Were Presolar Grains Destroyed by the Nebular Process Responsible for the Volatile Element Fractionation?

We present SiC abundances from a number of CM and CR chondrites using NanoSIMS raster ion imaging of acid residues. We find higher SiC abundances for CRs than previously estimated based on noble gases

Cosmic History and a Candidate Parent Asteroid for the Quasicrystal-bearing Meteorite Khatyrka

The unique CV-type meteorite Khatyrka is the only natural sample in which "quasicrystals" and associated crystalline Cu,Al-alloys, including khatyrkite and cupalite, have been found. They are suspected to have formed in the early Solar System. To better understand the origin of these exotic phases, and the relationship of Khatyrka to other CV chondrites, we have measured He and Ne in six individual, ~40-{\mu}m-sized olivine grains from Khatyrka. We find a cosmic-ray exposure age of about 2-4 Ma (if the meteoroid was <3 m in diameter, more if it was larger). The U,Th-He ages of the olivine grains suggest that Khatyrka experienced a relatively recent (<600 Ma) shock event, which created pressure and temperature conditions sufficient to form both the quasicrystals and the high-pressure phases found in the meteorite. We propose that the parent body of Khatyrka is the large K-type asteroid 89 Julia, based on its peculiar, but matching reflectance spectrum, evidence for an impact/shock event within the last few 100 Ma (which formed the Julia family), and its location close to strong orbital resonances, so that the Khatyrka meteoroid could plausibly have reached Earth within its rather short cosmic-ray exposure age.Comment: Submitted to Earth and Planetary Science Letter

Ruthenium-based PACT agents based on bisquinoline chelates: synthesis, photochemistry, and cytotoxicity

The known ruthenium complex [Ru(tpy)(bpy)(Hmte)](PF6)(2) ([1](PF6)(2), where tpy = 2,2':6',2 ''-terpyridine, bpy = 2,2'-bipyridine, Hmte = 2-(methylthio)ethanol) is photosubstitutionally active but non-toxic to cancer cells even upon light irradiation. In this work, the two analogs complexes [Ru(tpy)(NN)(Hmte)](PF6)(2), where NN = 3,3'-biisoquinoline (i-biq, [2](PF6)(2)) and di(isoquinolin-3-yl)amine (i-Hdiqa, [3](PF6)(2)), were synthesized and their photochemistry and phototoxicity evaluated to assess their suitability as photoactivated chemotherapy (PACT) agents. The increase of the aromatic surface of [2](PF6)(2) and [3](PF6)(2), compared to [1](PF6)(2), leads to higher lipophilicity and higher cellular uptake for the former complexes. Such improved uptake is directly correlated to the cytotoxicity of these compounds in the dark: while [2](PF6)(2) and [3](PF6)(2) showed low EC50 values in human cancer cells, [1](PF6)(2) is not cytotoxic due to poor cellular uptake. While stable in the dark, all complexes substituted the protecting thioether ligand upon light irradiation (520 nm), with the highest photosubstitution quantum yield found for [3](PF6)(2) (phi([3]) = 0.070). Compounds [2](PF6)(2) and [3](PF6)(2) were found both more cytotoxic after light activation than in the dark, with a photo index of 4. Considering the very low singlet oxygen quantum yields of these compounds, and the lack of cytotoxicity of the photoreleased Hmte thioether ligand, it can be concluded that the toxicity observed after light activation is due to the photoreleased aqua complexes [Ru(tpy)(NN)(OH2)](2+), and thus that [2](PF6)(2) and [3](PF6)(2) are promising PACT candidates.[GRAPHICS].Metals in Catalysis, Biomimetics & Inorganic Material

Alkyne Functionalization of a Photoactivated Ruthenium Polypyridyl Complex for Click-Enabled Serum Albumin Interaction Studies

Studying metal-protein interactions is key for understanding the fate of metallodrugs in biological systems. When a metal complex is not emissive and too weakly bound for mass spectrometry analysis, however, it may become challenging to study such interactions. In this work a synthetic procedure was developed for the alkyne functionalization of a photolabile ruthenium polypyridyl complex, [Ru(tpy)(bpy)(Hmte)](PF6)2, where tpy = 2,2′:6′,2′′-terpyridine, bpy = 2,2′-bipyridine, and Hmte = 2-(methylthio)ethanol. In the functionalized complex [Ru(HCC-tpy)(bpy)(Hmte)](PF6)2, where HCC-tpy = 4′-ethynyl-2,2′:6′,2′′-terpyridine, the alkyne group can be used for bioorthogonal ligation to an azide-labeled fluorophore using copper-catalyzed “click” chemistry. We developed a gel-based click chemistry method to study the interaction between this ruthenium complex and bovine serum albumin (BSA). Our results demonstrate that visualization of the interaction between the metal complex and the protein is possible, even when this interaction is too weak to be studied by conventional means such as UV–vis spectroscopy or ESI mass spectrometry. In addition, the weak metal complex-protein interaction is controlled by visible light irradiation, i.e., the complex and the protein do not interact in the dark, but they do interact via weak van der Waals interactions after light activation of the complex, which triggers photosubstitution of the Hmte ligand.Metals in Catalysis, Biomimetics & Inorganic MaterialsBio-organic Synthesi

Overview of the results of the organics PET Study of the cometary samples returned from comet Wild 2 by the Stardust mission

This presenation will provide an overview of the efforts and results produced by the Organics Preliminary Examination Team during their studies of the samples returned from comet Wild 2 by the Stardust spacecraft

Shifted Excitation Raman Difference Spectroscopy Applied to Extraterrestrial Particles Returned from the Asteroid Itokawa

Two extraterrestrial particles from the asteroid Itokawa are investigated applying Shifted Excitation Raman Difference Spectroscopy (SERDS). These particles were returned by the Hayabusa mission of the Japanese Space Agency JAXA. For SERDS a diode laser based microsystem light source at 488 nm is used for excitation. It has been found that fluorescence signals masking the Raman spectral features of interest can be substantially separated by applying SERDS. Therefore, SERDS improves the information obtained from the Raman spectra and enables a reliable analysis for investigations on extraterrestrial samples

A divergent heritage for complex organics in Isheyevo lithic clasts

Primitive meteorites are samples of asteroidal bodies that contain a high proportion of chemically complex organic matter (COM) including prebiotic molecules such as amino acids, which are thought to have been delivered to Earth via impacts during the early history of the Solar System. Thus, understanding the origin of COM, including their formation pathway(s) and environment(s), is critical to elucidate the origin of life on Earth as well as assessing the potential habitability of exoplanetary systems. The Isheyevo CH/CBb carbonaceous chondrite contains chondritic lithic clasts with variable enrichments in 15N believed to be of outer Solar System origin. Using transmission electron microscopy (TEM-EELS) and in situ isotope analyses (SIMS and NanoSIMS), we report on the structure of the organic matter as well as the bulk H and N isotope composition of Isheyevo lithic clasts. These data are complemented by electron microprobe analyses of the clast mineral chemistry and bulk Mg and Cr isotopes obtained by inductively coupled plasma and thermal ionization mass spectrometry, respectively (MC-ICPMS and TIMS). Weakly hydrated (A) clasts largely consist of Mg-rich anhydrous silicates with local hydrated veins composed of phyllosilicates, magnetite and globular and diffuse organic matter. Extensively hydrated clasts (H) are thoroughly hydrated and contain Fe-sulfides, sometimes clustered with organic matter, as well as magnetite and carbonates embedded in a phyllosilicate matrix. The A-clasts are characterized by a more 15N-rich bulk nitrogen isotope composition (δ15N = 200–650‰) relative to H-clasts (δ15N = 50–180‰) and contain extremely 15N-rich domains with δ15N 15N-rich domains show that the lithic clast diffuse organic matter is typically more 15N-rich than globular organic matter. The correlated δ15N values and C/N ratios of nanoglobules require the existence of multiple organic components, in agreement with the H isotope data. The combined H and N isotope data suggest that the organic precursors of the lithic clasts are defined by an extremely 15N-poor (similar to solar) and D-rich component for H-clasts, and a moderately 15N-rich and D-rich component for A-clasts. In contrast, the composition of the putative fluids is inferred to include D-poor but moderately to extremely 15N-rich H- and N-bearing components. The variable 15N enrichments in H- and A-clasts are associated with structural differences in the N bonding environments of their diffuse organic matter, which are dominated by amine groups in H-clasts and nitrile functional groups in A-clasts. We suggest that the isotopically divergent organic precursors in Isheyevo clasts may be similar to organic moieties in carbonaceous chondrites (CI, CM, CR) and thermally recalcitrant organic compounds in ordinary chondrites, respectively. The altering fluids, which are inferred to cause the 15N enrichments observed in the clasts, may be the result of accretion of variable abundances of NH3 and HCN ices. Finally, using bulk Mg and Cr isotope composition of clasts, we speculate on the accretion regions of the various primitive chondrites and components and the origin of the Solar System’s N and H isotope variability

Mineralogy and petrology of the Murrili meteorite

No abstract available

Annama H chondrite-Mineralogy, physical properties, cosmic ray exposure, and parent body history

The fall of the Annama meteorite occurred early morning (local time) on April 19, 2014 on the Kola Peninsula (Russia). Based on mineralogy and physical properties, Annama is a typical H chondrite. It has a high Ar-Ar age of 4.4 Ga. Its cosmic ray exposure history is atypical as it is not part of the large group of H chondrites with a prominent 7-8 Ma peak in the exposure age histograms. Instead, its exposure age is within uncertainty of a smaller peak at 30 +/- 4 Ma. The results from short-lived radionuclides are compatible with an atmospheric pre-entry radius of 30-40 cm. However, based on noble gas and cosmogenic radionuclide data, Annama must have been part of a larger body (radius >65 cm) for a large part of its cosmic ray exposure history. The Be-10 concentration indicates a recent (3-5 Ma) breakup which may be responsible for the Annama parent body size reduction to 30-35 cm pre-entry radius.Peer reviewe

Triple F - a comet nucleus sample return mission

The Triple F (Fresh From the Fridge) mission, a Comet Nucleus Sample Return, has been proposed to ESA's Cosmic Vision program. A sample return from a comet enables us to reach the ultimate goal of cometary research. Since comets are the least processed bodies in the solar system, the proposal goes far beyond cometary science topics (like the explanation of cometary activity) and delivers invaluable information about the formation of the solar system and the interstellar molecular cloud from which it formed. The proposed mission would extract three sample cores of the upper 50cm from three locations on a cometary nucleus and return them cooled to Earth for analysis in the laboratory. The simple mission concept with a touch-and-go sampling by a single spacecraft was proposed as an M-class mission in collaboration with the Russian space agency ROSCOSMOS. © The Author(s) 2008