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Bada, JL, Chalmers JH, Cleaves HJ.  2016.  Is formamide a geochemically plausible prebiotic solvent? Physical Chemistry Chemical Physics. 18:20085-20090.   10.1039/c6cp03290g   AbstractWebsite

From a geochemical perspective, significant amounts of pure formamide (HCONH2) would have likely been rare on the early Earth. There may have been mixed formamide-water solutions, but even in the presence of catalyst, solutions with >= 20 weight% water in formamide would not have produced significant amounts of prebiotic compounds. It might be feasible to produce relatively pure formamide by a rare occurrence of freezing formamide/water mixtures at temperatures lower than formamide's freezing point (2.55 degrees C) but greater than the freezing point of water. Because of the high density of formamide ice it would have sunk and accumulated at the bottom of the solution. If the remaining water froze on the surface of this ice, and was then removed by a sublimation-ablation process, a small amount of pure formamide ice might have been produced. In addition a recent report suggested that similar to 85 weight% formamide could be prepared by a geochemical type of fractional distillation process, offering another possible route for prebiotic formamide production.

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.

Bennett, RV, Cleaves HJ, Davis JM, Sokolov DA, Orlando TM, Bada JL, Fernandez FM.  2013.  Desorption Electrospray Ionization Imaging Mass Spectrometry as a Tool for Investigating Model Prebiotic Reactions on Mineral Surfaces. Analytical Chemistry. 85:1276-1279.   10.1021/ac303202n   AbstractWebsite

Mineral-assisted thermal decomposition of formamide (HCONH2) is a heavily studied model prebiotic reaction that has offered valuable insights into the plausible pathways leading to the chemical building blocks of primordial informational polymers. To date, most efforts have focused on the analysis of formamide reaction products released in solution, although several studies have examined the role of mineral catalysts in promoting this chemistry. We show here that the direct investigation of reactive mineral surfaces by desorption electrospray ionization-mass spectrometry imaging (DESI-MSI) gives a new perspective on the important role of the mineral surface in the formation of reaction products. As a proof-of-principle example, we show that DESI-MSI allows interrogation of the molecular products produced on heterogeneous granite samples with minimal sample preparation. Purine and pyrimidine nucleobases and their derivatives are successfully detected by DESI-MSI, with a strong correlation of the spatial product distribution with the mineral microenvironment. To our knowledge, this study is the first application of DESI-MSI to the study of complex and porous mineral surfaces and their roles in chemical evolution. This DESI-MSI approach is generally applicable to a wide range of reactions or other processes involving minerals.

Parker, ET, Cleaves HJ, Callahan MP, Dworkin JP, Glavin DP, Lazcano A, Bada JL.  2011.  Prebiotic Synthesis of Methionine and Other Sulfur-Containing Organic Compounds on the Primitive Earth: A Contemporary Reassessment Based on an Unpublished 1958 Stanley Miller Experiment. Origins of Life and Evolution of Biospheres. 41:201-212.   10.1007/s11084-010-9228-8   AbstractWebsite

Original extracts from an unpublished 1958 experiment conducted by the late Stanley L. Miller were recently found and analyzed using modern state-of-the-art analytical methods. The extracts were produced by the action of an electric discharge on a mixture of methane (CH(4)), hydrogen sulfide (H(2)S), ammonia (NH(3)), and carbon dioxide (CO(2)). Racemic methionine was formed in significant yields, together with other sulfur-bearing organic compounds. The formation of methionine and other compounds from a model prebiotic atmosphere that contained H(2)S suggests that this type of synthesis is robust under reducing conditions, which may have existed either in the global primitive atmosphere or in localized volcanic environments on the early Earth. The presence of a wide array of sulfur-containing organic compounds produced by the decomposition of methionine and cysteine indicates that in addition to abiotic synthetic processes, degradation of organic compounds on the primordial Earth could have been important in diversifying the inventory of molecules of biochemical significance not readily formed from other abiotic reactions, or derived from extraterrestrial delivery.

Parker, ET, Cleaves HJ, Dworkin JP, Glavin DP, Callahan M, Aubrey A, Lazcano A, Bada JL.  2011.  Primordial synthesis of amines and amino acids in a 1958 Miller H2S-rich spark discharge experiment. Proceedings of the National Academy of Sciences of the United States of America. 108:5526-5531.   10.1073/pnas.1019191108   AbstractWebsite

Archived samples from a previously unreported 1958 Stanley Miller electric discharge experiment containing hydrogen sulfide (H2S) were recently discovered and analyzed using high-performance liquid chromatography and time-of-flight mass spectrometry. We report here the detection and quantification of primary amine-containing compounds in the original sample residues, which were produced via spark discharge using a gaseous mixture of H2S, CH4, NH3, and CO2. A total of 23 amino acids and 4 amines, including 7 organosulfur compounds, were detected in these samples. The major amino acids with chiral centers are racemic within the accuracy of the measurements, indicating that they are not contaminants introduced during sample storage. This experiment marks the first synthesis of sulfur amino acids from spark discharge experiments designed to imitate primordial environments. The relative yield of some amino acids, in particular the isomers of aminobutyric acid, are the highest ever found in a spark discharge experiment. The simulated primordial conditions used by Miller may serve as a model for early volcanic plume chemistry and provide insight to the possible roles such plumes may have played in abiotic organic synthesis. Additionally, the overall abundances of the synthesized amino acids in the presence of H2S are very similar to the abundances found in some carbonaceous meteorites, suggesting that H2S may have played an important role in prebiotic reactions in early solar system environments.

Cleaves, HJ, Aubrey AD, Bada JL.  2009.  An Evaluation of the Critical Parameters for Abiotic Peptide Synthesis in Submarine Hydrothermal Systems. Origins of Life and Evolution of Biospheres. 39:109-126.   10.1007/s11084-008-9154-1   AbstractWebsite

It has been proposed that oligopeptides may be formed in submarine hydrothermal systems (SHSs). Oligopeptides have been synthesized previously under simulated SHS conditions which are likely geochemically implausible. We have herein investigated the oligomerization of glycine under SHS-like conditions with respect to the limitations imposed by starting amino acid concentration, heating time, and temperature. When 10(-1) M glycine solutions were heated at 250A degrees C for < 20 min glycine oligomers up to tetramers and diketopiperazine (DKP) were detectable. At 200A degrees C, less oligomerization was noted. Peptides beyond glycylglycine (gly(2)) and DKP were not detected below 150A degrees C. At 10(-2) M initial glycine concentration and below, only gly(2), DKP, and gly(3) were detected, and then only above 200A degrees C at < 20 min reaction time. Gly(3) was undetectable at longer reaction times. The major parameters limiting peptide synthesis in SHSs appear to be concentration, time, and temperature. Given the expected low concentrations of amino acids, the long residence times and range of temperatures in SHSs, it is unlikely that SHS environments were robust sources of even simple peptides. Possible unexplored solutions to the problems presented here are also discussed.

Aubrey, AD, Cleaves HJ, Bada JL.  2009.  The Role of Submarine Hydrothermal Systems in the Synthesis of Amino Acids. Origins of Life and Evolution of Biospheres. 39:91-108.   10.1007/s11084-008-9153-2   AbstractWebsite

There is little consensus regarding the plausibility of organic synthesis in submarine hydrothermal systems (SHSs) and its possible relevance to the origin of life. The primary reason for the persistence of this debate is that most experimental high temperature and high-pressure organic synthesis studies have neglected important geochemical constraints with respect to source material composition. We report here the results of experiments exploring the potential for amino acid synthesis at high temperature from synthetic seawater solutions of varying composition. The synthesis of amino acids was examined as a function of temperature, heating time, starting material composition and concentration. Using very favorable reactant conditions (high concentrations of reactive, reduced species), small amounts of a limited set of amino acids are generated at moderate temperature conditions (similar to 125-175A degrees C) over short heating times of a few days, but even these products are significantly decomposed after exposure times of approximately 1 week. The high concentration dependence observed for these synthetic reactions are demonstrated by the fact that a 10-fold drop in concentration results in orders of magnitude lower yields of amino acids. There may be other synthetic mechanisms not studied herein that merit investigation, but the results are likely to be similar. We conclude that although amino acids can be generated from simple likely environmentally available precursors under SHS conditions, the equilibrium at high temperatures characteristic of SHSs favors net amino acid degradation rather than synthesis, and that synthesis at lower temperatures may be more favorable.

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.

Skelley, AM, Aubrey AD, Willis PA, Amashukeli X, Ehrenfreund P, Bada JL, Grunthaner FJ, Mathies RA.  2007.  Organic amine biomarker detection in the Yungay region of the Atacama Desert with the Urey instrument. Journal of Geophysical Research-Biogeosciences. 112   10.1029/2006jg000329   AbstractWebsite

The Urey in situ organic compound analysis instrument, consisting of a subcritical water extractor ( SCWE) and a portable microchip capillary electrophoresis instrument called the Mars Organic Analyzer ( MOA), was field tested in the Atacama Desert, Chile, in June 2005. Soil samples from the most arid Yungay region were collected, biomarkers were extracted by the SCWE, and organic amine composition and amino acid chirality analysis was performed by the MOA. Samples collected from the top 1 cm of duracrust soil but shielded from the ambient environment by rocks were compared to the exposed duracrust. The shielded duracrust yielded amines and amino acids ranging from 50 to 100 ppb, while amino acid signals from the exposed duracrust were below blank levels. Samples from buried gypsum deposits located directly above a water flow channel contained amino acids ranging from 13 to 90 ppb. Chiral analysis revealed D/L ratios of 0.39 +/- 0.08 and 0.34 +/- 0.07 for alanine/serine and 0.78 +/- 0.06 for aspartic acid, indicating significant racemization of biologically produced amino acids. On the basis of the D/L ratios, we estimate sample ages ranging from 10(3) to 10(5) years. These results demonstrate the successful field testing of the Urey instrument, as well as the detection of biomarkers from past terrestrial life in one of the most arid and Mars-like regions on Earth.

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.

Skelley, AM, Scherer JR, Aubrey AD, Grover WH, Ivester RHC, Ehrenfreund P, Grunthaner FJ, Bada JL, Mathies RA.  2005.  Development and evaluation of a microdevice for amino acid biomarker detection and analysis on Mars. Proceedings of the National Academy of Sciences of the United States of America. 102:1041-1046.   10.1073/pnas.0406798102   AbstractWebsite

The Mars Organic Analyzer (MOA), a microfabricated capillary electrophoresis (CE) instrument for sensitive amino acid biomarker analysis, has been developed and evaluated. The microdevice consists of a four-wafer sandwich combining glass CE separation channels, microfabricated pneumatic membrane valves and pumps, and a nanoliter fluidic network. The portable MOA instrument integrates high voltage CE power supplies, pneumatic controls, and fluorescence detection optics necessary for field operation. The amino acid concentration sensitivities range from micromolar to 0.1 nM, corresponding to part-per-trillion sensitivity. The MOA was first used in the lab to analyze soil extracts from the Atacama Desert, Chile, detecting amino acids ranging from 10-600 parts per billion. Field tests of the MOA in the Panoche Valley, CA, successfully detected amino acids at 70 parts per trillion to 100 parts per billion in jarosite, a sulfate-rich mineral associated with liquid water that was recently detected on Mars. These results demonstrate the feasibility of using the MOA to perform sensitive in situ amino acid biomarker analysis on soil samples representative of a Mars-like environment.

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.

Levy, M, Miller SL, Brinton K, Bada JL.  2000.  Prebiotic synthesis of adenine and amino acids under Europa-like conditions. Icarus. 145:609-613.   10.1006/icar.2000.6365   AbstractWebsite

In order to simulate prebiotic synthetic processes on Europa and other ice-covered planets and satellites, we have investigated the prebiotic synthesis of organic compounds from dilute solutions of NH(4)CN frozen for 25 years at -20 and -78 degrees C. In addition, the aqueous products of spark discharge reactions from a reducing atmosphere were frozen for 5 years at -20 degrees C. We find that both adenine and guanine, as well as a simple set of amino acids dominated by glycine, are produced in substantial yields under these conditions, These results indicate that some of the key components necessary for the origin of life may have been available on Europa throughout its history and suggest that the circumstellar zone where life might arise may be wider than previously thought. (C) 2000 Academic Press.

Brinton, KLF, Bada JL.  1996.  A reexamination of amino acids in lunar soils: Implications for the survival of exogenous organic material during impact delivery. Geochimica Et Cosmochimica Acta. 60:349-354.   10.1016/0016-7037(95)00404-1   AbstractWebsite

Using a sensitive high performance liquid chromatography technique, we have analyzed both the hot water extract and the acid hydrolyzed hot water extract of lunar soil collected during the Apollo 17 mission. Both free amino acids and those derived from acid labile precursors are present at a level of roughly 15 ppb. Based on the D/L amino acid ratios, the free alanine and aspartic acid observed in the hot water extract can be entirely attributed to terrestrial biogenic contamination. However, in the acid labile fraction, precursors which yield amino acids are apparently present in the lunar soil. The amino acid distribution suggests that the precursor is probably solar wind implanted HCN. We have evaluated our results with regard to the meteoritic input of intact organic compounds to the moon based on an upper limit of less than or equal to 0.3 ppb for alpha-aminoisobutyric acid, a non-protein amino acid which does not generally occur in terrestrial organisms and which is not a major amino acid produced from HCN, but which is a predominant amino acid in many carbonaceous chondrites. We find that the survival of exogenous organic compounds during lunar impact is less than or equal to 0.8%. This result represents an example of minimum organic impact survivability. This is an important first step toward a better understanding of similar processes on Earth and on Mars, and their possible contribution to the budget of prebiotic organic compounds on the primitive Earth.

Bada, JL, Miller SL, Zhao MX.  1995.  The Stability of Amino-Acids at Submarine Hydrothermal Vent Temperatures. Origins of Life and Evolution of the Biosphere. 25:111-118.   10.1007/bf01581577   AbstractWebsite

It has been postulated that amino acid stability at hydrothermal vent temperatures is controlled by a metastable thermodynamic equilibrium rather than by kinetics. Experiments reported here demonstrate that the amino acids are irreversibly destroyed by heating at 240 degrees C and that quasi-equilibrium calculations give misleading descriptions of the experimental observations. Equilibrium thermodynamic calculations are not applicable to organic compounds under high-temperature submarine vent conditions.