Chemical Analysis of a “Miller-Type” Complex Prebiotic Broth
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In a famous experiment Stanley Miller showed that a large number of organic substances can emerge from sparking a mixture of methane, ammonia and hydrogen in the presence of water (Miller, Science 117:528–529, 1953). Among these substances Miller identified different amino acids, and he concluded that prebiotic events may well have produced many of Life’s molecular building blocks. There have been many variants of the original experiment since, including different gas mixtures (Miller, J Am Chem Soc 77:2351–2361, 1955; Oró Nature 197:862–867, 1963; Schlesinger and Miller, J Mol Evol 19:376–382, 1983; Miyakawa et al., Proc Natl Acad Sci 99:14,628–14,631, 2002). Recently some of Miller’s remaining original samples were analyzed with modern equipment (Johnson et al. Science 322:404–404, 2008; Parker et al. Proc Natl Acad Sci 108:5526–5531, 2011) and a total of 23 racemic amino acids were identified. To give an overview of the chemical variety of a possible prebiotic broth, here we analyze a “Miller type” experiment using state of the art mass spectrometry and NMR spectroscopy. We identify substances of a wide range of saturation, which can be hydrophilic, hydrophobic or amphiphilic in nature. Often the molecules contain heteroatoms, with amines and amides being prominent classes of molecule. In some samples we detect ethylene glycol based polymers. Their formation in water requires the presence of a catalyst. Contrary to expectations, we cannot identify any preferred reaction product. The capacity to spontaneously produce this extremely high degree of molecular variety in a very simple experiment is a remarkable feature of organic chemistry and possibly prerequisite for Life to emerge. It remains a future task to uncover how dedicated, organized chemical reaction pathways may have arisen from this degree of complexity.
KeywordsOrigin to life Complex chemical mixture Mass spectrometry NMR Miller-Urey experiment
We thank Karsten Kruse, Uli Kazmaier, Gerhard Wenz, Michael Veith, Josef Zapp, Hermann Sachdev, Daniel Krug and the Department of Pharmaceutical Biotechnology, Reiner Wintringer and the Institute for Bioanalytical Chemistry and Klaus Schappert. We thank Jörg Schmauch for contributing the SEM measurements and the EDS analysis.
Financial support from the National FT-ICR network (FR 3624 CNRS) for conducting the research is gratefully acknowledged.
- Bax A, Griffey R, Hawkins B (1983) Correlation of proton and nitrogen-15 chemical shifts by multiple quantum NMR. J Magn Reson 55:301–315Google Scholar
- Braunschweiler L, Ernst R (1983) Coherence transfer by isotropic mixing: application to proton correlation spectroscopy. J Magn Reson 53:521–528Google Scholar
- Ferus M, Nesvornýc D, Šponer J, Kubelíka P, Michalčíková R, Shestivská V, Šponer J, Civiš S (2014) High-energy chemistry of formamide: A unified mechanism of nucleobase formation. Proc Natl Acad Sci 112:657–662Google Scholar
- Miller SL (1957) The mechanism of synthesis of amino acids by electric discharges. Biochim Biophys Acta 23:490–498Google Scholar
- Selby TL, Wesdemiotis C, Lattimer RP (1994) Dissociation characteristics of [M + X] + ions (X = H, Li, Na, K) from linear and cyclic polyglycols. Int J Mass Spectrom Ion Process 5:1081–1092Google Scholar
- Starks CM, Liotta CL, Halpern ME (1994) Phase-transfer catalysis–fundamentals, applications and industrial perspectives. Springer-Science+Business Media, DordrechtGoogle Scholar
- Totten GE, Clinton NA (1998) Poly(ethylene glycol) and derivatives as phase transfer catalysts. J Macromol Sci-Pol R 38:77–142Google Scholar
- Watson JT, Sparkman OD (2008) Introduction to mass spectrometry: Instrumentation, applications and strategies for data interpretation. Wiley, ChichesterGoogle Scholar