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Raggi, L, Bada JL, Lazcano A.  2016.  On the lack of evolutionary continuity between prebiotic peptides and extant enzymes. Physical Chemistry Chemical Physics. 18:20028-20032.   10.1039/c6cp00793g   AbstractWebsite

The significance of experiments that claim to simulate the properties of prebiotic small peptides and polypeptides as models of the polymers that may have preceded proteins is critically addressed. As discussed here, most of these experiments are based only on a small number of a larger set of amino acids that may have been present in the prebiotic environment, supported by both experimental simulations and the repertoire of organic compounds reported in carbonaceous chondrites. Model experiments with small peptides may offer some insights into the processes that contributed to generate the chemical environment leading to the emergence of informational oligomers, but not to the origin of proteins. The large body of circumstantial evidence indicating that catalytic RNA played a key role in the origin of protein synthesis during the early stages of cellular evolution implies that the emergence of the genetic code and of protein biosynthesis are no longer synonymous with the origin of life. Hence, reports on the abiotic synthesis of small catalytic peptides under potential prebiotic conditions do not provide information on the origin of triplet encoded protein biosynthesis, but in some cases may serve as models to understand the properties of the earliest proteins.

Onstott, TC, Magnabosco C, Aubrey AD, Burton AS, Dworkin JP, Elsila JE, Grunsfeld S, Cao BH, Hein JE, Glavin DP, Kieft TL, Silver BJ, Phelps TJ, van Heerden E, Opperman DJ, Bada JL.  2014.  Does aspartic acid racemization constrain the depth limit of the subsurface biosphere? Geobiology. 12:1-19.   10.1111/gbi.12069   AbstractWebsite

Previous studies of the subsurface biosphere have deduced average cellular doubling times of hundreds to thousands of years based upon geochemical models. We have directly constrained the in situ average cellular protein turnover or doubling times for metabolically active micro-organisms based on cellular amino acid abundances, D/L values of cellular aspartic acid, and the in vivo aspartic acid racemization rate. Application of this method to planktonic microbial communities collected from deep fractures in South Africa yielded maximum cellular amino acid turnover times of similar to 89years for 1km depth and 27 degrees C and 1-2years for 3km depth and 54 degrees C. The latter turnover times are much shorter than previously estimated cellular turnover times based upon geochemical arguments. The aspartic acid racemization rate at higher temperatures yields cellular protein doubling times that are consistent with the survival times of hyperthermophilic strains and predicts that at temperatures of 85 degrees C, cells must replace proteins every couple of days to maintain enzymatic activity. Such a high maintenance requirement may be the principal limit on the abundance of living micro-organisms in the deep, hot subsurface biosphere, as well as a potential limit on their activity. The measurement of the D/L of aspartic acid in biological samples is a potentially powerful tool for deep, fractured continental and oceanic crustal settings where geochemical models of carbon turnover times are poorly constrained. Experimental observations on the racemization rates of aspartic acid in living thermophiles and hyperthermophiles could test this hypothesis. The development of corrections for cell wall peptides and spores will be required, however, to improve the accuracy of these estimates for environmental samples.

Elsila, JE, Glavin DP, Dworkin JP, Martins Z, Bada JL.  2012.  Inconclusive evidence for nonterrestrial isoleucine enantiomeric excesses in primitive meteorites. Proceedings of the National Academy of Sciences of the United States of America. 109:E3288-E3288.   10.1073/pnas.1213261109   Abstract

Pizzarello et al. (1) recently described the soluble organic content of eight Antarctic Renazzo-type (CR) carbonaceous chondrites and reported large enantiomeric excesses (ee) of l-isoleucine and d-alloisoleucine. The reported values of ee decrease with inferred increases in aqueous alteration. We believe the conclusions presented in the paper are not fully justified and the data are potentially flawed.

Potential terrestrial contamination of meteoritic amino acid data must always be considered. The manuscript states that “terrestrial contamination levels… were evaluated based on the presence of proteinogenic amino acids’ l-excesses and accounted for when needed,” but this “accounting” is not described. A wide range of l-proteinogenic amino acid excesses was measured …

Bada, JL.  2009.  Enantiomeric excesses in the Murchison meteorite and the origin of homochirality in terrestrial biology. Proceedings of the National Academy of Sciences of the United States of America. 106:E85-E85.   10.1073/pnas.0906490106   Website
Johnson, AP, Cleaves HJ, Dworkin JP, Glavin DP, Lazcano A, Bada JL.  2008.  The Miller volcanic spark discharge experiment. Science. 322:404-404.   10.1126/science.1161527   Website
Bada, JL, Ehrenfreund P, Grunthaner F, Blaney D, Coleman M, Farrington A, Yen A, Mathies R, Amudson R, Quinn R, Zent A, Ride S, Barron L, Botta O, Clark B, Glavin D, Hofmann B, Josset JL, Rettberg P, Robert F, Sephton M.  2008.  Urey: Mars Organic and Oxidant Detector. Space Science Reviews. 135:269-279.   10.1007/s11214-007-9213-3   AbstractWebsite

One of the fundamental challenges facing the scientific community as we enter this new century of Mars research is to understand, in a rigorous manner, the biotic potential both past and present of this outermost terrestrial-like planet in our solar system. Urey: Mars Organic and Oxidant Detector has been selected for the Pasteur payload of the European Space Agency's (ESA's) ExoMars rover mission and is considered a fundamental instrument to achieve the mission's scientific objectives. The instrument is named Urey in recognition of Harold Clayton Urey's seminal contributions to cosmochemistry, geochemistry, and the study of the origin of life. The overall goal of Urey is to search for organic compounds directly in the regolith of Mars and to assess their origin. Urey will perform a groundbreaking investigation of the Martian environment that will involve searching for organic compounds indicative of life and prebiotic chemistry at a sensitivity many orders of magnitude greater than Viking or other in situ organic detection systems. Urey will perform the first in situ search for key classes of organic molecules using state-of-the-art analytical methods that provide part-per-trillion sensitivity. It will ascertain whether any of these molecules are abiotic or biotic in origin and will evaluate the survival potential of organic compounds in the environment using state-of-the-art chemoresistor oxidant sensors.

Aubrey, AD, Chalmers JH, Bada JL, Grunthaner FJ, Amashukeli X, Willis P, Skelley AM, Mathies RA, Quinn RC, Zent AP, Ehrenfreund P, Amundson R, Glavin DP, Botta O, Barron L, Blaney DL, Clark BC, Coleman M, Hofmann BA, Josset JL, Rettberg P, Ride S, Robert F, Sephton MA, Yen A.  2008.  The Urey instrument: An advanced in situ organic and oxidant detector for Mars exploration. Astrobiology. 8:583-595.   10.1089/ast.2007.0169   AbstractWebsite

The Urey organic and oxidant detector consists of a suite of instruments designed to search for several classes of organic molecules in the martian regolith and ascertain whether these compounds were produced by biotic or abiotic processes using chirality measurements. These experiments will also determine the chemical stability of organic molecules within the host regolith based on the presence and chemical reactivity of surface and atmospheric oxidants. Urey has been selected for the Pasteur payload on the European Space Agency's (ESA's) upcoming 2013 ExoMars rover mission. The diverse and effective capabilities of Urey make it an integral part of the payload and will help to achieve a large portion of the mission's primary scientific objective: "to search for signs of past and present life on Mars." This instrument is named in honor of Harold Urey for his seminal contributions to the fields of cosmochemistry and the origin of life.

Cleaves, HJ, Chalmers JH, Lazcano A, Miller SL, Bada JL.  2008.  A reassessment of prebiotic organic synthesis in neutral planetary atmospheres. Origins of Life and Evolution of Biospheres. 38:105-115.   10.1007/s11084-007-9120-3   AbstractWebsite

The action of an electric discharge on reduced gas mixtures such as H(2)O, CH(4) and NH(3) (or N(2)) results in the production of several biologically important organic compounds including amino acids. However, it is now generally held that the early Earth's atmosphere was likely not reducing, but was dominated by N(2) and CO(2). The synthesis of organic compounds by the action of electric discharges on neutral gas mixtures has been shown to be much less efficient. We show here that contrary to previous reports, significant amounts of amino acids are produced from neutral gas mixtures. The low yields previously reported appear to be the outcome of oxidation of the organic compounds during hydrolytic workup by nitrite and nitrate produced in the reactions. The yield of amino acids is greatly increased when oxidation inhibitors, such as ferrous iron, are added prior to hydrolysis. Organic synthesis from neutral atmospheres may have depended on the oceanic availability of oxidation inhibitors as well as on the nature of the primitive atmosphere itself. The results reported here suggest that endogenous synthesis from neutral atmospheres may be more important than previously thought.

Aubrey, A, Cleaves HJ, Chalmers JH, Skelley AM, Mathies RA, Grunthaner FJ, Ehrenfreund P, Bada JL.  2006.  Sulfate minerals and organic compounds on Mars. Geology. 34:357-360.   10.1130/g22316.1   AbstractWebsite

Strong evidence for evaporitic sulfate minerals such as gypsum and jarosite has recently been found on Mars. Although organic molecules are often codeposited with terrestrial evaporitic minerals, there have been no systematic investigations of organic components in sulfate minerals. We report here the detection of organic material, including amino acids and their amine degradation products, in ancient terrestrial sulfate minerals. Amino acids and amines appear to be preserved for geologically long periods in sulfate mineral matrices. This suggests that sulfate minerals should be prime targets in the search for organic compounds, including those of biological origin, on Mars.

Glavin, DP, Schubert M, Bada JL.  2002.  Direct isolation of purines and pyrimidines from nucleic acids using sublimation. Analytical Chemistry. 74:6408-6412.   10.1021/ac0259663   AbstractWebsite

A sublimation technique was developed to isolate purines and pyrimidines directly from lambda-deoxyribonucleic acid (lambda-DNA) and Escherichia coli cells. The sublimation of adenine, cytosine, guanine, and thymine from lambda-DNA was tested under reduced pressure (similar to 0.5 Torr) at temperatures of > 150 degreesC. With the exception of guanine, approximately 60-75% of each base was sublimed directly from the lambda-DNA and recovered on a coldfinger of the sublimation apparatus after heating to 450 T. Several nucleobases including adenine, cytosine, thymine, and uracil were also recovered from E. coli bacteria after heating the cells to the same temperature, although some thermal decomposition of the bases also occurred. These results demonstrate the feasibility of using sublimation to isolate purines and pyrimidines from native E. coli DNA and RNA without any chemical treatment of the cells.

Bada, JL.  2001.  State-of-the-art instruments for detecting extraterrestrial life. Proceedings of the National Academy of Sciences of the United States of America. 98:797-800.   10.1073/pnas.98.3.797   Website
Glavin, DP, Schubert M, Botta O, Kminek G, Bada JL.  2001.  Detecting pyrolysis products from bacteria on Mars. Earth and Planetary Science Letters. 185:1-5.   10.1016/s0012-821x(00)00370-8   AbstractWebsite

A pyrolysis/sublimation technique was developed to isolate volatile amine compounds from a Mars soil analogue inoculated with similar to 10 billion Escherichia coli cells. In this technique, the inoculated soil is heated to 500 degreesC for several seconds at Martian ambient pressure and the sublimate, collected by a cold finger, then analyzed using high performance liquid chromatography. Methylamine and ethylamine, produced from glycine and alanine decarboxylation, were the most abundant amine compounds detected after pyrolysis of the cells. A heating cycle similar to that utilized in our experiment was also used to release organic compounds from the Martian soil in the 1976 Viking gas chromatography/mass spectrometry (GC/MS) pyrolysis experiment. The Viking GC/MS did not detect any organic compounds of Martian origin above a level of a few parts per billion in the Martian surface soil. Although the Viking GC/MS instruments were not specifically designed to search for the presence of living cells on Mars, our experimental results indicate that at the part per billion level, the degradation products generated from several million bacterial cells per gram of Martian soil would not have been detected. (C) 2001 Elsevier Science B.V. All rights reserved.

Kminek, G, Bada JL, Botta O, Glavin DP, Grunthaner F.  2000.  MOD: an organic detector for the future robotic exploration of Mars. Planetary and Space Science. 48:1087-1091.   10.1016/s0032-0633(00)00082-9   AbstractWebsite

Searching for extinct or extant life on Mars is part of the future NASA surveyor class missions. Looking for key organic compounds that are essential for biochemistry as we know it or indicative of extraterrestrial organic influx is the primary goal of the Mars Organic Detector (MOD). MOD is able to detect amino acids, amines and PAHs with at least 100 times higher sensitivity than the Viking GCMS experiment. MOD is not capable of identifying specific organic molecules but can assess the organic inventory of amines and PAHs on the planet. MOD can also quantify adsorbed and chemisorbed water and evolved carbon dioxide in a stepped heating cycle to determine specific carbon-bearing minerals. All that comes with no sample preparation and no wet chemistry. The organics can be isolated from the carrier matrix by heating the sample and recovering the volatile organics on a cold finger. This sublimation technique can be used for extracting amino acids, amines and PAHs under Mars ambient conditions. The detection of amino acids, amines and PAHs is based on a fluorescence detection scheme. The MOD concept has functioned as a laboratory breadboard since 1998. A number of natural samples including shells, clays, bones, lambda -DNA and E.-coli bacteria have been used and organic molecules have been extracted successfully in each case. The first prototype of MOD is operational as of early fall of 1999. MOD has been selected for the definition phase of the NASA-MSR 2003 mission. (C) 2000 Elsevier Science Ltd. All rights reserved.

Brinton, KL, Bada JL.  1995.  Aspartic-Acid Racemization and Protein Diagenesis in Corals over the Last 350 Years - Comment. Geochimica Et Cosmochimica Acta. 59:415-416.Website
Zhao, MX, Bada JL.  1995.  Determination of Alpha-Dialkylamino Acids and Their Enantiomers in Geological Samples by High-Performance Liquid-Chromatography after Derivatization with a Chiral Adduct of O-Phthaldialdehyde. Journal of Chromatography A. 690:55-63.   10.1016/0021-9673(94)00927-2   AbstractWebsite

Derivatization with o-phthaldialdehyde (OPA) and the chiral thiol N-acetyl-L-cysteine (NAG) is a convenient and sensitive technique for the HPLC detection and resolution of protein amino acid enantiomers. The kinetics of the reaction of OPA-NAC with alpha-dialkylamino acids was investigated. The fluorescence yield of alpha-dialkylamino acids was only about 10% of that of protein amino acids when the derivatization was carried out at room temperature for 1-2 min, which is the procedure generally used for protein amino acid analyses. The fluorescence yield of alpha-dialkylamino acids can be enhanced by up to ten-fold when the derivatization reaction time is increased to 15 min at room temperature. The OPA-NAC technique was optimized for the detection and enantiomeric resolution of alpha-dialkylamino acids in geological samples which contain a large excess of protein amino acids. The estimated detection limit for alpha-dialkylamino acids is 1-2 pmol, comparable to that for protein amino acids.

Chen, RF, Bada JL.  1994.  The Fluorescence of Dissolved Organic-Matter in Porewaters of Marine-Sediments. Marine Chemistry. 45:31-42.   10.1016/0304-4203(94)90089-2   AbstractWebsite

The fluorescence of porewaters from marine sediment cores from six different areas was measured. In most cases, fluorescence was affected primarily by the diagenesis of organic carbon first through sulfate reduction and subsequently by methane generation. Typically, fluorescence, dissolved organic carbon (DOC), absorbance, alkalinity, and ammonium ion concentrations correlate quite well, increasing in the upper sections of anoxic sediments and co-varying in deeper sections of these cores. The good correlation of DOC with fluorescence in the three cores in which DOC was measured indicates that fluorescence can be used to make a first order estimate of DOC concentration in anoxic porewaters. Data are consistent with a model in which labile organic matter in the sediments is broken down by sulfur reducing bacteria to low molecular weight monomers. These monomers are either remineralized to CO2 or polymerize to form dissolved, fluorescent, high molecular weight molecules. The few exceptions to this model involve hydrothermally generated hydrocarbons that are formed in situ in the Guaymas Basin or are horizontally advected along the decollement in the Nankai Trench.

Bada, JL, Bigham C, Miller SL.  1994.  Impact Melting of Frozen Oceans on the Early Earth - Implications for the Origin of Life. Proceedings of the National Academy of Sciences of the United States of America. 91:1248-1250.   10.1073/pnas.91.4.1248   AbstractWebsite

Without sufficient greenhouse gases in the atmosphere, the early Earth would have become a permanently frozen planet because the young Sun was less luminous than it is today. Several resolutions to this faint young Sun-frozen Earth paradox have been proposed, with an atmosphere rich in CO2 being the one generally favored. However, these models assume that there were no mechanisms for melting a once frozen ocean. Here we show that bolide impacts between about 3.6 and 4.0 billion years ago could have episodically melted an ice-covered early ocean. Thaw-freeze cycles associated with bolide impacts could have been important for the initiation of abiotic reactions that gave rise to the first living organisms.

Sagan, C, Khare BN, Thompson WR, McDonald GD, Wing MR, Bada JL, Tuan VD, Arakawa ET.  1993.  Polycyclic Aromatic-Hydrocarbons in the Atmospheres of Titan and Jupiter. Astrophysical Journal. 414:399-405.   10.1086/173086   AbstractWebsite

Polycyclic aromatic hydrocarbons (PAHs) are important components of the interstellar medium and carbonaceous chondrites, but have never been identified in the reducing atmospheres of the outer solar system. Incompletely characterized complex organic solids (tholins) produced by irradiating simulated Titan atmospheres reproduce well the observed UV/visible/IR optical constants of the Titan stratospheric haze. Titan tholin and a tholin generated in a crude simulation of the atmosphere of Jupiter are examined by two-step laser desorption/multiphoton ionization mass spectrometry. A range of two- to four-ring PAHs, some with one to four alkylation sites are identified, with net abundance approximately 10(-4) g g-1 (grams per gram) of tholins produced. Synchronous fluorescence techniques confirm this detection. Titan tholins have proportionately more one- and two-ring PAHs than do Jupiter tholins, which in turn have more four-ring and larger PAHs. The four-ringed PAH chrysene, prominent in some discussions of interstellar grains, is found in Jupiter tholins. Solid state C-13 NMR spectroscopy suggests congruent-to 25% of the total C in both tholins is tied up in aromatic and/or aliphatic alkenes. IR spectra indicate an upper limit in both tholins of congruent-to 6% by mass in benzenes, heterocyclics, and PAHs with more than four rings. Condensed PAHs may contribute at most approximately 10% to the observed detached limb haze layers on Titan. As with interstellar PAHs, the synthesis route of planetary PAHs is likely to be via acetylene addition reactions.

Chen, RF, Bada JL, Suzuki Y.  1993.  The Relationship between Dissolved Organic-Carbon (Doc) and Fluorescence in Anoxic Marine Porewaters - Implications for Estimating Benthic Doc Fluxes. Geochimica Et Cosmochimica Acta. 57:2149-2153.   10.1016/0016-7037(93)90102-3   AbstractWebsite

Fluorescence and dissolved organic carbon (DOC) measurements of porewaters from the Santa Barbara Basin, the Guaymas Basin, and the upper sections of the Nankai Trough suggest that ultraviolet fluorescence (lambda(ex) = 325 nm, lambda(em) = 450 nm) may be used as a first order estimate of DOC in anoxic marine porewaters. The majority of porewater organic carbon appears to be fluorescent, while a constant approximately 1 mM DOC, probably the low molecular weight compounds, is not fluorescent. These data are consistent with a model in which low molecular weight compounds dissolved in porewater act as the common intermediate between labile sedimentary organic matter and remineralization or polymerization products. Fluorescence may also be used to sensitively estimate benthic DOC fluxes to the overlying water column. Results from the Santa Barbara Basin, if representative of global anoxic oceanic regions, indicate that DOC release from anoxic sediments is not a major source of oceanic DOC when compared to internal recycling rates, but may be comparable to external input or permanent removal processes.

Zenobi, R, Philippoz JM, Zare RN, Wing MR, Bada JL, Marti K.  1992.  Organic-Compounds in the Forest Vale, H4 Ordinary Chondrite. Geochimica Et Cosmochimica Acta. 56:2899-2905.   10.1016/0016-7037(92)90366-q   AbstractWebsite

We have analyzed the H4 ordinary chondrite Forest Vale for polycyclic aromatic hydrocarbons (PAHs) using two-step laser mass spectrometry (L2MS) and for amino acids using a standard chromatographic method. Indigenous PAHs were identified in the matrices of freshly cleaved interior faces but could not be detected in pulverized silicates and chondrules. No depth dependence of the PAHs was found in a chipped interior piece. Amino acids, taken from the entire sample, consisted of protein amino acids that were nonracemic, indicating that they are terrestrial contaminants. The presence of indigenous PAHs and absence of indigenous amino acids provides support for the contention that different processes and environments contributed to the synthesis of the organic matter in the solar system.

Wing, MR, Bada JL.  1992.  The Origin of the Polycyclic Aromatic-Hydrocarbons in Meteorites. Origins of Life and Evolution of the Biosphere. 21:375-383. AbstractWebsite

Polycyclic aromatic hydrocarbons (PAHs) in Cl and C2 Carbonaceous Chondrites appear to be the product of a high-temperature synthesis. This observation counters a prevailing view that PAHs in meteorites are a thermal alternation product of preexisting aliphatic compounds, which in turn required the presence of low-temperature mineral phases such as magnetite and hydrated phyllosilicates for their formation. Such a process would necessarily lead to a more low-temperature assemblage of PAHs, as many low-temperature minerals and compounds are extant in meteorites. Ivuna, a C1 carbonaceous chondrite, has been shown to contain abundant amounts of the three-ring PAHs phenanthrene/anthracene, but no detectable levels of the two- and four-ring PAHs naphthalene and pyrene/fluoranthene. Ivuna and other C1 carbonaceous chondrites are known to have been extensively altered by water. The aqueous solubilities of PAHs indicate that some PAHs would have been mobilized during the aqueous alteration phase in meteorite parent bodies. Model geochromatography experiments using crushed serpentine or beach sand as the solid phase and water for elution suggest that the complete separation of two, three, and four-ring PAHs could be expected to occur in the parent body of C1 carbonaceous chondrites. It is proposed that aqueous fluids driven by heat in the parent body of Ivuna migrated from the interior to the surface, in the process transporting, separating and concentrating PAHs at various zones in the parent body. The presence of indigenous PAHs and absence of indigenous amino acids in the H4 ordinary chondrite Forest Vale provides support for the contention that different processes and environments contributed to the synthesis of the organic matter in the solar system.