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At least 1,081 records · Page 60

Giant Angular Nernst Effect in the Organic Metal α-(BEDT-TTF) 2 KHg(SCN) 4

We have detected a large Nernst effect in the charge density wave state of the multiband organic metal α-(BEDT-TTF) 2 KHg(SCN) 4 . We find that apart from the phonon drag effect, the energy relaxation processes that govern the electron–phonon interactions and the momentum relaxation processes that determine the mobility of the q1D charge carriers have a significant role in observing the large Nernst signal in the CDW state in this organic metal. The emphasised momentum relaxation dynamics in the low field CDW state (CDW 0 ) is a clear indicator of the presence of a significant carrier mobility that might be the main source for observation of the largest Nernst signal. The momentum relaxation is absent with increasing angle and magnetic field, i.e., in the high-field CDW state (CDW x ) as evident from the much smaller Nernst effect amplitude in this state. In this case, only the phonon drag effect and electron–phonon interactions are contributing to the transverse thermoelectric signal. Our findings advance and change previous observations on the complex properties of this organic metal.

36 MATERIALS SCIENCE↗

Effect of inorganic-to-organic mass ratio on the heterogeneous OH reaction rates of erythritol: implications for atmospheric chemical stability of 2-methyltetrols

The 2-methyltetrols have been widely chosen as chemical tracers for isoprene-derived secondary organic aerosols. While they are often assumed to be relatively unreactive, a laboratory study reported that pure erythritol particles (an analog of 2-methyltetrols) can be heterogeneously oxidized by gas-phase OH radicals at a significant rate. This might question the efficacy of these compounds as tracers in aerosol source-apportionment studies. Additional uncertainty could arise as organic compounds and inorganic salts often coexist in atmospheric particles. To gain more insights into the chemical stability of 2-methyltetrols in atmospheric particles, this study investigates the heterogeneous OH oxidation of pure erythritol particles and particles containing erythritol and ammonium sulfate (AS) at different dry inorganic-to-organic mass ratios (IOR) in an aerosol flow tube reactor at a high relative humidity of 85 %. The same reaction products are formed upon heterogenous OH oxidation of erythritol and erythritol–AS particles, suggesting that the reaction pathways are not strongly affected by the presence and amount of AS. On the other hand, the effective OH uptake coefficient, $γ_{eff}$, is found to decrease by about a factor of ~20 from 0.45±0.025 to 0.02±0.001 when the relative abundance of AS increases and the IOR increases from 0.0 to 5.0. One likely explanation is the presence of dissolved ions slows down the reaction rates by decreasing the surface concentration of erythritol and reducing the frequency of collision between erythritol and gas-phase OH radicals at the particle surface. Hence, the heterogeneous OH reactivity of erythritol and likely 2-methyltetrols in atmospheric particles would be slower than previously thought when the salts are present. Given 2-methyltetrols often coexist with a significant amount of AS in many environments, where ambient IOR can vary from ~1.89 to ~250, our kinetic data would suggest that 2-methyltetrols in atmospheric particles are likely chemically stable against heterogeneous OH oxidation under humid conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exploration of oxidative chemistry and secondary organic aerosol formation in the Amazon during the wet season: explicit modeling of the Manaus urban plume with GECKO-A

The GoAmazon 2014/5 field campaign took place in Manaus, Brazil, and allowed the investigation of the interaction between background-level biogenic air masses and anthropogenic plumes. We present in this work a box model built to simulate the impact of urban chemistry on biogenic secondary organic aerosol (SOA) formation and composition. An organic chemistry mechanism is generated with the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to simulate the explicit oxidation of biogenic and anthropogenic compounds. A parameterization is also included to account for the reactive uptake of isoprene oxidation products on aqueous particles. The biogenic emissions estimated from existing emission inventories had to be reduced to match measurements. The model is able to reproduce ozone and NO x for clean and polluted situations. The explicit model is able to reproduce background case SOA mass concentrations but does not capture the enhancement observed in the urban plume. The oxidation of biogenic compounds is the major contributor to SOA mass. A volatility basis set (VBS) parameterization applied to the same cases obtains better results than GECKO-A for predicting SOA mass in the box model. The explicit mechanism may be missing SOA-formation processes related to the oxidation of monoterpenes that could be implicitly accounted for in the VBS parameterization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Growth and morphogenesis of embryonic mouse organs on non-coated and extracellular matrix-coated Biopore membrane

Embryonic mouse salivary glands, pancreata, and kidneys were isolated from embryos of appropriate gestational age by microdissection, and were cultured on Biopore membrane either non-coated or coated with type I collagen or Matrigel. As expected, use of Biopore membrane allowed high quality photomicroscopy of the living organs. In all organs extensive mesenchymal spreading was observed in the presence of type I collagen or Matrigel. However, differences were noted in the effects of extracellular matrix (ECM) coatings on epithelial growth and morphogenesis: salivary glands were minimally affected, pancreas morphogenesis was adversely affected, and kidney growth and branching apparently was enhanced. It is suggested that these differences in behaviour reflect differences in the strength of interactions between the mesenchymal cells and their surrounding endogenous matrix, compared to the exogenous ECM macromolecules. This method will be useful for culture of these and other embryonic organs. In particular, culture of kidney rudiments on ECM-coated Biopore offers a great improvement over previously used methods which do not allow morphogenesis to be followed in vitro.

NASA Discipline Number 93-10↗

The oxygen content of ocean bottom waters, the burial efficiency of organic carbon, and the regulation of atmospheric oxygen

Data for the burial efficiency of organic carbon with marine sediments have been compiled for 69 locations. The burial efficiency as here defined is the ratio of the quantity of organic carbon which is ultimately buried to that which reaches the sediment-water interface. As noted previously, the sedimentation rate exerts a dominant influence on the burial efficiency. The logarithm of the burial efficiency is linearly related to the logarithm of the sedimentation rate at low sedimentation rates. At high sedimentation rates the burial efficiency can exceed 50% and becomes nearly independent of the sedimentation rate. The residual of the burial efficiency after the effect of the sedimentation rate has been subtracted is a weak function of the O2 concentration in bottom waters. The scatter is sufficiently large, so that the effect of the O2 concentration in bottom waters on the burial efficiency of organic matter could be either negligible or a minor but significant part of the mechanism that controls the level of O2 in the atmosphere.

Non-NASA Center↗

Shape deformation of the organ of Corti associated with length changes of outer hair cell

Cochlear outer hair cells (OHC) are commonly assumed to function as mechanical effectors as well as sensory receptors in the organ of Corti (OC) of the inner ear. OHC in vitro and in organ explants exhibit mechanical responses to electrical, chemical or mechanical stimulation which may represent an aspect of their effector process that is expected in vivo. A detailed description, however, of an OHC effector operation in situ is still missing. Specifically, little is known as to how OHC movements influence the geometry of the OC in situ. Previous work has demonstrated that the motility of isolated OHCs in response to electrical stimulation and to K(+)-gluconate is probably under voltage control and causes depolarisation (shortening) and hyperpolarization (elongation). This work was undertaken to investigate if the movements that were observed in isolated OHC, and which are induced by ionic stimulation, could change the geometry of the OC. A synchronized depolarization of OHC was induced in guinea pig cochleae by exposing the entire OC to artificial endolymph (K+). Subsequent morphometry of mid-modiolar sections from these cochleae revealed that the distance between the basilar membrane (BM) and the reticular lamina (RL) had decreased considerably. Furthermore, in the three upper turns OHC had significantly shortened in all rows. The results suggest that OHC can change their length in the organ of Corti (OC) thus deforming the geometry of the OC. The experiments reveal a tonic force generation within the OC that may change the position of RL and/or BM, contribute to damping, modulate the BM-RL-distance and control the operating points of RL and sensory hair bundles. Thus, the results suggest active self-adjustments of cochlear mechanics by slow OHC length changes. Such mechanical adjustments have recently been postulated to correspond to timing elements of animal communication, speech or music.

Non-NASA Center↗

Hydrogen emission in meteors as a potential marker for the exogenous delivery of organics and water

We detected hydrogen Balmer-alpha (H(alpha)) emission in the spectra of bright meteors and investigated its potential use as a tracer for exogenous delivery of organic matter. We found that it is critical to observe the meteors with high enough spatial resolution to distinguish the 656.46 nm H(alpha) emission from the 657.46 nm intercombination line of neutral calcium, which was bright in the meteor afterglow. The H(alpha) line peak stayed in constant ratio to the atmospheric emissions of nitrogen during descent of the meteoroid. If all of the hydrogen originates in the Earth's atmosphere, the hydrogen atoms are expected to have been excited at T = 4400 K. In that case, we measured an H(2)O abundance in excess of 150 +/- 20 ppm at 80-90 km altitude (assuming local thermodynamic equilibrium in the air plasma). This compares with an expected <20 ppm from H(2)O in the gas phase. Alternatively, meteoric refractory organic matter (and water bound in meteoroid minerals) could have caused the observed H(alpha) emission, but only if the line is excited in a hot T approximately 10000 K plasma component that is unique to meteoric ablation vapor emissions such as Si(+). Assuming that the Si(+) lines of the Leonid spectrum would need the same hot excitation conditions, and a typical [H]/[C] = 1 in cometary refractory organics, we calculated an abundance ratio [C]/[Si] = 3.9 +/- 1.4 for the dust of comet 55P/Tempel-Tuttle. This range agreed with the value of [C]/[Si] = 4.4 measured for comet 1P/Halley dust. Unless there is 10 times more water vapor in the upper atmosphere than expected, we conclude that a significant fraction of the hydrogen atoms in the observed meteor plasma originated in the meteoroid.

Water↗

Meteor wake in high frame-rate images--implications for the chemistry of ablated organic compounds

Extraterrestrial organic matter may have been chemically altered into forms more ameanable for prebiotic chemistry in the wake of a meteor after ablation. We measured the rate of cooling of the plasma in the meteor wake from the intensity decay just behind a meteoroid by freezing its motion in high frame-rate 1000 frames/s video images, with an intensified camera that has a short phosphor decay time. Though the resulting cooling rate was found to be lower than theoretically predicted, our calculations indicated that there would have been insufficient collisions to break apart large organic compounds before most reactive radicals and electrons were lost from the air plasma. Organic molecules delivered from space to the early Earth via meteors might therefore have survived in a chemically altered form. In addition, we discovered that relatively small meteoroids generated far-ultraviolet emission that is absorbed in the immediate environment of the meteoroid, which may chemically alter the atmosphere over a much larger region than previously recognized.

Meteoroids↗

XANES Analysis of Organic Residues Produced from the UV Irradiation of Astrophysical Ice Analogs

Organic residues formed in the laboratory from the ultraviolet (UV) photo-irradiation or ion bombardment of astrophysical ice analogs have been extensively studied for the last 15 years with a broad suite of techniques, including infrared (IR) and UV spectroscopies, as well as mass spectrometry. Analyses of these materials show that they consist of complex mixtures of organic compounds stable at room temperature, mostly soluble, that have not been fully characterized. However, the hydrolysis products of these residues have been partly identified using chromatography techniques, which indicate that they contain molecular precursors of prebiotic interest such as amino acids, nitrile-bearing compounds, and amphiphilic compounds. In this study, we present the first X-ray absorption near-edge structure (XANES) spectroscopy measurements of three organic residues made from the UV irradiation of ices having different starting compositions. XANES spectra confirm the presence of different chemical functions in these residues, and indicate that they are rich in nitrogenand oxygen-bearing species. These data can be compared with XANES measurements of extraterrestrial materials. Finally, this study also shows how soft X rays can alter the chemical composition of samples.

XANES(X-RAY ABSORPTION NEAR-EDGE STRUCTURE)↗

The Organization and Management of the Virtual Astronomical Observatory

The U.S. Virtual Astronomical Observatory (VAO; http://www.us-vao.org/) has been in operation since May 2010. Its goal is to enable new science through efficient integration of distributed multi-wavelength data. This paper describes the management and organization of the VAO, and emphasizes the techniques used to ensure efficiency in a distributed organization. Management methods include using an annual program plan as the basis for establishing contracts with member organizations, regular communication, and monitoring of processes.

management↗

Origin of Chlorobenzene Detected by the Curiosity Rover in Yellowknife Bay: Evidence for Martian Organics in the Sheepbed Mudstone?

The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally evolved from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. The first solid samples analyzed by SAM, a scoop of windblown dust and sand at Rocknest (RN), revealed chlorinated hydrocarbons derived primarily from reactions between a martian oxychlorine phase (e.g. perchlorate) and terrestrial carbon from N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA) vapor present in the SAM instrument background. Chlorobenzene (CBZ) was also identified by SAM GCMS at RN at trace levels (approx.0.007 nmol) and was attributed to the reaction of chlorine with the Tenax polymers used in the hydrocarbon traps. After the RN analyses, Curiosity traveled to Yellowknife Bay and drilled two separate holes designated John Klein (JK) and Cumberland (CB). Analyses of JK and CB by both SAM and the CheMin x-ray diffraction instrument revealed a mudstone consisting of approx.20 wt% smectite clays, which on Earth are known to aid the concentration and preservation of organic matter. In addition, higher abundances and a more diverse suite of chlorinated hydrocarbons in CB compared to RN suggests that martian or meteoritic organic sources may be preserved in the mudstone. Here we discuss the SAM EGA and GCMS measurements of volatiles released from the Sheepbed mudstone. We focus primarily on the elevated CBZ detections at CB and laboratory analog experiments conducted to help determine if CBZ is derived from primarily terrestrial, martian, or a combination of sources.

origin of↗

Organics in Space: Results from Space Exposure Platforms and Nanosatellites

A series of successful laboratory astrophysics experiments performed on International Space Station(ISS) external platforms such as EXPOSE have provided insights into the evolution of organic and biological materials in space and planetary environments. The study of the reactions, destruction, and longevity of organics in the space environment is of fundamental interest. To provide an accurate outer space environment for extended durations, exposure experiments in low Earth orbit have been conducted in the last decades in order to examine the consequences of actual space conditions including combinations of solar and cosmic radiation, space vacuum, and microgravity. The OOREOS (OrganismORganic Exposure to Orbital Stresses) nanosatellite studied in situ during the 6-month primary and 1-year extended mission the photochemical processing of selected PAHs in low Earth orbit (650 km altitude); results were autonomously telemetered to Earth. We report on the methods and flight preparation of samples for space exposure platforms and results on the stability of organic thin-films. The UV-vis degradation process of thin-films was recorded over time, which revealed intriguing and counter-intuitive photolytic kinetics that will be re-investigated on the ISS in a space environment.

Space weathering↗

Design and Demonstration of the Mars Organic Molecule Analyzer (MOMA) on the ExoMars 2018 Rover

The Mars Organic Molecule Analyzer (MOMA) investigation is a key astrobiology experiment scheduled to launch on the joint ESA-Roscosmos ExoMars 2018 rover mission. MOMA will examine the chemical composition of geological samples acquired from depths of up to two meters below the martian surface, where fragile organic molecules may be protected from destructive cosmic radiation and/or oxidative chemical reactions. The heart of the MOMA mass spectrometer subsystem (i.e., MOMA-MS) is a miniaturized linear ion trap (LIT) that supports two distinct modes of operation to detect: i) volatile and semi-volatile, low-to-moderate mass organics (less than or equal to 500 Da) via pyrolysis coupled with gas chromatography mass spectrometry (pyr/GCMS); and, ii) more refractory, moderate-to-high mass compounds (up to 1000 Da) via laser desorption (LDMS) at ambient Mars pressures. Additionally, the LIT mass analyzer enables selective ion trapping via multi-frequency waveform ion excitation (e.g., stored waveform inverse Fourier transform, or SWIFT), and structural characterization of complex molecules using tandem mass spectrometry (MSIMS). A high-fidelity Engineering Test Unit (ETU) of MOMAMS, including the LIT subassembly, dual-gun electron ionization source, micropirani pressure gauge, solenoid-driven aperture valve, redundant detection chains, and control electronics, has been built and tested at NASA GSFC under relevant operational conditions (pressure, temperature, etc.). Spaceflight qualifications of individual hardware components and integrated subassemblies have been validated through vibration, shock, thermal, lifetime, and performance evaluations. The ETU serves as a pathfinder for the flight model buildup, integration and test, as the ETU meets the form, fit and function of the flight unit that will be delivered to MPS in late 2015. To date, the ETU of MOMA-MS has been shown to meet or exceed all functional requirements, including mass range, resolution, accuracy, instrumental drift, and Iimit-of-detection specifications, thereby enabling the primary science objectives of the MOMA investigation and ExoMars 2018 mission.

Mars Organic Molecule Analyzer↗

Organic Components of Small Bodies in the Outer Solar System: Some Results of the New Horizons Mission

The close encounters of the Pluto–Charon system and the Kuiper Belt object Arrokoth (formerly 2014 MU 69 ) by NASA’s New Horizons spacecraft in 2015 and 2019, respectively, have given new perspectives on the most distant planetary bodies yet explored. These bodies are key indicators of the composition, chemistry, and dynamics of the outer regions of the Solar System’s nascent environment. Pluto and Charon reveal characteristics of the largest Kuiper Belt objects formed in the dynamically evolving solar nebula inward of ~30 AU, while the much smaller Arrokoth is a largely undisturbed relic of accretion at ~45 AU. The surfaces of Pluto and Charon are covered with volatile and refractory ices and organic components, and have been shaped by geological activity. On Pluto, N 2 , CO and CH 4 are exchanged between the atmosphere and surface as gaseous and condensed phases on diurnal, seasonal and longer timescales, while Charon’s surface is primarily inert H 2 O ice with an ammoniated component and a polar region colored with a macromolecular organic deposit. Arrokoth is revealed as a fused binary body in a relatively benign space environment where it originated and has remained for the age of the Solar System. Its surface is a mix of CH 3 OH ice, a red-orange pigment of presumed complex organic material, and possibly other undetected components.

Solar System↗

Reduced Organic Outgassing in the NASA Osiris-Rex and Hayabusa2 Curation Facility by Careful Selection and Implementation of Cleanroom Construction Materials

In October 2021, NASA Johnson Space Center (JSC) Astromaterials Acquisition and Cu-ration Office in JSC bldg. 31 completed construction and commissioning of the OSIRIS-REx and Hayabusa2cleanroom laboratory suites along with new precision cleaning and advanced curation laboratories: •OSIRIS-REx Curation Cleanroom: ISO Class 5•Hayabusa2 Curation Cleanroom: ISO Class 5•Final Precision Cleaning Cleanroom: ISO Class 5•Advanced Precision Cleaning Cleanroom: ISO Class 6•PreClean Precision Cleaning Cleanroom: ISO Class 6•Advanced Curation Cleanroom: ISO Class 7The new curation facilities are designed for initial receiving, basic characterization, curation processing, and preliminary examination of carbonaceous asteroidal material. The facilities are also designed to enable long-term pristine sample storage to preserve the scientific integrity of each sample to enable decades of future re-search by the international science community. The scientific study of organics in general is critical for both missions. The OSIRIS-REx mission executed a stringent contamination control plan [1] where all sample hardware at time of sample acquisition would be at Level 100 A/2 per IEST-STD-CC1246D (non-volatile residue (NVR) < 500 ng/cm2). In addition, the mission imposed a requirement of <180 ng/cm2 for amino acids (and hydrazine) [1]. Given these mission requirements, long-term storage preservation requirements, and information from the Organic Contamination Baseline Study at JSC [2], the JSC Curation team decided to carefully select cleanroom construction materials that would not hinder the scientific search for amino acids and the study of organics in the samples [3].

astromaterials curation↗

Indigenous Organic Matter Associated with Unusual Low Temperature Aqueous Secondary Phases in the Mars Meteorite Nakhla

The Martian meteorite Nakhla provides demonstrates evidence of mineral-water interactions that occurred in the Martian regolith within the last 1 Ga, as well as the presence of trace indigenous organic matter. The aim of our research is threefold: [1] provide a context in which to interpret alteration features; [2] determine the physical and chemical environment during alteration; and, [3] investigate the hypothesis that the formation of alteration phases was intimately involved in the accumulation and/or preservation of organic matter. In freshly fractured chips of the Mars meteorite Nakhla, we found carbonaceous matter intimately associated with secondary aqueous alteration phases interpreted to have formed through the low-temperature, mineral-water dissolution of the host Martian basalt. We have characterized the nature of carbonaceous matter and spatially associated secondary phases within Nakhla using a multidisciplinary suite of analytical instrumentation. The aim of our research is to provide a context to interpret the formation of secondary alteration assemblages within the Mars meteorite Nakhla and determine whether, and if so the extent to which, these phases participated in the accumulation and preservation of Martian organic matter.

Mars meteorite↗

Surface-Enhanced Raman Spectroscopy (SERS) for Venus Atmospheric Characterization and Trace Organics Identification

The chemical composition of Venus’ clouds has attracted considerable attention since the first atmospheric probes entered the planet in the early 1980s. We know from these early studies that cloud aerosols consist of micron and submicron droplets of sulfuric acid (~85%) and water (~15%), but outstanding questions still exist regarding their trace chemical composition, especially the identity of the unknown UV absorber(s) and the possible presence of organic material (Spacek & Benner, 2021). Veritas and DaVinci will launch at the end of the decade to advance our understanding of Venus’ surface and atmosphere, however these missions are not designed to sample and analyze cloud aerosols at trace levels. Raman spectroscopy is an ideal candidate for characterizing aerosols and has a track record in studies of Earth’s atmosphere. Raman provides broad chemical screening of organic and inorganic molecules within seconds, and Raman instrumentation can be miniaturized to meet the stringent size, weight, and power (SWaP) constraints of an atmospheric probe while retaining sensitivity and specificity that allow spectral fingerprinting of compounds and functional groups. Raman alone is insufficient to characterize trace constituents however, as limits of detection are typically in the 10s to 100s of ppm at best for planetary Raman spectrometers. Surface-Enhanced Raman Spectroscopy (SERS), a method that utilizes nanoscale materials interacting with a sample to enhance weak Raman signals by orders of magnitude when probed by a laser, has the potential to drastically improve the sensitivity of a Raman instrument while adding little-to-no SWaP nor complexity to a scientific payload. We aim to de-risk SERS technology for rapid infusion in future planetary science missions by developing custom SERS substrates tailored towards Venus atmospheric exploration. We have developed SERS substrates consisting of nanotextured silver films and tested them on potential Venus-relevant organic compounds, with preliminary results indicating sub-ppm sensitivity. Additionally, we have planned tests to investigate durability, longevity, and other key characteristics that impact SERS substrate performance to prepare SERS technology for flight.

Venus↗

Organic semiconductor compounds and methods of use

Organic perylene diimide-based compounds are provided. Methods of producing the organic compounds is also provided as well as methods of their use including, among other things, their use as organic semiconductor materials.

36 MATERIALS SCIENCE↗