Stable hydrogen and carbon isotope ratios of extractable hydrocarbons in the Murchison meteorite

A fairly fool-proof method to ensure that the compounds isolated from meteorites are truly part of the meteorites and not an artifact introduced by exposure to the terrestrial environment, storage, or handling is presented. The stable carbon and hydrogen isotope ratios in several of the chemical compounds extracted from the Murchison meteorite were measured. The results obtained by studying the amino acids in this meteorite gave very unusual hydrogen and carbon isotope ratios. The technique was extended to the different classes of hydrocarbons and the hydrocarbons were isolated using a variety of separation techniques. The results and methods used in this investigation are described in this two page paper

The Insoluble Carbonaceous Material of CM Chondrites as Possible Source of Discrete Organics During the Asteroidal Aqueous Phase

The larger portion of the organic carbon in carbonaceous chondrites (CC) is present as a complex and heterogeneous macromolecular material that is insoluble in acids and most solvents (IOM). So far, it has been analyzed only as a whole by microscopy (TEM) and spectroscopy (IR, NMR, EPR), which have offered and overview of its chemical nature, bonding, and functional group composition. Chemical or pyrolytic decomposition has also been used in combination with GC-MS to identify individual compounds released by these processes. Their value in the recognition of the original IOM structure resides in the ability to properly interpret the decomposition pathways for any given process. We report here a preliminary study of IOM from the Murray meteorite that combines both the analytical approaches described above, under conditions that would realistically model the IOM hydrothermal exposure in the meteorite parent body. The aim is to document the possible release of water and solvent soluble organics, determine possible changes in NMR spectral features, and ascertain, by extension, the effect of this loss on the frame of the IOM residue. Additional information is included in the original extended abstract

Reaction of Q to thermal metamorphism in parent bodies: Experimental simulation

Planetary noble gases in chondrites are concentrated in an unidentified carrier phase, called “Q.” Phase Q oxidized at relatively low temperature in pure oxygen is a very minor part of insoluble organic matter (IOM), but has not been separated in a pure form. High‐pressure (HP) experiments have been used to test the effects of thermal metamorphism on IOM from the Orgueil (CI1) meteorite, at conditions up to 10 GPa and 700 °C. The effect of the treatment on carbon structural order was characterized by Raman spectroscopy of the carbon D and G bands. The Raman results show that the IOM becomes progressively more graphite‐like with increasing intensity and duration of the HP treatment. The carbon structural transformations are accompanied by an increase in the release temperatures for IOM carbon and Ar during stepped combustion (the former to a greater extent than the latter for the most HP treated sample) when compared with the original untreated Orgueil (CI1) sample. The Ar/C ratio also appears to vary in response to HP treatment. Since Ar is a part of Q, its release temperature corresponds to that for Q oxidation. Thus, the structural transformations of Q and IOM upon HP treatment are not equal. These results correspond to observations of thermal metamorphism in the meteorite parent bodies, in particular those of type 4 enstatite chondrites, e.g., Indarch (EH4), where graphitized IOM oxidized at significantly higher temperatures than Q (Verchovsky et al. 2002). Our findings imply that Q is less graphitized than most of the macromolecular carbonaceous material present during parent body metamorphism and is thus a carbonaceous phase distinct from other meteoritic IOM

An Extended Model for the Evolution of Prebiotic Homochirality: A Bottom-Up Approach to the Origin of Life

A generalized autocatalytic model for chiral polymerization is investigated in detail. Apart from enantiomeric cross-inhibition, the model allows for the autogenic (non-catalytic) formation of left and right-handed monomers from a substrate with reaction rates $\epsilon_L$ and $\epsilon_R$, respectively. The spatiotemporal evolution of the net chiral asymmetry is studied for models with several values of the maximum polymer length, N. For N=2, we study the validity of the adiabatic approximation often cited in the literature. We show that the approximation obtains the correct equilibrium values of the net chirality, but fails to reproduce the short time behavior. We show also that the autogenic term in the full N=2 model behaves as a control parameter in a chiral symmetry- breaking phase transition leading to full homochirality from racemic initial conditions. We study the dynamics of the N -> infinity model with symmetric ($\epsilon_L = \epsilon_R$) autogenic formation, showing that it only achieves homochirality for $\epsilon < \epsilon_c$, where $\epsilon_c$ is an N-dependent critical value. For $\epsilon \leq \epsilon_c$ we investigate the behavior of models with several values of N, showing that the net chiral asymmetry grows as tanh(N). We show that for a given symmetric autogenic reaction rate, the net chirality and the concentrations of chirally pure polymers increase with the maximum polymer length in the model. We briefly discuss the consequences of our results for the development of homochirality in prebiotic Earth and possible experimental verification of our findings

Organics preserved in anhydrous interplanetary dust particles: Pristine or not?

The chondritic‐porous subset of interplanetary dust particles (CP‐IDPs) are thought to have a cometary origin. Since the CP‐IDPs are anhydrous and unaltered by aqueous processes that are common to chondritic organic matter (OM), they represent the most pristine material of the solar system. However, the study of IDP OM might be hindered by their further alteration by flash heating during atmospheric entry, and we have limited understanding on how short‐term heating influences their organic content. In order to investigate this problem, five CP‐IDPs were studied for their OM contents, distributions, and isotopic compositions at the submicro‐ to nanoscale levels. The OM contained in the IDPs in this study spans the spectrum from primitive OM to that which has been significantly processed by heat. Similarities in the Raman D bands of the meteoritic and IDP OMs indicate that the overall gain in the sizes of crystalline domains in response to heating is similar. However, the Raman ΓG values of the OM in all of the five IDPs clearly deviate from those of chondritic OM that had been processed during a prolonged episode of parent body heating. Such disparity suggests that the nonaromatic contents of the OM are different. Short duration heating further increases the H/C ratio and reduces the δ13C and δD values of the IDP OM. Our findings suggest that IDP OM contains a significant proportion of disordered C with low H content, such as sp2 olefinic C=C, sp3 C–C, and/or carbonyl contents as bridging material

A Rapid Assessment of Avoidable Blindness in Southern Zambia

INTRODUCTION: A rapid assessment of avoidable blindness (RAAB) was conducted in Southern Zambia to establish the prevalence and causes of blindness in order to plan effective services and advocate for support for eye care to achieve the goals of VISION 2020: the right to sight. METHODS: Cluster randomisation was used to select villages in the survey area. These were further subdivided into segments. One segment was selected randomly and a survey team moved from house to house examining everyone over the age of 50 years. Each individual received a visual acuity assessment and simple ocular examination. Data was recorded on a standard proforma and entered into an established software programme for analysis. RESULTS: 2.29% of people over the age of 50 were found to be blind (VA <3/60 in the better eye with available correction). The major cause of blindness was cataract (47.2%) with posterior segment disease being the next main cause (18.8%). 113 eyes had received cataract surgery with 30.1% having a poor outcome (VA <6/60) following surgery. Cataract surgical coverage showed that men (72%) received more surgery than women (65%). DISCUSSION: The results from the RAAB survey in Zambia were very similar to the results from a similar survey in Malawi, where the main cause of blindness was cataract but posterior segment disease was also a significant contributor. Blindness in this part of Zambia is mainly avoidable and there is a need for comprehensive eye care services that can address both cataract and posterior segment disease in the population if the aim of VISION 2020 is to be achieved. Services should focus on quality and gender equity of cataract surgery

The cometary composition of a protoplanetary disk as revealed by complex cyanides

Observations of comets and asteroids show that the Solar Nebula that spawned our planetary system was rich in water and organic molecules. Bombardment brought these organics to the young Earth's surface, seeding its early chemistry. Unlike asteroids, comets preserve a nearly pristine record of the Solar Nebula composition. The presence of cyanides in comets, including 0.01% of methyl cyanide (CH3CN) with respect to water, is of special interest because of the importance of C-N bonds for abiotic amino acid synthesis. Comet-like compositions of simple and complex volatiles are found in protostars, and can be readily explained by a combination of gas-phase chemistry to form e.g. HCN and an active ice-phase chemistry on grain surfaces that advances complexity[3]. Simple volatiles, including water and HCN, have been detected previously in Solar Nebula analogues - protoplanetary disks around young stars - indicating that they survive disk formation or are reformed in situ. It has been hitherto unclear whether the same holds for more complex organic molecules outside of the Solar Nebula, since recent observations show a dramatic change in the chemistry at the boundary between nascent envelopes and young disks due to accretion shocks[8]. Here we report the detection of CH3CN (and HCN and HC3N) in the protoplanetary disk around the young star MWC 480. We find abundance ratios of these N-bearing organics in the gas-phase similar to comets, which suggests an even higher relative abundance of complex cyanides in the disk ice. This implies that complex organics accompany simpler volatiles in protoplanetary disks, and that the rich organic chemistry of the Solar Nebula was not unique.Comment: Definitive version of the manuscript is published in Nature, 520, 7546, 198, 2015. This is the author's versio

Extraterrestrial nucleobases in the Murchison meteorite

Carbon-rich meteorites, carbonaceous chondrites, contain many biologically relevant organic molecules and delivered prebiotic material to the young Earth. We present compound-specific carbon isotope data indicating that measured purine and pyrimidine compounds are indigenous components of the Murchison meteorite. Carbon isotope ratios for uracil and xanthine of delta13C=+44.5per mil and +37.7per mil, respectively, indicate a non-terrestrial origin for these compounds. These new results demonstrate that organic compounds, which are components of the genetic code in modern biochemistry, were already present in the early solar system and may have played a key role in life's origin.Comment: 31 pages, 4 figures, 3 table

The reactive species interactome: evolutionary emergence, biological significance, and opportunities for redox metabolomics and personalized medicine

SIGNIFICANCE: Oxidative stress is thought to account for aberrant redox homeostasis and contribute to aging and disease. However, more often than not administration of antioxidants is ineffective, suggesting our current understanding of the underlying regulatory processes is incomplete. Recent Advances. Similar to reactive oxygen and nitrogen species (ROS, RNS), reactive sulfur species (RSS) are now emerging as important signaling molecules, targeting regulatory cysteine redox switches in proteins, affecting gene regulation, ion transport, intermediary metabolism and mitochondrial function. To rationalize the complexity of chemical interactions of reactive species with themselves and their targets and help define their role in systemic metabolic control, we here introduce a novel integrative concept coined the reactive species interactome (RSI). The RSI is a primeval multi-level redox-regulatory system whose architecture, together with the physicochemical characteristics of its constituents, allows efficient sensing and rapid adaptation to environmental changes and various other stresses to enhance fitness and resilience at the local and whole-organism level. CRITICAL ISSUES: To better characterise the RSI-related processes that determine fluxes through specific pathways and enable integration, it is necessary to disentangle the chemical biology and activity of reactive species (including precursors and reaction products), their targets, communication systems and effects on cellular, organ and whole-organism bioenergetics using systems-level/network analyses. FUTURE DIRECTIONS: Understanding the mechanisms through which the RSI operates will enable a better appreciation of the possibilities to modulate the entire biological system; moreover, unveiling molecular signatures that characterize specific environmental challenges or other stresses will provide new prevention/intervention opportunities for personalized medicine