Luther W. Beegle

Investigation of drift gas selectivity in high resolution ion mobility spectrometry with mass spectrometry detection

Recent studies in electrospray ionization (ESI)/ion mobility spectrometry (IMS) have focussed on employing different drift gases to alter separation efficiency for some molecules. This study investigates four structurally similar classes of molecules (cocaine and metabolites, amphetamines, benzodiazepines, and small peptides) to determine the effect of structure on relative mobility changes in four drift gases (helium, nitrogen, argon, carbon dioxide). Collision cross sections were plotted against drift gas polarizability and a linear relationship was found for the nineteen compounds evaluated in the study. Based on the reduced mobility database, all nineteen compounds could be separated in one of the four drift gases, however, the drift gas that provided optimal separation was specific for the two compounds.

Structural characterization of unsaturated phosphatidylcholines using traveling wave ion mobility spectrometry.

A number of phosphatidylcholine (PC) cations spanning a mass range of 400-1000 Da are investigated using electrospray ionization mass spectrometry coupled with traveling wave ion mobility spectrometry (TWIMS). A high correlation between mass and mobility is demonstrated with saturated phosphatidylcholine cations in N(2). A significant deviation from this mass-mobility correlation line is observed for the unsaturated PC cation. We found that the double bond in the acyl chain causes a 5% reduction in drift time. The drift time is reduced at a rate of approximately 1% for each additional double bond. Theoretical collision cross sections of PC cations exhibit good agreement with experimentally evaluated values. Collision cross sections are determined using the recently derived relationship between mobility and drift time in TWIMS stacked ring ion guide (SRIG) and compared to estimated collision cross sections using an empiric calibration method. Computational analysis was performed using the modified trajectory (TJ) method with nonspherical N(2) molecules as the drift gas. The difference between estimated collision cross sections and theoretical collision cross sections of PC cations is related to the sensitivity of the PC cation collision cross sections to the details of the ion-neutral interactions. The origin of the observed correlation and deviation between mass and mobility of PC cations is discussed in terms of the structural rigidity of these molecules using molecular dynamic simulations.

Effects of drift-gas polarizability on glycine peptides in ion mobility spectrometry

This investigation is a continuation of our previous work on the feasibility of utilizing ultra-high resolution electrospray ionization/ion mobility spectrometry (ESI/IMS) for in situ analysis of biomolecular compounds. The compounds we studied, in this investigation, were glycine, the smallest amino acid and four of its oligomers, namely triglycine, tetraglycine, pentaglycine, and hexaglycine. Experimental effects of drift-gas polarizability on target ions in IMS were explored by utilizing four different drift-gases with differing polarizability values (He, Ar, N 2, and CO2). The gas-phase ion radii for all five compounds were calculated from the reduced ion mobilities, K m 0 , and the effective drift-gas radii employing a simple hard-sphere model. When ion radii were plotted against the polarizabilities of the drift-gases, linear plots with different slopes were produced. This empirical observation indicated that the polarizing of drift-gas can change the calculated ion radii in a linear fashion over a limited range of polarizability values and does not affect all ions equally. This effect can be exploited in order to alter the separation factors between different ions since all ions that yield different slopes can, theoretically, be separated with IMS using different drift-gases. We demonstrated that the separation factor ( α) is highly dependent on the drift-gas. The maximum separability and, hence, unique identification of target ions was achieved when He and CO 2 were used. (Int J Mass Spectrom 216 (2002) 257–268)

Experimental and Theoretical Investigation into the Correlation between Mass and Ion Mobility for Choline and Other Ammonium Cations in N2

A number of tertiary amine and quaternary ammonium cations spanning a mass range of 60-146 amu (trimethylamine, tetramethylammonium, trimethylethylammonium, N,N-dimethylaminoethanol, choline, N,N-dimethylglycine, betaine, acetylcholine, (3-carboxypropyl)trimethylammonium) were investigated using electrospray ionization ion mobility spectrometry. Measured ion mobilities demonstrate a high correlation between mass and mobility in N(2). In addition, identical mobilities within experimental uncertainties are observed for structurally dissimilar ions with similar ion masses. For example, dimethylethylammonium (88 amu) cations and protonated N,N-dimethylaminoethanol cations (90 amu) show identical mobilities (1.93 cm(2) V(-1) s(-1)) though N,N-dimethylaminoethanol contains a hydroxyl functional group while dimethylethylammonium only contains alkyl groups. Computational analysis was performed using the modified trajectory (TJ) method with nonspherical N(2) molecules as the drift gas. The sensitivity of the ammonium cation collision cross sections to the details of the ion-neutral interactions was investigated and compared to other classes of organic molecules (carboxylic acids and abiotic amino acids). The specific charge distribution of the molecular ions in the investigated mass range has an insignificant affect on the collision cross section.

Interfacial Reactions of Ozone with Surfactant Protein B in a Model Lung Surfactant System

Oxidative stresses from irritants such as hydrogen peroxide and ozone (O(3)) can cause dysfunction of the pulmonary surfactant (PS) layer in the human lung, resulting in chronic diseases of the respiratory tract. For identification of structural changes of pulmonary surfactant protein B (SP-B) due to the heterogeneous reaction with O(3), field-induced droplet ionization (FIDI) mass spectrometry has been utilized. FIDI is a soft ionization method in which ions are extracted from the surface of microliter-volume droplets. We report structurally specific oxidative changes of SP-B(1-25) (a shortened version of human SP-B) at the air-liquid interface. We also present studies of the interfacial oxidation of SP-B(1-25) in a nonionizable 1-palmitoyl-2-oleoyl-sn-glycerol (POG) surfactant layer as a model PS system, where competitive oxidation of the two components is observed. Our results indicate that the heterogeneous reaction of SP-B(1-25) at the interface is quite different from that in the solution phase. In comparison with the nearly complete homogeneous oxidation of SP-B(1-25), only a subset of the amino acids known to react with ozone are oxidized by direct ozonolysis in the hydrophobic interfacial environment, both with and without the lipid surfactant layer. Combining these experimental observations with the results of molecular dynamics simulations provides an improved understanding of the interfacial structure and chemistry of a model lung surfactant system subjected to oxidative stress.

Time Resolved Studies of Interfacial Reactions of Ozone with Pulmonary Phospholipid Surfactants Using Field Induced Droplet Ionization Mass Spectrometry

Field induced droplet ionization mass spectrometry (FIDI-MS) comprises a soft ionization method to sample ions from the surface of microliter droplets. A pulsed electric field stretches neutral droplets until they develop dual Taylor cones, emitting streams of positively and negatively charged submicrometer droplets in opposite directions, with the desired polarity being directed into a mass spectrometer for analysis. This methodology is employed to study the heterogeneous ozonolysis of 1-palmitoyl-2-oleoyl-sn-phosphatidylglycerol (POPG) at the air-liquid interface in negative ion mode using FIDI mass spectrometry. Our results demonstrate unique characteristics of the heterogeneous reactions at the air-liquid interface. We observe the hydroxyhydroperoxide and the secondary ozonide as major products of POPG ozonolysis in the FIDI-MS spectra. These products are metastable and difficult to observe in the bulk phase, using standard electrospray ionization (ESI) for mass spectrometric analysis. We also present studies of the heterogeneous ozonolysis of a mixture of saturated and unsaturated phospholipids at the air-liquid interface. A mixture of the saturated phospholipid 1,2-dipalmitoyl-sn-phosphatidylglycerol (DPPG) and unsaturated POPG is investigated in negative ion mode using FIDI-MS while a mixture of 1,2-dipalmitoyl-sn-phosphatidylcholine (DPPC) and 1-stearoyl-2-oleoyl-sn-phosphatidylcholine (SOPC) surfactant is studied in positive ion mode. In both cases FIDI-MS shows the saturated and unsaturated pulmonary surfactants form a mixed interfacial layer. Only the unsaturated phospholipid reacts with ozone, forming products that are more hydrophilic than the saturated phospholipid. With extensive ozonolysis only the saturated phospholipid remains at the droplet surface. Combining these experimental observations with the results of computational analysis provides an improved understanding of the interfacial structure and chemistry of a surfactant layer system when subject to oxidative stress.

Hydrogenation of polycyclic aromatic hydrocarbons as a factor affecting the cosmic 6.2 micron emission band

While many of the characteristics of the cosmic unidentified infrared (UIR) emission bands observed for interstellar and circumstellar sources within the Milky Way and other galaxies, can be best attributed to vibrational modes of the variants of the molecular family known as polycyclic aromatic hydrocarbons (PAH), there are open questions that need to be resolved. Among them is the observed strength of the 6.2 micron (1600 cm(-1)) band relative to other strong bands, and the generally low strength for measurements in the laboratory of the 1600 cm(-1) skeletal vibration band of many specific neutral PAH molecules. Also, experiments involving laser excitation of some gas phase neutral PAH species while producing long lifetime state emission in the 3.3 micron (3000 cm(-1)) spectral region, do not result in significant 6.2 micron (1600 cm(-1)) emission. A potentially important variant of the neutral PAH species, namely hydrogenated-PAH (H(N)-PAH) which exhibit intriguing spectral correlation with interstellar and circumstellar infrared emission and the 2175 A extinction feature, may be a factor affecting the strength of 6.2 micron emission. These species are hybrids of aromatic and cycloalkane structures. Laboratory infrared absorption spectroscopy augmented by density function theory (DFT) computations of selected partially hydrogenated-PAH molecules, demonstrates enhanced 6.2 micron (1600 cm(-1)) region skeletal vibration mode strength for these molecules relative to the normal PAH form. This along with other factors such as ionization or the incorporation of nitrogen or oxygen atoms could be a reason for the strength of the cosmic 6.2 micron (1600 cm(-1)) feature.

SHERLOC: Scanning habitable environments with Raman & luminescence for organics & chemicals

SHERLOC is an arm-mounted fluorescence and Raman spectrometer that was recently selected to be part of the payload for the next proposed NASA rover mission to Mars, scheduled for launch in 2020. SHERLOC enables non-contact, spatially resolved, high sensitivity detection and characterization of organics and minerals on the Martian surface. The investigation goals are to assess past aqueous history, detect the presence and preservation potential of biosignatures, and support the selection of samples for caching and potential return to Earth.

Middle ultraviolet and visible spectrum of SO2 by electron impact

[i] Electron-impact-induced fluorescence spectra of SO 2 in the middle ultraviolet and visible wavelength regions (200-600 nm) have been measured in the laboratory using a crossed beam experiment at three electron impact energies. The emission spectra at 8, 18, and 98 eV exhibit a broad and continuous emission region extending from 225 to near 600 nm with a peak emission close to 330 nm. The quasicontinuous SO 2 bands arise primarily from direct excitation of SO 2 . At 18 and 98 eV, simultaneous excitation and dissociation of SO 2 produces distinct vibrational bands from SO and from atomic emission lines from S I, S II, O I, and O II that are superimposed on the SO 2 electronic transitions. The laboratory spectra were compared to green/violet color ratios obtained at lo by the Galileo Orbiter Solid State Imaging experiment. The laboratory spectra were also applied to the Cassini Imaging Subsystem to determine which filter combinations are particularly sensitive to electron energy, if the atmospheric gas present in the auroral atmosphere is solely or primarily SO 2 .

Deep Drilling and Sampling via the Wireline Auto-Gopher Driven by Piezoelectric Percussive Actuator and EM Rotary Motor

The ability to penetrate subsurfaces and perform sample acquisition at depths of meters is critical for future NASA in-situ exploration missions to bodies in the solar system, including Mars, Europa, and Enceladus. A corer/sampler was developed with the goal of acquiring pristine samples by reaching depths on Mars beyond the oxidized and sterilized zone. The developed rotary-hammering coring drill, called Auto-Gopher, employs a piezoelectric actuated percussive mechanism for breaking formations and an electric motor rotates the bit to remove the powdered cuttings. This sampler is a wireline drill that is incorporated with an inchworm mechanism allowing thru cyclic coring and core removal to reach great depths. The penetration rate is optimized by simultaneously activating the percussive and rotary motions of the Auto-Gopher. The percussive mechanism is based on the Ultrasonic/Sonic Drill/Corer (USDC) mechanism, which is driven by a piezoelectric stack, demonstrated to require low axial preload. The Auto-Gopher has been produced taking into account the lessons learned from the development of the Ultrasonic/Sonic Gopher that was designed as a percussive ice drill and was demonstrated in Antarctica in 2005 to reach about 2 meters deep. A field demonstration of the Auto-Gopher is currently being planned with the objective of reaching as deep as 3 to 5 meters in tufa formation.