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We have analyzed the chemical variety obtained by Miller-Urey-type experiments using nuclear magnetic resonance (NMR) spectroscopy and coherent anti-Stokes Raman scattering (CARS) spectroscopy, gas chromatography followed by mass spectrometry (GC/MS) and two-dimensional gas chromatography followed by mass spectrometry (GCxGC/MS). In the course of a running Miller-Urey-type experiment, a hydrophobic organic layer emerged besides the hydrophilic aqueous phase and the gaseous phase that were initially present. The gas phase mainly consisted of aromatic compounds and molecules containing C≡C or C≡N triple bonds. The hydrophilic phase contained at least a few thousands of different molecules, primarily distributed in a range of 50 and 500 Da. The hydrophobic phase is characterized by carbon-rich, oil-like compounds and their amphiphilic derivatives containing oxygen with tensioactive properties. The presence of a wide range of oxidized molecules hints to the availability of oxygen radicals. We suggest that they intervene in the formation of alkylated polyethylene glycol (PEG) in the oil/water interface. CARS spectroscopy revealed distinct vibrational molecular signatures. In particular, characteristic spectral bands for cyanide compounds were observed if the broth was prepared with electric discharges in the gaseous phase. The characteristic spectral bands were absent if discharges were released onto the water surface. NMR spectroscopy on the same set of samples independently confirmed the observation. In addition, NMR spectroscopy revealed overall high chemical variability that suggests strong non-linearities due to interdependent, sequential reaction steps. Electronic supplementary material The online version of this article (doi:10.1007/s11084-016-9528-8) contains supplementary material, which is available to authorized users.

Das Prinzip der Musterbildung ist aus nichtlinearen und dissipativen Systemen, die in der Physik ausführlich behandelt wurden (z. B. Laser), bekannt. Es ist unklar, unter welchen Bedingungen in einem organischen, chemischen System spontan eine Strukturbildung einsetzt. Diese Frage ist fundamental für das Verständnis der Entstehung des Lebens auf der Erde. In dieser Arbeit wurden verschiedene komplexe, chemische Mischungen untersucht. Sie entstanden unkontrolliert aus einfachen organischen Verbindungen. Die zeitliche Entwicklung der getriebenen Gemische wurde mittels Massenspektrometrie kontinuierlich verfolgt. Es wurde reproduzierbar eine spontane, aperiodische Oszillation mehrerer oligomerer Spezies beobachtet. Die Oligomere tauchten mehrfach innerhalb von Sekunden auf und blieben einige Sekunden oder Minuten in den Massenspektren sichtbar, bevor sie verschwanden. Die Gesamtheit der Ergebnisse spricht für eine auto- oder kreuzkatalytische Bildung der Oligomere. Der hier vorgestellte Reaktor erzeugt zufällig neue Moleküle und legt auf diese Weise selbstständig neue Reaktionswege fest. In einem Laser relaxiert ein angeregter Zustand in einer selbstreproduzierenden optischen Mode. Analog relaxieren in dem Reaktor angeregte Zustände durch spontane Ausbrüche autokatalytischer, chemischer Moden. Das selbstreproduzierende Verhalten ist in der organischen Chemie offenbar bereits eingebaut. Es führt unter verschiedenen Bedingungen zur Bildung autokatalytischer, dynamischer Oligomere. Pattern formation is well-known from non-linear, dissipative systems (e. g. lasers) and was intensively studied in physics. However, the conditions needed for structure formation in an organic, chemical system are not known. This question is fundamental for the understanding of the origin of life on Earth. In this thesis many complex, chemical mixtures were analysed. They evolved unregulated from simple, organic compounds. We continuously monitored the temporal development of the mixture by mass spectrometry. We observed the spontaneous, aperiodic oscillation of several oligomeric species. The oligomers appeared repeatedly within seconds, stayed for minutes until they disappeared. The observations can be explained by auto- or cross-catalytic chemical reaction mechanisms. The presented reactor produces randomly new molecules. It redefines autonomously possible reaction pathways. In a laser, an excited state relaxes through a self-reproducing optical mode. In analogy, in the reactor the excited states relax through spontaneous bursts of autocatalytic, chemical modes. This self-reproducing behaviour is obviously built into the rules of organic chemistry. It delivers autocatalytic, dynamic oligomers under various conditions.