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At least 91 records · Page 5

Assessing Organic Preservation and the Implications for Potential Biosignatures in the Bastide Member of the Séítah Formation, Jezero Crater

Introduction: Olivine has the highest CO2 trapping potential of ultramafic minerals, due to its rapid rate of dissolution and high percentage of divalent cations/unpolymerized silicate tetrahedra [1]. It generates divalent carbonates from CO2 and sequesters CO2 into the mineral matrix of the target lithology. The co-occurrence of olivine and carbonate within abraded targets from the Bastide Member of the Séítah Formation (Fm) of the Jezero crater floor [2] suggests the carbonation of olivine occurred within the mineral matrix hosted in a subsurface system. Hydrothermal origins for the subsurface system are hypothesized from orbital data [3]. This is supported by the detection of hydration features within the rock as well as the carbonate features are solely detected within the abrasion patch but not the rock’s surface. Organic preservation potential of abrasion patches: We incorporated the SHERLOC/WATSON results acquired from the Dourbes, Garde, and Quartier abrasion patches in the Séítah Fm to investigate the organomineral associations, and determine the biosignature preservation potential of these rocks. Dourbes is dominated by olivine and has minor amounts of carbonate, hydrated Ca-sulfate, and amorphous or microcrystalline silicate. Fluorescence features (330-340 nm) are detected in discrete locales and could be consistent with double ring aromatic organic molecules; yet, these features do not appear to be associated with an identified mineral phase. Dark subhedral to euhedral olivine grains within the Garde abrasion patch often co-occur with carbonate-consistent spectral signatures in all analyzed scans. The availability of Fe2+ is a known influence on olivine dissolution rates [1] and SuperCam estimates of the olivine composition (Forsterite-60 average for Sols 202-234) may thereby provide a constraint on the carbonation extent. Carbonated olivine phenocrysts within the matrix may be due to aqueous alteration, as the carbonation of nodules is consistent with observations in other hydrothermal systems and within Martian meteorites (ALH84001) [4]. In comparison, the Quartier abrasion patch represents an extensively altered endmember within the Bastide Member of the Séítah Fm. It contains a fluorescence doublet at 305/325 nm that coexists with multiple species of Na-sulfate and Mg-sulfate, Mg-carbonates, olivine [5]. Aqueous alteration and implications for habitability: The identification of primary and secondary mineral phases observed in the Bastide Member suggests the release of cations from primary ultramafic minerals through aqueous alteration. Within Garde, the carbonate detected appears to be Mg-rich and likely formed from the in situ alteration of Mg-rich olivine within the region as carbonate has only been detected within the rock via in situ analysis. Carbonates derived from abiotic and biotic reactions preserve biosignatures (i.e. indices of habitability) on Earth. The detected carbonate phase found in association with fluorescent features within the rock matrix may also indicate potential organic compounds preserved in a putative hydrothermal system. Fluorescent features (~330 nm) are unique to Garde and Dourbes, though they are co-located to carbonate signatures solely within Garde, and between the light toned minerals. Identification of these fluorescent features may be consistent with 1-2 ring aromatic compounds. The limit of detection for Raman is multiple orders of magnitude greater than the limit of detection required for fluorescence [6]. Implications for provenance: Hydrothermal systems represent disequilibrium chemical conditions that are hypothesized to have supported the emergence of life and also preserve ancient carbon within precipitated carbonates [7]. Hydrothermal system associated carbonates are capable of preserving biosignatures up to an estimated ~3.77 – 4.28 Gya [8]. Thus, carbonated olivine found within the Séítah Fm may represent a high-potential biosignature preserving environment on Mars. The formation of carbonates by an aqueous alteration process, such as carbonation of olivine is also consistent with hypotheses for carbonate within the greater regional-olivine bearing unit [2,3], which contains Garde, Dourbes, and Quartier. Acknowledgments: This work was carried out at the Jet Propulsion Laboratory, The California Institute of Technology under a contract from NASA. References: [1] Wood et al., (2019) ES&T, 6, 10. [2] Stack, K. et al., (2020) Space Sci Rev, 216, 127. [3] Tarnas, J. et al., (2021) JGR: Planets, 126, 11. [4] Steele et al., (2007) Meteorit. Planet. Sci., 42, 9. [5] Murphy, A.E. et al., (2022) LPSC [6] Bhartia et al., (2021) Space Sci Rev, 217, 58. [7] Luther (2021) GRL, 48, e2021GL094869. [8] Dodd et al., (2017) Nature, 543, 60-64

E L Cardarelli↗

Asteroid (90) Antiope: Another Icy Member of the Themis Family?

Many members of the Themis family show evidence of hydration in the form of oxidized iron in phyllosilicates (Florczak, M. et al. [1999]. Astron. Astrophys. Suppl. Ser. 134, 463–471), and OH-bearing minerals (Takir, D., Emery, J.P. [2012]. Icarus 219, 641–654). The largest member, (24) Themis, has H2O ice covering its surface (Campins, H. et al. [2010]. Nature 464, 1320–1321; Rivkin, A.S., Emery, J.P. [2010]. Nature 464, 1322–1323). We have investigated the second largest Themis-family asteroid, (90) Antiope, which Castillo-Rogez and Schmidt (Castillo-Rogez, J.C., Schmidt, B.E. [2010]. Geophys. Res. Lett. 37, L10202) predict to have a composition that includes water ice and organics. We obtained 2–4-lm spectroscopy of (90) Antiope in 2006 and 2008, and we find an absorption in the 3-lm region clearly present in our 2008 spectrum and likely in our 2006 spectrum. Both spectra have rounded, bowl-shaped absorptions consistent with those ascribed to water ice as in the spectrum of Asteroid (24) Themis. We also present and compare Spitzer 8–12-lm mid-infrared spectra of (24) Themis and (90) Antiope. We find that (90) Antiope is lacking a ‘‘fairy castle’’ dusty surface, which is in contrast to (24) Themis, other Themis family members (Licandro, J. et al. [2012]. Astron. Astrophys. 537, A73), and Jupiter Trojans (e.g. Emery, J.P., Cruikshank, D.P., Van Cleve, J. [2006]. Icarus 182, 496–512). We conclude that the surface structure of (90) Antiope is most similar to Cybele Asteroid (121) Hermione (Hargrove, K.D. et al. [2012]. Icarus 221, 453–455).

Asteroids↗

Optoelectronic device with a support member

Optoelectronic devices with a support member and methods of manufacturing or assembling the same are provided. An example of an optoelectronic device according to the present disclosure includes a substrate and an optical component and an electronic component disposed thereon or therein. The optoelectronic device further includes a ferrule coupled to the optical fiber and an optical socket receiving the ferrule therein. The optoelectronic device includes a support member disposed between the substrate and the optical socket such that the optical socket is spaced from the substrate by the support member.

42 ENGINEERING↗

OC7 Project Phase II: Code Comparison and Experimental Validation of Hydroelastic Effects and Member-Level Loads in Floating Structures

This paper presents results from Phase II of the OC7 project, focusing on hydroelastic modeling and member-level load prediction for a flexible floating offshore structure. Numerical predictions from 11 academic and industrial partners are validated against experimental measurements obtained from a 1:70-scale test of the VolturnUS-S semisubmersible platform. A comprehensive set of verification and validation cases is examined. The results demonstrate that hydrodynamic added mass has a significant impact on predicted elastic natural frequencies. Under regular wave excitation, the numerical models reproduce platform motions and mooring line tensions with good accuracy. Member-level loads are also predicted with reasonable accuracy. Some discrepancies are observed for potential-flow models not accounting for higher-order effects associated with the instantaneous wetted surface.

17 WIND ENERGY↗

Implementation of Substructure Flexibility and Member-Level Load Capabilities for Floating Offshore Wind Turbines in OpenFAST

OpenFAST is an open-source, physics-based engineering tool applicable to the load analysis of land-based and offshore wind turbines, including floating offshore wind turbines. The substructure for a floating wind turbine has historically been modeled in OpenFAST as a rigid body with hydrodynamic loads lumped at a point, which enabled the tool to predict the global response of the floating substructure but not the structural loads within its individual members. This limitation is an impediment to designing floating substructures - especially newer designs that are more streamlined, flexible, and cost-effective. This paper presents the development of new functionality in OpenFAST to model floating substructure flexibility and member-level loads, as well as the concepts and mathematical background needed to understand and apply it correctly.

17 WIND ENERGY↗

The exo-β- N -acetylmuramidase NamZ from Bacillus subtilis is the founding member of a family of exo-lytic peptidoglycan hexosaminidases

Endo-β-N-acetylmuramidases, commonly known as lysozymes, are well-characterized antimicrobial enzymes that catalyze an endo-lytic cleavage of peptidoglycan; i.e., they hydrolyze the β-1,4-glycosidic bonds connecting N-acetylmuramic acid (MurNAc) and N-acetylglucosamine (GlcNAc). In contrast, little is known about exo-β-N-acetylmuramidases, which catalyze an exo-lytic cleavage of β-1,4-MurNAc entities from the non-reducing ends of peptidoglycan chains. Such an enzyme was identified earlier in the bacterium Bacillus subtilis, but the corresponding gene has remained unknown so far. We now report that ybbC of B. subtilis, renamed namZ, encodes the reported exo-β-N-acetylmuramidase. A ΔnamZ mutant accumulated specific cell wall fragments and showed growth defects under starvation conditions, indicating a role of NamZ in cell wall turnover and recycling. Recombinant NamZ protein specifically hydrolyzed the artificial substrate para-nitrophenyl β-MurNAc and the peptidoglycan-derived disaccharide MurNAc-β-1,4-GlcNAc. Together with the exo-β-N-acetylglucosaminidase NagZ and the exo-muramoyl-L-alanine amidase AmiE, NamZ degraded intact peptidoglycan by sequential hydrolysis from the non-reducing ends. A structure model of NamZ, built on the basis of two crystal structures of putative orthologs from Bacteroides fragilis, revealed a two-domain structure including a Rossmann-fold-like domain that constitutes a unique glycosidase fold. Thus, NamZ, a member of the DUF1343 protein family of unknown function, is now classified as the founding member of a new family of glycosidases (CAZy GH171). NamZ-like peptidoglycan hexosaminidases are mainly present in the phylum Bacteroidetes and less frequently found in individual genomes within Firmicutes (Bacilli, Clostridia), Actinobacteria, and γ-proteobacteria.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Vacuum-ultraviolet absorption cross-sections of functionalized cyclic hydrocarbons: Five-membered rings

Cross-sections were measured at 50 °C and 800 Torr using differential absorption spectroscopy in the vacuum-ultraviolet from 5.17 – 9.92 eV for a series of five-membered cyclic hydrocarbons: cyclopentane, cyclopentene, methylcyclopentane, tetrahydrofuran, furan, 2-methyltetrahydrofuran, 2,3-dihydro-5-methylfuran, tetrahydrofuran-3-one, 2-methyl-1,3-dioxolane, cyclopentanol, 2-hydroxytetrahydrofuran, cyclopentanone, 2-cyclopenten-1-one, 3-cyclopenten-1-one, 2-methylcyclopentan-1-one, 2-methylcyclopent-2-en-1-one, 1,2-epoxycyclopentane, 2,3-epoxycyclopentanone, and 3,4-epoxycyclopentanone. The majority of the species are functionalized and are directly related to chain-reactions relevant to combustion, such as substituted cyclic ethers and cycloalkenes. Uncertainty calculations were conducted as a function of photon energy to quantify errors associated with experimental repeatability, signal-to-noise ratio, and gas-phase concentration, yielding an upper limit of 5% in spectral regions where absorption is >2%. Here, the primary objective of the present work is to provide quantitative absorption cross-sections of species commonly produced in combustion reactions. Comparing qualitative differences among the five-membered cyclic species, in order to analyze the effect of functional groups on absorption, is a secondary objective. The majority of the spectra are reported for the first time and enable quantitative isomer-resolved speciation measurements in combustion chemistry.

74 ATOMIC AND MOLECULAR PHYSICS↗

A Six-Membered Concerted Mechanism for CO 2 Capture by Amines Studied under Charged Microdroplet Reaction Conditions

Carbon dioxide (CO 2 ) capture and storage represents an important technological challenge. A mechanistic understanding of interactions involved in the capture process is necessary not only for technological development but also for efficient conversion of captured CO 2 into value-added materials. Herein, we present a novel contained secondary electrospray ionization platform for studying the interactions of gaseous amines and CO 2 gas under microdroplet reaction conditions, which enables mass spectrometry (MS) characterization of CO 2 capture products and intermediates in real time. We detected [2 M + CO 2 + H] + species, which corresponds to a six-membered intermediate. DFT calculations confirmed the high stability of the protonated six-membered ring intermediate. This finding provides a plausible concerted mechanism in the microdroplet environment that excludes the involvement of thermodynamically disfavored ionic species. The carbamic acid counterpart of the final product/salt was readily characterized by tandem MS. The carbamic acid/amine salt was also isolated and characterized by Fourier transform infrared spectroscopy. By virtue of the fact that headspace vapors of amines are sampled, we were able to establish a high-throughput platform that enabled the CO 2 capture capacity of five different amines to be studied in under 2 min. The same device also enabled the absolute quantification of capture capacity.

Amines↗

Identifying Order and Disorder in Double Four-Membered Rings via Raman Spectroscopy during Crystallization of LTA Zeolite

Fluoride (F – ) has been essential for the synthesis of low-defect siliceous zeolites. It has been hypothesized that F – balances the positive charges from organic structure-directing agents (OSDAs) and stabilizes key building units during zeolite crystallization such as the double four-membered ring (D4R). However, due to the lack of characterization techniques for investigating medium-range structures, including rings and cages formed during zeolite crystallization, the roles of F – in stabilizing building units and maintaining local charge balance during zeolite assembly are not yet fully understood. Here, the crystallization of siliceous Linde type A (LTA) zeolite in the presence of F – was investigated using Raman spectroscopy and periodic density functional theory (DFT) calculations. We have discovered that the F – -filled double four-membered ring (F – /D4R) and the empty D4R exhibit rather distinct Raman features. Both the F – /D4R and empty D4R are formed in the LTA zeolite synthesized in the presence of F – using 1,2-dimethyl-3-(4-methylbenzyl) imidazolium as the OSDA. Observed Raman bands of the F – /D4R and empty D4R, along with predictive DFT calculations on LTA supercells, reveal an ordered distribution of these two D4R units in the final as-made LTA zeolite. The discovery of these distinct Raman signatures of F – /D4R and empty D4R units opens an interesting new window for studying defects in the D4R during zeolite formation. In particular, we have observed variation in Raman intensities of F – /D4R and empty D4R bands during LTA crystallization; periodic DFT calculations indicate that the observed Raman behavior is consistent with empty D4R units containing one or two Si vacancies surrounded by Q 3 Si—consistent also with solid-state nuclear magnetic resonance measurement. These defects appear to heal during further crystallization, leading to the formation of defect-free LTA zeolite crystals. Altogether, our results provide deeper understanding on the roles of F – in charge balancing and stabilizing intact D4R units during zeolite formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anaerobic methane oxidation coupled to manganese reduction by members of the Methanoperedenaceae

Abstract Anaerobic oxidation of methane (AOM) is a major biological process that reduces global methane emission to the atmosphere. Anaerobic methanotrophic archaea (ANME) mediate this process through the coupling of methane oxidation to different electron acceptors, or in concert with a syntrophic bacterial partner. Recently, ANME belonging to the archaeal family Methanoperedenaceae (formerly known as ANME-2d) were shown to be capable of AOM coupled to nitrate and iron reduction. Here, a freshwater sediment bioreactor fed with methane and Mn(IV) oxides (birnessite) resulted in a microbial community dominated by two novel members of the Methanoperedenaceae, with biochemical profiling of the system demonstrating Mn(IV)-dependent AOM. Genomic and transcriptomic analyses revealed the expression of key genes involved in methane oxidation and several shared multiheme c-type cytochromes (MHCs) that were differentially expressed, indicating the likely use of different extracellular electron transfer pathways. We propose the names “Candidatus Methanoperedens manganicus” and “Candidatus Methanoperedens manganireducens” for the two newly described Methanoperedenaceae species. This study demonstrates the ability of members of the Methanoperedenaceae to couple AOM to the reduction of Mn(IV) oxides, which suggests their potential role in linking methane and manganese cycling in the environment.

54 ENVIRONMENTAL SCIENCES↗

A unified reaction network on the formation of five-membered ringed polycyclic aromatic hydrocarbons (PAHs) and their role in ring expansion processes through radical–radical reactions

Exploiting a chemical microreactor in combination with an isomer-selective product identification through fragment-free photoionization utilizing tunable vacuum ultraviolet (VUV) light in tandem with the detection of the ionized molecules by a high resolution reflection time-of-flight mass spectrometer (Re-TOF-MS), the present investigation reveals molecular mass growth processes to four distinct polycyclic aromatic hydrocarbons carrying two six- and one five-membered ring (C 13 H 10 ): 3H-cyclopenta[a]naphthalene, 1H-cyclopenta[b]naphthalene, 1H-cyclopenta[a]naphthalene, and fluorene in the gas phase. Temperatures of 973 and 1023 K simulating conditions in combustion settings along with circumstellar envelopes of carbon-rich stars and planetary nebulae. These reactions highlight the importance of methyl-substituted aromatic reactants (biphenyl, naphthalene) which can be converted to the methylene (–CH 2 ˙) motive by hydrogen abstraction or photolysis. Upon reaction with acetylene, methylene-substituted aromatics carrying a hydrogen atom at the ortho position of the ring can be then converted to cyclopentadiene-annulated aromatics thus providing a versatile pathway to five-membered ring aromatics at elevated temperatures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DCT4 —A New Member of the Dicarboxylate Transporter Family in C 4 Grasses

Malate transport shuttles atmospheric carbon into the Calvin–Benson cycle during NADP-ME C 4 photosynthesis. Previous characterizations of several plant dicarboxylate transporters (DCT) showed that they efficiently exchange malate across membranes. Here, we identify and characterize a previously unknown member of the DCT family, DCT4, in Sorghum bicolor. We show that SbDCT4 exchanges malate across membranes and its expression pattern is consistent with a role in malate transport during C 4 photosynthesis. SbDCT4 is not syntenic to the characterized photosynthetic gene ZmDCT2, and an ortholog is not detectable in the maize reference genome. We found that the expression patterns of DCT family genes in the leaves of Zea mays, and S. bicolor varied by cell type. Our results suggest that subfunctionalization, of members of the DCT family, for the transport of malate into the bundle sheath plastids, occurred during the process of independent recurrent evolution of C 4 photosynthesis in grasses of the PACMAD clade. We also show that this subfunctionalization is lineage independent. Our results challenge the dogma that key C 4 genes must be orthologues of one another among C 4 species, and shed new light on the evolution of C 4 photosynthesis.

59 BASIC BIOLOGICAL SCIENCES↗

Pseudo-atomic orbital behavior in graphene nanoribbons with four-membered rings

The incorporation of nonhexagonal rings into graphene nanoribbons (GNRs) is an effective strategy for engineering localized electronic states, bandgaps, and magnetic properties. Here, we demonstrate the successful synthesis of nanoribbons having four-membered ring (cyclobutadienoid) linkages by using an on-surface synthesis approach involving direct contact transfer of coronene-type precursors followed by thermally assisted [2 + 2] cycloaddition. The resulting coronene-cyclobutadienoid nanoribbons feature a narrow 600-meV bandgap and novel electronic frontier states that can be interpreted as linear chains of effective p x and p y pseudo-atomic orbitals. We show that these states give rise to exceptional physical properties, such as a rigid indirect energy gap. This provides a previously unexplored strategy for constructing narrow gap GNRs via modification of precursor molecules whose function is to modulate the coupling between adjacent four-membered ring states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Diagnosing Open Cluster Stock 2: Member Candidates and Mass Distribution with Gaia DR2 and LAMOST

We identify 1325 member candidates of the open cluster (OC) Stock 2 using data from Gaia DR2. We use the algorithms Clusterix 2.0 and HDBSCAN to select cluster candidates and further refine the final cluster membership by defining neighbors in 5D phase space (X {sub cp}, Y {sub cp}, Z{sub cp},κ⋅μ{sub α}{sup ∗}/ϖ, κ · μ {sub δ}/ϖ). Among these candidates, less than half have G, G {sub BP}, and G {sub RP} extinctions from Gaia. When Gaia extinctions are unavailable, we compute extiction using empirical formulas and E(B − V) = 0.350. We analyze the spatial distribution and mass profile of Stock 2. Our results reveal Stock 2 is still a bound OC and we find evidence of mass segregation. By comparing initial mass functions, the present-day mass function indicates that Stock 2 is a massive stellar cluster with a mass of 4000 M {sub ⊙}. The core radius and tidal radius, calculated via the radial density profile and total mass, are 3.97 pc and 22.65 pc, respectively. Common stars between our selected member candidates and the Large Sky Area Multi-Object Fiber Spectroscopic Telescope DR7 medium-resolution catalog give a metalliclity of [Fe/H] = −0.040 ± 0.147.

47 OTHER INSTRUMENTATION↗

Follow-up of Young Stars Identified with BANYAN Σ: New Low-mass Members of Nearby Moving Groups

The characterization of moving groups offers a powerful means to identify large populations of young stars. In this paper, we present a sample of follow-up observations for 56 systems that have previously been proposed as members of young stellar associations through the application of the BANYAN Σ kinematic classification tool. Our measurements, which probe seven different associations, provide a sample of 39 stellar systems that either are confirmed or appear consistent with being young members of their respective associations. Nineteen of these are single M dwarfs. This sample expands our knowledge of Upper Centaurus Lupus, Coma Berenices, and AB Doradus Major to cooler temperatures and also significantly increases the known population of the Carina-Near association. The young systems present excellent targets for future planet searches and would also be valuable for studies of star formation and evolution. Additionally, we find two stellar systems that show indications of being rare instances of late-stage circumstellar accretion. Lastly, our follow-up measurements serve as a test of BANYAN Σ, finding an overall contamination rate that is consistent with previous findings (29% for systems with RV measurements, 37% without).

79 ASTRONOMY AND ASTROPHYSICS↗

Method of laminating structural members

A laminate is obtained by providing a lightweight core material, such as a honeycombed plastic or metal, within the cavity defined by an annular mold cavity frame. Face sheets, which are to be bonded to the core material, are provided on opposite sides of the frame and extend over the frame, thus sealing the core material in the cavity. An adhesive is provided between the core material and the face sheets and the combined thickness of the core material and adhesive is a close fit within the opposed face sheets. A gas tight seal, such as an O-ring gasket, is provided between the frame and the face sheet members to form a gas tight cavity between the face sheet members and the frame. External heat and pressure are used to bond the face sheets to the core material. Gas pressure is introduced into the sealed cavity to minimize out-gasing of the adhesive.

Heier, W. C.↗

Extruded edge members for honeycombs

Edge members in bonded honeycomb panel structures are conventionally made by machining channels in aluminum bars. Open ends are stuffed with honeycomb core, using intumescent adhesive. Less expensive technique eliminates need for stuffing. Extended edges are more reliable, lighter, and easier to install. New manufacturing method may prove useful in fabricating structures such as air-frames, recreational-vehicle frame members, and the like in which weight savings is primary goal.

Haskell, D. R.↗

Load concentration due to missing members in planar faces of a large space truss

A large space structure with members missing was investigated using a finite element analysis. The particular structural configuration was the tetrahedral truss, with attention restricted to one of its planar faces. Initially the finite element model of a complete face was verified by comparing it with known results for some basic loadings. Then an analysis was made of the structure with members near the center removed. Some calculations were made on the influence of the mesh size of a structure containing a hexagonal hole, and an analysis was also made of a structure with a rigid hexagonal insert. In general, load concentration effects in these trusses were significantly lower than classical stress concentration effects in an infinitely wide isotropic plate with a circular rigid inclusion, although larger effects were obtained when a hole extended over several rings of elements.

Waltz, J. E.↗