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      Synthesis of Autofluorescent Phenanthrene Microparticles via Emulsification: A Useful Synthetic Mimic for Polycyclic Aromatic Hydrocarbon-Based Cosmic Dust

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          Abstract

          Phenanthrene is the simplest example of a polycyclic aromatic hydrocarbon (PAH). Herein, we exploit its relatively low melting point (101 °C) to prepare microparticles from molten phenanthrene droplets by conducting high-shear homogenization in a 3:1 water/ethylene glycol mixture at 105 °C using poly( N-vinylpyrrolidone) as a non-ionic polymeric emulsifier. Scanning electron microscopy studies confirm that this protocol produces polydisperse phenanthrene microparticles with a spherical morphology: laser diffraction studies indicate a volume-average diameter of 25 ± 21 μm. Such projectiles are fired into an aluminum foil target at 1.87 km s –1 using a two-stage light gas gun. Interestingly, the autofluorescence exhibited by phenanthrene aids analysis of the resulting impact craters. More specifically, it enables assessment of the spatial distribution of any surviving phenanthrene in the vicinity of each crater. Furthermore, these phenanthrene microparticles can be coated with an ultrathin overlayer of polypyrrole, which reduces their autofluorescence. In principle, such core–shell microparticles should be useful for assessing the extent of thermal ablation that is likely to occur when they are fired into aerogel targets. Accordingly, polypyrrole-coated microparticles were fired into an aerogel target at 2.07 km s –1. Intact microparticles were identified at the end of carrot tracks and their relatively weak autofluorescence suggests that thermal ablation during aerogel capture did not completely remove the polypyrrole overlayer. Thus, these new core–shell microparticles appear to be useful model projectiles for assessing the extent of thermal processing that can occur in such experiments, which have implications for the capture of intact PAH-based dust grains originating from cometary tails or from plumes emanating from icy satellites (e.g., Enceladus) in future space missions.

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          A salt-water reservoir as the source of a compositionally stratified plume on Enceladus.

          The discovery of a plume of water vapour and ice particles emerging from warm fractures ('tiger stripes') in Saturn's small, icy moon Enceladus raised the question of whether the plume emerges from a subsurface liquid source or from the decomposition of ice. Previous compositional analyses of particles injected by the plume into Saturn's diffuse E ring have already indicated the presence of liquid water, but the mechanisms driving the plume emission are still debated. Here we report an analysis of the composition of freshly ejected particles close to the sources. Salt-rich ice particles are found to dominate the total mass flux of ejected solids (more than 99 per cent) but they are depleted in the population escaping into Saturn's E ring. Ice grains containing organic compounds are found to be more abundant in dense parts of the plume. Whereas previous Cassini observations were compatible with a variety of plume formation mechanisms, these data eliminate or severely constrain non-liquid models and strongly imply that a salt-water reservoir with a large evaporating surface provides nearly all of the matter in the plume.
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            Macromolecular organic compounds from the depths of Enceladus

            Saturn’s moon Enceladus harbours a global ocean 1 , which lies under an ice crust and above a rocky core 2 . Through warm cracks in the crust 3 a cryo-volcanic plume ejects ice grains and vapour into space 4–7 , providing access to materials originating from the ocean 8,9 . Hydrothermal activity is suspected to be occurring deep inside the water-percolated porous core 10–12 , powered by tidal dissipation 13 . So far only simple organic compounds with molecular masses mostly below 50u have been observed in the plume 6,14,15 . Here we report observations of emitted ice grains containing concentrated, complex, macromolecular organic material with molecular masses above 200u. The data provides key constraints on the macromolecular structure and is suggestive of a thin organic-rich film on top of the oceanic water table. There, organic nucleation cores generated by bubble bursting allow probing of Enceladus’ organic inventory in drastically enhanced concentrations.
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              A reduced organic carbon component in martian basalts.

              The source and nature of carbon on Mars have been a subject of intense speculation. We report the results of confocal Raman imaging spectroscopy on 11 martian meteorites, spanning about 4.2 billion years of martian history. Ten of the meteorites contain abiotic macromolecular carbon (MMC) phases detected in association with small oxide grains included within high-temperature minerals. Polycyclic aromatic hydrocarbons were detected along with MMC phases in Dar al Gani 476. The association of organic carbon within magmatic minerals indicates that martian magmas favored precipitation of reduced carbon species during crystallization. The ubiquitous distribution of abiotic organic carbon in martian igneous rocks is important for understanding the martian carbon cycle and has implications for future missions to detect possible past martian life.
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                Author and article information

                Journal
                ACS Appl Mater Interfaces
                ACS Appl Mater Interfaces
                am
                aamick
                ACS Applied Materials & Interfaces
                American Chemical Society
                1944-8244
                1944-8252
                09 November 2023
                22 November 2023
                : 15
                : 46
                : 54039-54049
                Affiliations
                []Dainton Building, Department of Chemistry, University of Sheffield , Brook Hill, Sheffield, South Yorkshire S3 7HF, U.K.
                []School of Physics and Astronomy, University of Kent , Canterbury, Kent CT2 7NH, U.K.
                [§ ]School of Chemistry and Forensic Science, University of Kent , Canterbury, Kent CT2 7NZ, U.K.
                Author notes
                Author information
                https://orcid.org/0000-0002-2680-8943
                https://orcid.org/0000-0002-8289-6351
                Article
                10.1021/acsami.3c08585
                10685351
                37944021
                c05ad610-6294-43ba-8f6b-4713e6cc3ff1
                © 2023 The Authors. Published by American Chemical Society

                Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained ( https://creativecommons.org/licenses/by/4.0/).

                History
                : 14 June 2023
                : 24 October 2023
                : 19 October 2023
                Funding
                Funded by: Engineering and Physical Sciences Research Council, doi 10.13039/501100000266;
                Award ID: EP/R003009/1
                Funded by: Leverhulme Trust, doi 10.13039/501100000275;
                Award ID: RPG-2022-260
                Funded by: Science and Technology Facilities Council, doi 10.13039/501100000271;
                Award ID: NA
                Categories
                Research Article
                Custom metadata
                am3c08585
                am3c08585

                Materials technology
                phenanthrene,polycyclic aromatic hydrocarbons,polypyrrole,cosmic dust,synthetic mimics,emulsification

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