More than 4 billion years ago, the Earth was very far from being the Blue Planet it would later become. At that point it had just begun to cool and, in the course of that process, the concentric structural zones that lie ever deeper beneath our feet were formed. The early Earth was dominated by volcanism, and the atmosphere was made up of carbon dioxide, nitrogen, methane, ammonia, hydrogen sulfide and water vapor. In this decidedly inhospitable environment the building blocks of life were formed. How then might this have come about?
Researchers have puzzled over the question for decades. The first breakthrough was made in 1953 by two chemists, named Stanley Miller and Harold C. Urey, at the University of Chicago. In their experiments, they simulated the atmosphere of the primordial Earth in a closed reaction system that contained the gases mentioned above. A miniature ‘ocean’ was heated to provide water vapor, and electrical discharges were passed through the system to mimic the effects of lightning. When they analyzed the chemicals produced under these conditions, Miller and Urey detected amino acids – the basic constituents of proteins – as well as a number of other organic acids.
It is now known that the conditions employed in these experiments did not reflect those that prevailed on the early Earth. Nevertheless, the Miller-Urey experiment initiated the field of prebiotic chemical evolution. However, it not throw much light on how other classes of molecules found in all biological cells – such as sugars, fats and nucleic acids – might have been generated. These compounds are however indispensable ingredients of the process that led to the first bacteria and subsequently to photosynthetic cyanobacteria that produced oxygen. This is why Oliver Trapp, Professor of Organic Chemistry at LMU, decided to focus his research on the prebiotic synthesis of these substances.
From formaldehyde to sugar
The story of synthetic routes from smaller precursors to sugars goes back almost a century prior to the Miller-Urey experiment. In 1861, the Russian chemist Alexander Butlerov showed that formaldehyde could give rise to various sugars via what became known as the formose reaction. Miller und Urey in fact found formic acid in their experiments, and it can be readily reduced to yield formaldehyde. Butlerov also discovered that the formose reaction is promoted by a number of metal oxides and hydroxides, including those of calcium, barium, thallium and lead. Notably calcium is abundantly available on and below the Earth’s surface.
However, the hypothesis that sugars could have been produced via the formose reaction runs into two difficulties. The ‘classical’ formose reaction produces a diverse mixture of compounds, and it takes place only in aqueous media. These requirements are at odds with the fact that sugars have been detected in meteorites.
Together with colleagues at LMU and the Max Planck Institute for Astronomy in Heidelberg, Trapp therefore decided to explore whether formaldehyde could give rise to sugars in a solid-phase system. With a view to simulating the kinds of mechanical forces to which solid minerals would have been subjected, all the reaction components were combined in a ball mill – in the absence of solvents, but adding enough formaldehyde to saturate the powdered solids
And indeed, the formose reaction was observed and several different minerals were found to catalyze it. The formaldehyde was adsorbed onto the solid particles, and the interaction resulted in the formation of the formaldehyde dimer (glycolaldehyde) – and ribose, the 5-carbon sugar that is an essential constituent of ribonucleic acid (RNA). RNA is thought to have merged prior to DNA, and it serves as the repository of genetic information in many viruses, as well as providing the templates for protein synthesis in all cellular organisms. More complex sugars were also obtained in the experiments, together with a few byproducts, such as lactic acid and methanol.
“Our results provide a plausible explanation for the formation of sugars in the solid phase, even under extraterrestrial settings in the absence of water,” says Trapp. They also prompt new questions that may point to new and unexpected prebiotic routes to the basic components of life as we know it, as Trapp affirms. “We are convinced that these new insights will open up entirely new perspectives for research on prebiotic, chemical evolution,” he says.Communications Chemistry – Nature, 2020