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The presence and distribution of preserved organic matter on the surface of Mars can provide key information about the Martian carbon cycle and the potential of the planet to host life throughout its history. Several types of organic molecules have been previously detected in Martian meteorites1 and at Gale crater, Mars2-4. Evaluating the diversity and detectability of organic matter elsewhere on Mars is important for understanding the extent and diversity of Martian surface processes and the potential availability of carbon sources1,5,6. Here we report the detection of Raman and fluorescence spectra consistent with several species of aromatic organic molecules in the Máaz and Séítah formations within the Crater Floor sequences of Jezero crater, Mars. We report specific fluorescence-mineral associations consistent with many classes of organic molecules occurring in different spatial patterns within these compositionally distinct formations, potentially indicating different fates of carbon across environments. Our findings suggest there may be a diversity of aromatic molecules prevalent on the Martian surface, and these materials persist despite exposure to surface conditions. These potential organic molecules are largely found within minerals linked to aqueous processes, indicating that these processes may have had a key role in organic synthesis, transport or preservation.
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We report deep ultraviolet (DUV) Raman and Fluorescence spectra obtained on a SHERLOC (Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals) analog instrument for 51 pure organic compounds, including 5 carboxylic acids, 10 polycyclic aromatic hydrocarbons, 24 amino acids, 6 nucleobases, and 6 different grades of macromolecular carbon from humic acid to graphite. Organic mixtures were not investigated. We discuss how the DUV fluorescence and Raman spectra exhibited by different organic compounds allow for detection, classification, and identification of organics by SHERLOC. We find that 1- and 2-ring aromatic compounds produce detectable fluorescence within SHERLOC's spectral range (250-355 nm), but fluorescence spectra are not unique enough to enable easy identification of particular compounds. However, both aromatic and aliphatic compounds can be identified by their Raman spectra, with the number of Raman peaks and their positions being highly specific to chemical structure, within SHERLOC's reported spectral uncertainty of ±5 cm-1. For compounds that are not in the Library, classification is possible by comparing the general number and position of dominant Raman peaks with trends for different kinds of organic compounds.
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Grafite , Marte , Fluorescência , Compostos Orgânicos , Ácidos Carboxílicos , Carbono , Análise Espectral RamanRESUMO
The NASA/ESA Cassini probe of Saturn analyzed the molecular composition of plumes emanating from one of its moons, Enceladus, and the upper atmosphere of another, Titan. However, interpretation of this data is complicated by the hypervelocity (HV) flybys of up to ~18 km/sec that cause substantial molecular fragmentation. To interpret this data we use quantum mechanical based reactive force fields to simulate the HV impact of various molecular species and ice clathrates on oxidized titanium surfaces mimicking those in Cassini's neutral and ion mass spectrometer (INMS). The predicted velocity dependent fragmentation patterns and composition mixing ratios agree with INMS data providing the means for identifying the molecules in the plume. We used our simulations to predict the surface damage from the HV impacts on the INMS interior walls, which we suggest acts as a titanium sublimation pump that could alter the instrument's readings. These results show how the theory can identify chemical events from hypervelocity impacts in space plumes and atmospheres, providing in turn clues to the internal structure of the corresponding sources (e.g., Enceladus). This may be valuable in steering modifications in future missions.
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The NASA Mars 2020 Perseverance rover is currently exploring Jezero crater, a Noachian-Hesperian locality that once hosted a delta-lake system with high habitability and biosignature preservation potential. Perseverance conducts detailed appraisals of rock targets using a synergistic payload capable of geological characterization from kilometer to micron scales. The highest-resolution textural and chemical information will be provided by correlated WATSON (imaging), SHERLOC (deep-UV Raman and fluorescence spectroscopy), and PIXL (X-ray lithochemistry) analyses, enabling the distributions of organic and mineral phases within rock targets to be comprehensively established. Herein, we analyze Paleoarchean microbial mats from the â¼3.42 Ga Buck Reef Chert (Barberton greenstone belt, South Africa)-considered astrobiological analogues for a putative ancient martian biosphere-following a WATSON-SHERLOC-PIXL protocol identical to that conducted by Perseverance on Mars during all sampling activities. Correlating deep-UV Raman and fluorescence spectroscopic mapping with X-ray elemental mapping, we show that the Perseverance payload has the capability to detect thermally and texturally mature organic materials of biogenic origin and can highlight organic-mineral interrelationships and elemental colocation at fine spatial scales. We also show that the Perseverance protocol obtains very similar results to high-performance laboratory imaging, Raman spectroscopy, and µXRF instruments. This is encouraging for the prospect of detecting microscale organic-bearing textural biosignatures on Mars using the correlative micro-analytical approach enabled by WATSON, SHERLOC, and PIXL; indeed, laminated, organic-bearing samples such as those studied herein are considered plausible analogues of biosignatures from a potential Noachian-Hesperian biosphere. Were similar materials discovered at Jezero crater, they would offer opportunities to reconstruct aspects of the early martian carbon cycle and search for potential fossilized traces of life in ancient paleoenvironments. Such samples should be prioritized for caching and eventual return to Earth.
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Meio Ambiente Extraterreno , Marte , Planeta Terra , Exobiologia/métodos , Minerais/análiseRESUMO
The Perseverance rover landed in Jezero crater, Mars, in February 2021. We used the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument to perform deep-ultraviolet Raman and fluorescence spectroscopy of three rocks within the crater. We identify evidence for two distinct ancient aqueous environments at different times. Reactions with liquid water formed carbonates in an olivine-rich igneous rock. A sulfate-perchlorate mixture is present in the rocks, which probably formed by later modifications of the rocks by brine. Fluorescence signatures consistent with aromatic organic compounds occur throughout these rocks and are preserved in minerals related to both aqueous environments.
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The search for organic biosignatures on Mars will depend on finding material protected from the destructive ambient radiation. Solar ultraviolet can induce photochemical degradation of organic compounds, but certain clays have been shown to preserve organic material. We examine how the SHERLOC instrument on the upcoming Mars 2020 mission will use deep-ultraviolet (UV) (248.6 nm) Raman and fluorescence spectroscopy to detect a plausible biosignature of adenosine 5'-monophosphate (AMP) adsorbed onto Ca-montmorillonite clay. We found that the spectral signature of AMP is not altered by adsorption in the clay matrix but does change with prolonged exposure to the UV laser over dosages equivalent to 0.2-6 sols of ambient martian UV. For pure AMP, UV exposure leads to breaking of the aromatic adenine unit, but in the presence of clay the degradation is limited to minor alteration with new Raman peaks and increased fluorescence consistent with formation of 2-hydroxyadenosine, while 1 wt % Mg perchlorate increases the rate of degradation. Our results confirm that clays are effective preservers of organic material and should be considered high-value targets, but that pristine biosignatures may be altered within 1 sol of martian UV exposure, with implications for Mars 2020 science operations and sample caching.
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Meio Ambiente Extraterreno , Marte , Monofosfato de Adenosina , Percloratos , Espectrometria de Fluorescência , Raios UltravioletaRESUMO
We describe the wavelength calibration of the spectrometer for the scanning of habitable environments with Raman and luminescence for organics and chemicals (SHERLOC) instrument onboard NASA's Perseverance Rover. SHERLOC utilizes deep ultraviolet Raman and fluorescence (DUV R/F) spectroscopy to enable analysis of samples from the Martian surface. SHERLOC employs a 248.6 nm deep ultraviolet laser to generate Raman-scattered photons and native fluorescence emission photons from near-surface material to detect and classify chemical and mineralogical compositions. The collected photons are focused on a charge-coupled device and the data are returned to Earth for analysis. The compact DUV R/F spectrometer has a spectral range from 249.9 nm to 353.6 nm (â¼200 cm-1 to 12 000 cm-1) (with a spectral resolution of 0.296 nm (â¼40 cm-1)). The compact spectrometer uses a custom design to project a high-resolution Raman spectrum and a low-resolution fluorescence spectrum on a single charge-coupled device. The natural spectral separation enabled by deep ultraviolet excitation enables wavelength separation of the Raman/fluorescence spectra. The SHERLOC spectrometer was designed to optimize the resolution of the Raman spectral region and the wavelength range of the fluorescence region. The resulting illumination on the charge-coupled device is curved, requiring a segmented, nonlinear wavelength calibration in order to understand the mineralogy and chemistry of Martian materials.
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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.
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Ozônio/química , Fragmentos de Peptídeos/química , Proteína B Associada a Surfactante Pulmonar/química , Sequência de Aminoácidos , Dicroísmo Circular , Diglicerídeos/química , Humanos , Cinética , Lipídeos/química , Pulmão/metabolismo , Modelos Moleculares , Dados de Sequência Molecular , Oxirredução , Ozônio/metabolismo , Fragmentos de Peptídeos/metabolismo , Proteína B Associada a Surfactante Pulmonar/metabolismo , Espectrometria de Massas por Ionização por Electrospray/métodosRESUMO
Raman spectroscopy is an invaluable technique for identifying compounds by the unique pattern of their molecular vibrations and is capable of quantifying the individual concentrations of those compounds provided that certain parameters about the sample and instrument are known. We demonstrate the development of an optical model to describe the intensity distribution of incident laser photons as they pass through the sample volume, determine the limitations of that volume that may be detected by the spectrometer optics, and account for light absorption by molecules within the sample in order to predict the total Raman intensity that would be obtained from a given, uniform sample such as an aqueous solution. We show that the interplay between the shape and divergence of the laser beam, the position of the focal plane, and the dimensions of the spectrometer slit are essential to explaining experimentally observed trends in deep ultraviolet Raman intensities obtained from both planar and volumetric samples, including highly oriented pyrolytic graphite and binary mixtures of organic nucleotides. This model offers the capability to predict detection limits for organic compounds in different matrices based on the parameters of the spectrometer, and to define the upper/lower limits within which concentration can be reliably determined from Raman intensity for such samples. We discuss the potential to quantify more complex samples, including as solid phase mixtures of organics and minerals, that are investigated by the unique instrument parameters of the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) investigation on the upcoming Mars 2020 rover mission.
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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.
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Gorduras Insaturadas/química , Espectrometria de Massas/métodos , Movimento (Física) , Fosfatidilcolinas/química , Calibragem , Peso Molecular , Fatores de TempoRESUMO
The next NASA-led Mars mission (Mars 2020) will carry a suite of instrumentation dedicated to investigating Martian history and the in situ detection of potential biosignatures. SHERLOC, a deep UV Raman/Fluorescence spectrometer has the ability to detect and map the distribution of many organic compounds, including the aromatic molecules that are fundamental building blocks of life on Earth, at concentrations down to 1 ppm. The mere presence of organic compounds is not a biosignature: there is widespread distribution of reduced organic molecules in the Solar System. Life utilizes a select few of these molecules creating conspicuous enrichments of specific molecules that deviate from the distribution expected from purely abiotic processes. The detection of far from equilibrium concentrations of a specific subset of organic molecules, such as those uniquely enriched by biological processes, would comprise a universal biosignature independent of specific terrestrial biochemistry. The detectability and suitability of a small subset of organic molecules to adequately describe a living system is explored using the bacterium Escherichia coli as a model organism. The DUV Raman spectra of E. coli cells are dominated by the vibrational modes of the nucleobases adenine, guanine, cytosine, and thymine, and the aromatic amino acids tyrosine, tryptophan, and phenylalanine. We demonstrate that not only does the deep ultraviolet (DUV) Raman spectrum of E. coli reflect a distinct concentration of specific organic molecules, but that a sufficient molecular complexity is required to deconvolute the cellular spectrum. Furthermore, a linear combination of the DUV resonant compounds is insufficient to fully describe the cellular spectrum. The residual in the cellular spectrum indicates that DUV Raman spectroscopy enables differentiating between the presence of biomolecules and the complex uniquely biological organization and arrangements of these molecules in living systems. This study demonstrates the ability of DUV Raman spectroscopy to interrogate a complex biological system represented in a living cell, and differentiate between organic detection and a series of Raman features that derive from the molecular complexity inherent to life constituting a biosignature.
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Terrestrial icy environments have been found to preserve organic material and contain habitable niches for microbial life. The cryosphere of other planetary bodies may therefore also serve as an accessible location to search for signs of life. The Wireline Analysis Tool for the Subsurface Observation of Northern ice sheets (WATSON) is a compact deep-UV fluorescence spectrometer for nondestructive ice borehole analysis and spatial mapping of organics and microbes, intended to address the heterogeneity and low bulk densities of organics and microbial cells in ice. WATSON can be either operated standalone or integrated into a wireline drilling system. We present an overview of the WATSON instrument and results from laboratory experiments intended to determine (i) the sensitivity of WATSON to organic material in a water ice matrix and (ii) the ability to detect organic material under various thicknesses of ice. The results of these experiments show that in bubbled ice the instrument has a depth of penetration of 10 mm and a detection limit of fewer than 300 cells. WATSON incorporates a scanning system that can map the distribution of organics and microbes over a 75 by 25 mm area. WATSON demonstrates a sensitive fluorescence mapping technique for organic and microbial detection in icy environments including terrestrial glaciers and ice sheets, and planetary surfaces including Europa, Enceladus, or the martian polar caps.
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Exobiologia/métodos , Meio Ambiente Extraterreno/química , Camada de Gelo/química , Compostos Orgânicos/análise , Júpiter , Marte , Espectrometria de Fluorescência/métodos , Raios UltravioletaRESUMO
The capability of detecting biomarkers, such as amino acids, in chemically complex field samples is essential to establishing the knowledge required to search for chemical signatures of life in future planetary explorations. However, due to the complexities of in situ investigations, it is important to establish a new analytical scheme that utilizes a minimal amount of sample preparation. This paper reports the feasibility of a novel and sensitive technique, which has been established to quantitate amino acids in terrestrial crust samples directly without derivatization using volatile ion-pairing liquid chromatography and tandem mass spectrometry equipped with an electrospray ionization source. Adequate separation of 20 underivatized amino acids was achieved on a C(18) capillary column within 26 min with nonafluoropentanoic acid (NFPA) as ion-pairing reagent. Each amino acid was identified from its retention time as well as from its characteristic parent-to-daughter ion transition. Using tandem mass spectrometry as a detection technique allows co-elution of some amino acids, as it is more specific than traditional spectrophotometric methods. In the present study, terrestrial samples collected from 3 different locations were analyzed for their water-extractable free amino acid contents, following the removal of metal and organic interferences via ion exchange procedures. This is the first time that amino acids in geological samples were directly determined quantitatively without complicated derivatization steps. Depending on the amino acid, the detection limits varied from 0.02 to 5.7 pmol with the use of a 1 microl sample injection loop.
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Aminoácidos/análise , Cromatografia Líquida/métodos , Geologia , Espectrometria de Massas por Ionização por Electrospray/métodos , Aminoácidos/química , Técnicas de Laboratório Clínico , Estudos de Viabilidade , Fenômenos Geológicos , Sensibilidade e EspecificidadeRESUMO
The Mars Program Plan includes an integrated and coordinated set of future candidate missions and investigations that meet fundamental science objectives of NASA and the Mars Exploration Program (MEP). At the time this paper was written, these possible future missions are planned in a manner consistent with a projected budget profile for the Mars Program in the next decade (2007-2016). As with all future missions, the funding profile depends on a number of factors that include the exact cost of each mission as well as potential changes to the overall NASA budget. In the current version of the Mars Program Plan, the Astrobiology Field Laboratory (AFL) exists as a candidate project to determine whether there were (or are) habitable zones and life, and how the development of these zones may be related to the overall evolution of the planet. The AFL concept is a surface exploration mission equipped with a major in situ laboratory capable of making significant advancements toward the Mars Program's life-related scientific goals and the overarching Vision for Space Exploration. We have developed several concepts for the AFL that fit within known budget and engineering constraints projected for the 2016 and 2018 Mars mission launch opportunities. The AFL mission architecture proposed here assumes maximum heritage from the 2009 Mars Science Laboratory (MSL). Candidate payload elements for this concept were identified from a set of recommendations put forth by the Astrobiology Field Laboratory Science Steering Group (AFL SSG) in 2004, for the express purpose of identifying overall rover mass and power requirements for such a mission. The conceptual payload includes a Precision Sample Handling and Processing System that would replace and augment the functionality and capabilities provided by the Sample Acquisition Sample Processing and Handling system that is currently part of the 2009 MSL platform.
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Exobiologia , Marte , Laboratórios , Voo Espacial , Estados Unidos , United States National Aeronautics and Space AdministrationRESUMO
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.
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Gases/química , Espectrometria de Massas por Ionização por Electrospray/instrumentação , Algoritmos , Anfetaminas/química , Cocaína/química , Indicadores e Reagentes , Peso Molecular , Peptídeos/química , Análise de RegressãoRESUMO
If life ever evolved on the surface of Mars, it is unlikely that it would still survive there today, but as Mars evolved from a wet planet to an arid one, the subsurface environment may have presented a refuge from increasingly hostile surface conditions. Since the last glacial maximum, the Mojave Desert has experienced a similar shift from a wet to a dry environment, giving us the opportunity to study here on Earth how subsurface ecosystems in an arid environment adapt to increasingly barren surface conditions. In this paper, we advocate studying the vadose zone ecosystem of the Mojave Desert as an analogue for possible subsurface biospheres on Mars. We also describe several examples of Mars-like terrain found in the Mojave region and discuss ecological insights that might be gained by a thorough examination of the vadose zone in these specific terrains. Examples described include distributary fans (deltas, alluvial fans, etc.), paleosols overlain by basaltic lava flows, and evaporite deposits.
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Vida , Marte , EcossistemaRESUMO
Stable isotope ratios of H, C, and O are powerful indicators of a wide variety of planetary geophysical processes, and for Mars they reveal the record of loss of its atmosphere and subsequent interactions with its surface such as carbonate formation. We report in situ measurements of the isotopic ratios of D/H and (18)O/(16)O in water and (13)C/(12)C, (18)O/(16)O, (17)O/(16)O, and (13)C(18)O/(12)C(16)O in carbon dioxide, made in the martian atmosphere at Gale Crater from the Curiosity rover using the Sample Analysis at Mars (SAM)'s tunable laser spectrometer (TLS). Comparison between our measurements in the modern atmosphere and those of martian meteorites such as ALH 84001 implies that the martian reservoirs of CO2 and H2O were largely established ~4 billion years ago, but that atmospheric loss or surface interaction may be still ongoing.
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Life Investigation For Enceladus (LIFE) presents a low-cost sample return mission to Enceladus, a body with high astrobiological potential. There is ample evidence that liquid water exists under ice coverage in the form of active geysers in the "tiger stripes" area of the southern Enceladus hemisphere. This active plume consists of gas and ice particles and enables the sampling of fresh materials from the interior that may originate from a liquid water source. The particles consist mostly of water ice and are 1-10 µ in diameter. The plume composition shows H(2)O, CO(2), CH(4), NH(3), Ar, and evidence that more complex organic species might be present. Since life on Earth exists whenever liquid water, organics, and energy coexist, understanding the chemical components of the emanating ice particles could indicate whether life is potentially present on Enceladus. The icy worlds of the outer planets are testing grounds for some of the theories for the origin of life on Earth. The LIFE mission concept is envisioned in two parts: first, to orbit Saturn (in order to achieve lower sampling speeds, approaching 2 km/s, and thus enable a softer sample collection impact than Stardust, and to make possible multiple flybys of Enceladus); second, to sample Enceladus' plume, the E ring of Saturn, and the Titan upper atmosphere. With new findings from these samples, NASA could provide detailed chemical and isotopic and, potentially, biological compositional context of the plume. Since the duration of the Enceladus plume is unpredictable, it is imperative that these samples are captured at the earliest flight opportunity. If LIFE is launched before 2019, it could take advantage of a Jupiter gravity assist, which would thus reduce mission lifetimes and launch vehicle costs. The LIFE concept offers science returns comparable to those of a Flagship mission but at the measurably lower sample return costs of a Discovery-class mission.
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Exobiologia/métodos , Meio Ambiente Extraterreno/química , Atmosfera , Gases/química , Planetas , Estados Unidos , United States National Aeronautics and Space Administration , Água/químicaRESUMO
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.
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Ozônio/química , Fosfolipídeos/química , Surfactantes Pulmonares/química , Tensoativos/química , 1,2-Dipalmitoilfosfatidilcolina/química , Ar , Oxirredução , Fosfatidilcolinas/química , Fosfatidilgliceróis/química , Espectrometria de Massas por Ionização por Electrospray , Fatores de TempoRESUMO
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.