Export 5 results:
Sort by: Author Title Type [ Year  (Desc)]
Parker, ET, Cleaves HJ, Bada JL, Fernandez FM.  2016.  Quantitation of alpha-hydroxy acids in complex prebiotic mixtures via liquid chromatography/tandem mass spectrometry. Rapid Communications in Mass Spectrometry. 30:2043-2051.   10.1002/rcm.7684   AbstractWebsite

RationaleSpark discharge experiments, like those performed by Stanley Miller in the 1950s, generate complex, analytically challenging mixtures that contain biopolymer building blocks. Recently, -amino acids and -hydroxy acids (AHAs) were subjected to environmental cycling to form simple depsipeptides (peptides with both amide and ester linkages). The synthesis of AHAs under possible primordial environments must be examined to better understand this chemistry. MethodsWe report a direct, quantitative method for AHAs using ultrahigh-performance liquid chromatography and triple quadrupole mass spectrometry. Hexylamine ion-pairing chromatography and selected reaction monitoring detection were combined for the rapid analysis of ten AHAs in a single run. Additionally, prebiotic simulation experiments, including the first-ever reproduction of Miller's 1958 cyanamide spark discharge experiment, were performed to evaluate AHA synthesis over a wide range of possible primitive terrestrial environments. ResultsThe quantitating transition for each of the AHAs targeted in this study produced a limit of detection in the nanomolar concentration range. For most species, a linear response over a range spanning two orders of magnitude was found. The AHAs glycolic acid, lactic acid, malic acid, and -hydroxyglutaric acid were detected in electric discharge experiments in the low micromolar concentration range. ConclusionsThe results of this work suggest that the most abundant building blocks available for prebiotic depsipeptide synthesis would have been glycolic, lactic, malic, and -hydroxyglutaric acids, and their corresponding amino acids, glycine, alanine, and aspartic and glutamic acids. Copyright (c) 2016 John Wiley & Sons, Ltd.

Parker, ET, Cleaves JH, Burton AS, Glavin DP, Dworkin JP, Zhou MS, Bada JL, Fernandez FM.  2014.  Conducting Miller-Urey experiments. Jove-Journal of Visualized Experiments.   10.3791/51039   AbstractWebsite

In 1953, Stanley Miller reported the production of biomolecules from simple gaseous starting materials, using an apparatus constructed to simulate the primordial Earth's atmosphere-ocean system. Miller introduced 200 ml of water, 100 mmHg of H-2, 200 mmHg of CH4, and 200 mmHg of NH3 into the apparatus, then subjected this mixture, under reflux, to an electric discharge for a week, while the water was simultaneously heated. The purpose of this manuscript is to provide the reader with a general experimental protocol that can be used to conduct a Miller-Urey type spark discharge experiment, using a simplified 3 L reaction flask. Since the experiment involves exposing inflammable gases to a high voltage electric discharge, it is worth highlighting important steps that reduce the risk of explosion. The general procedures described in this work can be extrapolated to design and conduct a wide variety of electric discharge experiments simulating primitive planetary environments.

Botta, O, Martins Z, Emmenegger C, Dworkin JP, Glavin DP, Harvey RP, Zenobi R, Bada JL, Ehrenfreund P.  2008.  Polycyclic aromatic hydrocarbons and amino acids in meteorites and ice samples from LaPaz Icefield, Antarctica. Meteoritics & Planetary Science. 43:1465-1480. AbstractWebsite

We have analyzed ice samples and meteorites from the LaPaz region of Antarctica to investigate the composition of polycyclic aromatic hydrocarbons (PAHs) and amino acids with the goal to understand whether or not there is a compositional relationship between the two reservoirs. Four LL5 ordinary chondrites (OCs) and one CK carbonaceous chondrite were collected as part of the 2003/2004 ANSMET season. Ice samples collected from directly underneath the meteorites were extracted. In addition, exhaust particles from the snowmobiles used during the expedition were collected to investigate possible contributions from this source. The meteorite samples, the particulate matter and solid-state extracts of the ice samples and the exhaust filters were subjected to two-step laser mass spectrometry (L2MS) to investigate the PAH composition. For amino acids analysis, the meteorites were extracted with water and acid hydrolyzed, and the extracts were analyzed with offline OPA/NAC derivatization combined with liquid chromatography with UV fluorescence detection and time of flight mass spectrometry (LC-FC/ToF-MS). PAHs in the particulate matter of the ice were found to be qualitatively similar to the meteorite samples, indicating that micron-sized grains of the meteorite may be embedded in the ice samples. The concentration levels of dissolved PAHs in all the ice samples were found to be below the detection limit of the L2MS. The PAH composition of the snowmobile exhaust is significantly different to the one in particulate matter, making it an unlikely Source of contamination for Antarctic meteorites. The amino acids glycine, beta-alanine and gamma-amino-n-butyric acid that were detected at concentrations of 3 to 19 parts per billion (ppb) are probably indigenous to the Antarctic meteorites. Some of the LaPaz ice samples were also found to contain amino acids at concentration levels of 1 to 33 parts per trillion (ppt), in particular alpha-aminoisobutyric acid (AIB), an abundant non-protein amino acid of extraterrestrial Origin found in some carbonaceous chondrites. We hypothesize that this amino acid could have been extracted from Antarctic micrometeorites and the particulate matter of the meteorites during the concentration procedure of the ice samples.

Botta, O, Bada JL, Gomez-Elvira J, Javaux E, Selsis F, Summons R.  2008.  "Strategies of life detection": Summary and outlook. Space Science Reviews. 135:371-380.   10.1007/s11214-008-9357-9   Website
Bada, JL.  2004.  How life began on Earth: a status report. Earth and Planetary Science Letters. 226:1-15.   10.1016/j.epsl.2004.07.036   AbstractWebsite

There are two fundamental requirements for life as we know it, liquid water and organic polymers, such as nucleic acids and proteins. Water provides the medium for chemical reactions and the polymers carry out the central biological functions of replication and catalysis. During the accretionary phase of the Earth, high surface temperatures would have made the presence of liquid water and an extensive organic carbon reservoir unlikely. As the Earth's surface cooled, water and simple organic compounds, derived from a variety of sources, would have begun to accumulate. This set the stage for the process of chemical evolution to begin in which one of the central facets was the synthesis of biologically important polymers, some of which had a variety of simple catalytic functions. Increasingly complex macromolecules were produced and eventually molecules with the ability to catalyze their own imperfect replication appeared. Thus began the processes of multiplication, heredity and variation, and this marked the point of both the origin of life and evolution. Once simple self-replicating entities originated, they evolved first into the RNA World and eventually to the DNA/Protein World, which had all the attributes of modern biology. If the basic components water and organic polymers were, or are, present on other bodies in our solar system and beyond, it is reasonable to assume that a similar series of steps that gave rise of life on Earth could occur elsewhere. (C) 2004 Elsevier B.V. All rights reserved.