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Review
. 2019 Jun 18;9(2):50.
doi: 10.3390/life9020050.

Evolutionary Steps in the Analytics of Primordial Metabolic Evolution

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Free PMC article
Review

Evolutionary Steps in the Analytics of Primordial Metabolic Evolution

Thomas Geisberger et al. Life (Basel). .
Free PMC article

Abstract

Experimental studies of primordial metabolic evolution are based on multi-component reactions which typically result in highly complex product mixtures. The detection and structural assignment of these products crucially depends on sensitive and selective analytical procedures. Progress in the instrumentation of these methods steadily lowered the detection limits to concentrations in the pico molar range. At the same time, conceptual improvements in chromatography, nuclear magnetic resonance (NMR) and mass spectrometry dramatically increased the resolution power as well as throughput, now, allowing the simultaneous detection and structural determination of hundreds to thousands of compounds in complex mixtures. In retrospective, the development of these analytical methods occurred stepwise in a kind of evolutionary process that is reminiscent of steps occurring in the evolution of metabolism under chemoautotrophic conditions. This can be nicely exemplified in the analytical procedures used in our own studies that are based on Wächtershäuser's theory for metabolic evolution under Fe/Ni-catalyzed volcanic aqueous conditions. At the onset of these studies, gas chromatography (GC) and GC-MS (mass spectrometry) was optimized to detect specific low molecular weight products (<200 Da) in a targeted approach, e.g., methyl thioacetate, amino acids, hydroxy acids, and closely related molecules. Liquid chromatography mass spectrometry (LC-MS) was utilized for the detection of larger molecules including peptides exceeding a molecular weight of 200 Da. Although being less sensitive than GC-MS or LC-MS, NMR spectroscopy benefitted the structural determination of relevant products, such as intermediates involved in a putative primordial peptide cycle. In future, Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) seems to develop as a complementary method to analyze the compositional space of the products and reaction clusters in a non-targeted approach at unprecedented sensitivity and mass resolution (700,000 for m/z 250). Stable isotope labeling was important to differentiate between reaction products and artifacts but also to reveal the mechanisms of product formation. In this review; we summarize some of the developmental steps and key improvements in analytical procedures mainly used in own studies of metabolic evolution.

Keywords: FT-ICR; GC-MS; LC-MS; NMR; origin of life; reaction network; stable isotopes.

Conflict of interest statement

The authors declare no conflict of interest.

Figures

Figure 1
Figure 1
Evolution of the molecular complexity in the “origin-of-life” scenario triggered by a chemoautotrophic evolution of metabolism and evolution of methods for its analysis. Catalyzed by minerals present in the crust of early Earth, simple organic molecules were formed from simple inorganic molecules. Through polymerization biomolecules could have emerged which allowed the evolution of cells and the “Pioneer organism”. This evolution of molecular complexity is reflected by the evolution of analytical tools and the amount of information delivered by them. PC: paper chromatography; TLC: thin layer chromatography; GC-FID: gas chromatography-flame ionization detector; HPLC-UV: high pressure liquid chromatography-UV; GC-MS: gas chromatography mass spectrometry; LC-MS: liquid chromatography mass spectrometry; NMR: nuclear magnetic resonance; FT-ICR-MS: Fourier transform ion cyclotron resonance mass spectrometry.
Figure 2
Figure 2
GC-MS trace with identified products from an experiment performed at 160 °C at 75 bar for 20 h with Ni, CO, and CN [38].
Figure 3
Figure 3
Formation of amino acid MTBSTFA derivatives used for GC-MS analysis.
Figure 4
Figure 4
LC-MS trace showing the TIC (total ion current) of a peptide forming experiment starting from phenylalanine [69]. Retention times are as follows: Phe: 1.75 min; PhePhe: 2.97 and 6.55 min; PhePhePhe: 7.97 and 10.97 min; PhePhe +44au: 9.6 and 11.1 min; PhePhe +26au: 12.57 PhePhePhe +44au: 13.87 min; PhePhePhe +26au: 15.39 min.
Figure 5
Figure 5
(a) Urea derivative of Phe–Phe; (b) Hydantoin derivative of Phe–Phe [69].
Figure 6
Figure 6
FeS, NiS catalyzed, CO driven peptide cycle as observed for phenylalanine [69].
Scheme 1
Scheme 1
Mixed use of CO and CN- in double carbonylation reactions as shown by stable isotope labelling. Freshly precipitated [Ni(OH)(13CN)] or [Co(OH)(13CN)] was used as catalyst at pH 12.6 and 60 °C [42].
Figure 7
Figure 7
(Inset) FT-ICR-MS spectrum ranging from 120 to 800 m/z of a typical product mixture in our “origin-of-life” research. The spectral region around the nominal mass 295 m/z is displayed showing the high resolution and annotated elemental composition of the negatively charged ions.
Figure 8
Figure 8
Van Krevelen diagram showing the CHOS chemical space from an experiment performed at 105 °C for 7 days with Ni, CO, and C2H2, analyzed by FT-ICR-MS.

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