.↗
DOE OSTI2019

Understanding the Binding of Aromatic Hydrocarbons on Rutile TiO2(110)

The adsorption of cyclohexane, benzene, and alkyl-substituted benzene derivatives is studied on rutile TiO2(110) by a combination of molecular beam dosing, temperature programmed desorption, and density functional theory (DFT). An inversion analysis is used to extract the coverage dependent desorption energies from TiO2(110). The values of the suitable prefactors are derived from simple statistical mechanical models assuming different limits in the adsorbate mobility on the surface. The prefactor values determined using the vibrational frequencies from DFT calculations corroborate this analysis and show that the adsorbates are mobile in 1- or 2-dimensions on corrugated TiO2(110) surface. The adsorption of benzene derivatives is found to be dominated by the dative Lewis acid-base interactions of the p system with the surface Ti ions. While the desorption energy generally increases with increasing the length and the number of substituents, the difference between the desorption energies decreases as the number and length of substituents is increased. This is a consequence of the destabilization of the optimum bonding configuration of the benzene ring and the alkyl groups with their increasing length and number. The absolute saturation coverages of uncompressed layers correspond approximately to one molecule per two Ti5c sites and decrease slightly with increasing molecule size in a good agreement with van der Waals sizes of the molecules.

Chen, Long↗
DOE OSTI2025

Electrically Conductive Amine Functionalized Reduced Graphite Oxide Foam for CO 2 Removal from the Air

Rapid regeneration of CO 2 adsorbents is critical to improving the productivity of direct air capture (DAC) systems. In this study, we codesigned a material to have appropriate electrical conductivity and CO 2 adsorption properties to enable efficient CO 2 capture from air. Specifically, we present a poly(ethylenimine) (PEI)-impregnated thermally annealed graphite oxide (TAGO900) foam adsorbent tailored for vacuum-assisted electrically driven thermal swing adsorption (V-ETSA). This structured adsorbent leverages the high electrical conductivity of the reduced graphite oxide framework to enable fast and direct heating of the adsorbent material by electrical resistance heating (Joule heating). An optimal sample, 40 wt % PEI (molecular weight 25k) impregnated TAGO900, shows the best balance between adsorption capacity (1.54 mmol g –1 ) and adsorption rates (0.016 mmol g –1 min –1 ) using fixed bed breakthrough experiments at 25 °C and 70% RH using 50 sccm 400 ppm of CO 2 /N 2 flow. Compared to conventional temperature vacuum swing adsorption (TVSA), the V-ETSA approach achieves substantially faster CO 2 desorption, achieving average desorption rates (including cooling time) of 0.09 mmol g –1 min –1 ─approximately 2.5 times faster than TVSA under similar operating conditions. The maximum desorption rate reaches 0.23 mmol/g/min during the desorption stage. These results underscore the importance of the direct heating strategy, such as Joule heating, for fast and highly productive vacuum swing adsorption in DAC systems.

amines↗
DOE OSTI2021

Selective butene formation in direct ethanol-to-C3+-olefin valorization over Zn-Y/Beta and single-atom alloy composite catalysts using in situ generated hydrogen

The selective production of C3+ olefins from renewable feedstocks, especially via C1 and C2 platform chemicals, is a critical challenge for obtaining economically viable low-carbon middle distillate transportation fuels (i.e., jet and diesel). Here, we report a multifunctional catalyst system composed of Zn-Y/Beta and “single-atom” alloy (SAA) Pt-Cu/Al2O3 which selectively catalyzes ethanol-to-olefins (C3+, ETO) valorization in the absence of cofed hydrogen, forming butenes as the primary olefin products. Beta zeolites containing predominately isolated Zn and Y metal sites catalyze ethanol upgrading steps (588 K, 3.1 kPa ethanol, ambient pressure) regardless of cofed hydrogen partial pressure (0-98.3 kPa H2), forming butadiene as the primary product (60% selectivity at 87% conversion). The Zn-Y/Beta catalyst possesses site-isolated Zn and Y Lewis acid sites (at ~7 wt% Y) and Brønsted acidic Y sites, the latter of which has been previously uncharacterized. A secondary bed of SAA Pt-Cu/Al2O3 selectively hydrogenates butadiene to butene isomers at a consistent reaction temperature using hydrogen generated in situ from ethanol-to-butadiene (ETB) conversion. This unique hydrogenation reactivity at near-stoichiometric hydrogen and butadiene partial pressures is not observed over monometallic Pt or Cu catalysts, highlighting these operating conditions as a critical SAA catalyst application area for conjugated diene selective hydrogenation at high reaction temperatures (>573 K) and low H2/diene ratios (e.g., 1:1). Single-bed steady state selective hydrogenation rates, associated apparent hydrogen and butadiene reaction orders, and DFT calculations of the Horiuti-Polanyi reaction mechanisms indicate that the unique butadiene selective hydrogenation reactivity over SAA Pt-Cu/Al2O3 reflects lower hydrogen scission barriers relative to monometallic Cu surfaces and limited butene binding energies relative to monometallic Pt surfaces. DFT calculations further indicate the preferential desorption of butene isomers over SAA Pt-Cu(111) and Cu(111) surfaces while Pt(111) surface favors subsequent butene hydrogenation reactions to form butane over butene desorption events. Under operating conditions without of hydrogen cofeeding, this combination of Zn-Y/Beta and SAA Pt-Cu catalysts can selectively form butenes (65% butenes, 78% C3+ selectivity at 94% conversion) and avoid butane formation using only in situ generated hydrogen, avoiding costly hydrogen cofeeding requirements that hinder many renewable energy processes.

Cordon, Michael↗
DOE OSTI2023

Multivariate Flexible Framework with High Usable Hydrogen Capacity in a Reduced Pressure Swing Process

Step-shaped adsorption-desorption of gaseous payloads by flexible metal-organic frameworks can facilitate the delivery of large usable capacities with significantly reduced energetic penalties. This is desirable for the storage, transport, and delivery of H 2 , as prototypical adsorbents require large swings in pressure and temperature to achieve usable capacities approaching their total capacities. However, the weak physisorption of H 2 typically necessitates undesirably high pressures to induce the framework phase change. As de novo design of flexible frameworks is exceedingly challenging, the ability to intuitively adapt known frameworks is required. We demonstrate that the multivariate linker approach is a powerful tool for tuning the phase change behavior of flexible frameworks. In this work, 2-methyl-5,6-difluorobenzimidazolate was solvothermally incorporated into the known framework CdIF-13 (sod-Cd(benzimidazolate) 2 ), resulting in the multivariate framework sod-Cd(benzimidazolate) 1.87 (2-methyl-5,6-difluorobenzimidazolate) 0.13 (ratio = 14:1), which exhibited a considerably reduced stepped adsorption threshold pressure while maintaining the desirable adsorption-desorption profile and capacity of CdIF-13. At 77 K, the multivariate framework exhibits stepped H 2 adsorption with saturation below 50 bar and minimal desorption hysteresis at 5 bar. At 87 K, saturation of step-shaped adsorption occurs by 90 bar, with hysteresis closing at 30 bar. These adsorption-desorption profiles enable usable capacities in a mild pressure swing process above 1 mass %, representing 85-92% of the total capacities. Here this work demonstrates that the desirable performance of flexible frameworks can be readily adapted through the multivariate approach to enable efficient storage and delivery of weakly physisorbing species.

08 HYDROGEN↗
DOE OSTI2020

Non-Contact Vapor Detection of Illicit Drugs via Atmospheric Flow Tube-Mass Spectrometry

Real-time, non-contact detection of illicit drugs is a desirable goal for the interdiction of these controlled substances, but the relatively low vapor pressures of such species present a challenge for trace vapor detection technologies. The introduction of atmospheric flow tube-mass spectrometry (AFT-MS), which has previously been demonstrated to detect gas-phase analytes at low parts-per-quadrillion levels for explosives and organophosphorus compounds, also enables the potential for non-contact drug detection. With AFT-MS, direct vapor detection of cocaine and methamphetamine from ~5 µg residues at room temperature is demonstrated herein. Furthermore, thermal desorption of low- to sub-picogram levels of cocaine, methamphetamine, fentanyl, and heroin is observed via AFT-MS using a carrier flow rate of several L/min of air. These low levels can permit non-contact sampling through collection of vapor, effectively preconcentrating the analyte before desorption and analysis. Quantitative evaluation of the thermal desorption approach has yielded limits of detection (LODs) on order of 10 fg for cocaine and fentanyl, 100 fg for methamphetamine, and 1.6 pg for heroin. The LOD for heroin was lowered to 200 fg by using tributyl phosphate as a dopant to form a proton-bound heterodimer with heroin. When used with AFT-MS, the intentional formation of specific drug-dopant adducts has the potential to enhance detection limits and selectivity of additional drug species. Species that are prone to form adducts present a challenge to analysis, but that difficulty can be overcome by the intentional addition of a dopant. Molecules unlikely to form adducts will remain essentially unimpacted, but the adduct-forming species will interact with the dopant to compress the analyte signal into a single peak. This approach would be valuable in the application of non-contact screening for illicit substances via vapor collection followed by thermal desorption for analysis.

methamphetamine, cocaine, heroin, fentanyl, atmosp↗
DOE OSTI2021

Development of the materials analysis and particle probe for Proto-MPEX

The Prototype Material Plasma Exposure eXperiment (Proto-MPEX) is a linear plasma device being used in plasma source research and development (R&D) for the proposed MPEX. Once the R&D is completed, this device can also be used to perform plasma–material interaction studies. To perform these studies, a new materials analysis and particle probe (MAPP) has been constructed. The MAPP’s components are a sample holder and manipulator and a custom vacuum chamber with ports to facilitate surface chemistry diagnostics. The MAPP’s overall design enables rapid sample turnaround and in vacuo surface characterization. The surface analysis vacuum chamber has ports for x-ray photoelectron spectroscopy, thermal desorption spectroscopy, back-scatter ion scattering spectroscopy, forward-scatter ion scattering spectroscopy, and direct recoil spectroscopy. The sample manipulator and holder is a Lesker/UHV Multi-Centre Analytical Stage, which is used to place the samples in the exposure region of the Proto-MPEX or the analysis position in the MAPP vacuum chamber. The sample holder has a heating capability of up to 1200 °C for heated exposure and for desorption studies. In this work, we present the MAPP’s design and the first tungsten sample exposure with ex situ analysis that shows a surface deposition layer on the exposed target, highlighting the need for additional in situ measurements on the Proto-MPEX.

Beers, C. J. (ORCID:0000000150985459)↗
DOE OSTI2024

Insights into the structure and dynamics of K + ions at the muscovite–water interface from machine learning potential simulations

The surfaces of many minerals are covered by naturally occurring cations that become partially hydrated and can be replaced by hydronium or other cations when the surface is exposed to water or an aqueous solution. These ion exchange processes are relevant to various chemical and transport phenomena, yet elucidating their microscopic details is challenging for both experiments and simulations. Here, in this work, we make a first step in this direction by investigating the behavior of the native K + ions at the interface between neat water and the muscovite mica (001) surface with ab-initio -based machine learning molecular dynamics and enhanced sampling simulations. Our results show that the desorption of the surface K + ions in pure ion-free water has a significant free energy barrier irrespective of their local surface arrangement. In contrast, facile K + diffusion between mica’s ditrigonal cavities characterized by different Al/Si orderings is observed. This behavior suggests that the K + ions may favor a dynamic disordered surface arrangement rather than complete desorption when exposed to deionized water.

Ab-initio molecular dynamics↗
DOE OSTI2019

Modeling the sharp deuterium release from beryllium co-deposits

Many studies have shown a sharp deuterium desorption from beryllium at around 450 K. In an attempt to model this sharp release, a new model was developed, describing the formation and decomposition of beryllium deuteride. Such a model was found to reproduce the sharp desorption peak in the thermal desorption spectrum. Moreover, in contrast to other models, the new model was able to reproduce the constant deuterium desorption from beryllium held at a constant elevated temperature. Further, fitting the modeling results to experimental data allowed us to determine the deuterium solubility limit in beryllium, which indicated an endothermic formation of beryllium deuteride. New values of the deuterium surface recombination coefficient were also obtained, differing from the ones found in the literature.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Atomistic simulations for investigation of substrate effects on lipid in-source fragmentation in secondary ion mass spectrometry

In beam-based ionization methods, the substrate plays an important role on the desorption mechanism of molecules from surfaces. Both the specific orientation that a molecule adopts at a surface and the strength of the molecule-surface interaction can greatly influence desorption processes, which in turn will affect the ion yield and the degree of in-source fragmentation of a molecule. In the beam-based method of secondary ion mass spectrometry (SIMS), in-source fragmentation can be significant and molecule specific due to the hard ionization method of using a primary ion beam for molecule desorption. To investigate the role of the substrate on orientation and in-source fragmentation, we have used atomistic simulations—molecular dynamics in combination with density functional theory calculations—to explore the desorption of a sphingolipid (palmitoylsphingomyelin) from a model surface (gold). We then compare SIMS data from this model system to our modeling findings. Using this approach, we found that the combined adsorption and binding energy of certain bonds associated with the headgroup fragments (C3H8N+, C5H12N+, C5H14NO+, and C5H15PNO4+) was a good predictor for fragment intensities (as indicated by relative ion yields). This is the first example where atomistic simulations have been applied in beam-based ionization of lipids, and it presents a new approach to study biointerfacial lipid ordering effects on SIMS imaging.

59 BASIC BIOLOGICAL SCIENCES↗