Detailed analysis of distorted retinal and its interaction with surrounding residues in the K intermediate of bacteriorhodopsin

The K intermediate of proton pumping bacteriorhodopsin is the first intermediate generated after isomerization of retinal to the 13-cis form. Although various structures have been reported for the K intermediate until now, these differ from each other, especially in terms of the conformation of the retinal chromophore and its interaction with surrounding residues. We report here an accurate X-ray crystallographic analysis of the K structure. The polyene chain of 13-cis retinal is observed to be S-shaped. The side chain of Lys216, which is covalently bound to retinal via the Schiff-base linkage, interacts with residues, Asp85 and Thr89. In addition, the Nζ-H of the protonated Schiff-base linkage interacts with a residue, Asp212 and a water molecule, W402. Based on quantum chemical calculations for this K structure, we examine the stabilizing factors of distorted conformation of retinal and propose a relaxation manner to the next L intermediate

Mixing model of Phobos' bulk elemental composition for the determination of its origin: Multivariate analysis of MMX/MEGANE data

The formation process of the two Martian moons, Phobos and Deimos, is still debated with two main competing hypotheses: the capture of an asteroid or a giant impact onto Mars. In order to reveal their origin, the Martian Moons eXploration (MMX) mission by Japan Aerospace Exploration Agency (JAXA) plans to measure Phobos' elemental composition by a gamma-ray and neutron spectrometer called MEGANE. This study provides a model of Phobos' bulk elemental composition, assuming the two formation hypotheses. Using the mixing model, we established a MEGANE data analysis flow to discriminate between the formation hypotheses by multivariate analysis. The mixing model expresses the composition of Phobos in 6 key lithophile elements that will be measured by MEGANE (Fe, Si, O, Ca, Mg, and Th) as a linear mixing of two mixing components: material from Mars and material from an asteroid as represented by primitive meteorite compositions. The inversion calculation includes consideration of MEGANE's measurement errors ($E_P$) and derives the mixing ratio for a given Phobos composition, based on which the formation hypotheses are judged. For at least 65\% of the modeled compositions, MEGANE measurements will determine the origin uniquely ($E_P$ = 30\%), and this increases from 74 to 87\% as $E_P$ decreases from 20 to 10\%. Although the discrimination performance depends on $E_P$, the current operation plan for MEGANE predicts an instrument performance for $E_P$ of 20--30\%, resulting in ~70\% discrimination between the original hypotheses. MEGANE observations can also enable the determination of the asteroid type of the captured body or the impactor. The addition of other measurements, such as MEGANE's measurements of the volatile element K, as well as observations by other MMX remote sensing instruments, will also contribute to the MMX mission's goal to constrain the origin of Phobos.Comment: 34 pages, 7 figures, accepted for publication in Icaru

Ryugu’s nucleosynthetic heritage from the outskirts of the Solar System

Little is known about the origin of the spectral diversity of asteroids and what it says about conditions in the protoplanetary disk. Here, we show that samples returned from Cb-type asteroid Ryugu have Fe isotopic anomalies indistinguishable from Ivuna-type (CI) chondrites, which are distinct from all other carbonaceous chondrites. Iron isotopes, therefore, demonstrate that Ryugu and CI chondrites formed in a reservoir that was different from the source regions of other carbonaceous asteroids. Growth and migration of the giant planets destabilized nearby planetesimals and ejected some inward to be implanted into the Main Belt. In this framework, most carbonaceous chondrites may have originated from regions around the birthplaces of Jupiter and Saturn, while the distinct isotopic composition of CI chondrites and Ryugu may reflect their formation further away in the disk, owing their presence in the inner Solar System to excitation by Uranus and Neptune

Water circulation in Ryugu asteroid affected the distribution of nucleosynthetic isotope anomalies in returned sample

Studies of material returned from Cb asteroid Ryugu have revealed considerable mineralogical and chemical heterogeneity, stemming primarily from brecciation and aqueous alteration. Isotopic anomalies could have also been affected by delivery of exogenous clasts and aqueous mobilization of soluble elements. Here, we show that isotopic anomalies for mildly soluble Cr are highly variable in Ryugu and CI chondrites, whereas those of Ti are relatively uniform. This variation in Cr isotope ratios is most likely due to physicochemical fractionation between 54Cr-rich presolar nanoparticles and Cr-bearing secondary minerals at the millimeter-scale in the bulk samples, likely due to extensive aqueous alteration in their parent bodies that occurred 5:2þ11::84 Ma after Solar System birth. In contrast, Ti isotopes were marginally affected by this process. Our results show that isotopic heterogeneities in asteroids are not all nebular or accretionary in nature but can also reflect element redistribution by water

On the origin and evolution of the asteroid Ryugu: A comprehensive geochemical perspective

Presented here are the observations and interpretations from a comprehensive analysis of 16 representative particles returned from the C-type asteroid Ryugu by the Hayabusa2 mission. On average Ryugu particles consist of 50% phyllosilicate matrix, 41% porosity and 9% minor phases, including organic matter. The abundances of 70 elements from the particles are in close agreement with those of CI chondrites. Bulk Ryugu particles show higher δ18O, Δ17O, and ε54Cr values than CI chondrites. As such, Ryugu sampled the most primitive and least-thermally processed protosolar nebula reservoirs. Such a finding is consistent with multi-scale H-C-N isotopic compositions that are compatible with an origin for Ryugu organic matter within both the protosolar nebula and the interstellar medium. The analytical data obtained here, suggests that complex soluble organic matter formed during aqueous alteration on the Ryugu progenitor planetesimal (several 10’s of km), <2.6 Myr after CAI formation. Subsequently, the Ryugu progenitor planetesimal was fragmented and evolved into the current asteroid Ryugu through sublimation

A pristine record of outer Solar System materials from asteroid Ryugu’s returned sample

Volatile and organic-rich C-type asteroids may have been one of the main sources of Earth’s water. Our best insight into their chemistry is currently provided by carbonaceous chondritic meteorites, but the meteorite record is biased: only the strongest types survive atmospheric entry and are then modified by interaction with the terrestrial environment. Here we present the results of a detailed bulk and microanalytical study of pristine Ryugu particles, brought to Earth by the Hayabusa2 spacecraft. Ryugu particles display a close compositional match with the chemically unfractionated, but aqueously altered, CI (Ivuna-type) chondrites, which are widely used as a proxy for the bulk Solar System composition. The sample shows an intricate spatial relationship between aliphatic-rich organics and phyllosilicates and indicates maximum temperatures of ~30 °C during aqueous alteration. We find that heavy hydrogen and nitrogen abundances are consistent with an outer Solar System origin. Ryugu particles are the most uncontaminated and unfractionated extraterrestrial materials studied so far, and provide the best available match to the bulk Solar System composition