Abstract

Solar radiation is the principal source of energy available to Earth and has unmatched potential for the synthesis of organic material from primordial molecular building blocks. As well as providing the energy for photochemical synthesis of (proto)biomolecules of interest in origins of life-related research, light has also been found to often provide remarkable selectivity in these processes, for molecules that function in extant biology and against those that do not. As such, light is heavily implicated as an environmental input on the nascent Earth that was important for the emergence of complex yet selective chemical systems underpinning life. Reactivity and selectivity in photochemical prebiotic synthesis are discussed, as are their implications for origins of life scenarios and their plausibility, and the future directions of this research.

Highlights

  • Attempts to understand the provenance of life’s building blocks on Earth have led to the study of the innate reactivity of diverse planetary chemical feedstocks

  • Refinement of these scenarios is best served by a two-way discourse, by which we consider our knowledge of chemical reactivity and how it might lead us to important biomolecules, and by which we confine ourselves to plausible proposed geochemical scenarios and attempt to discover new chemistries within them to achieve our chemical ends

  • Hydrogen cyanide is one of the simplest and most readily available planetary carbon feedstocks that can be converted into organic and biological molecules.[33−35] Our laboratory discovered the propensity of HCN to undergo photoreductive homologation to generate carbohydrates in a prebiotic context.[36−40] Over the past decade, we have demonstrated that this reductive homologation process results in the conversion of HCN and simple building blocks into a “cyanosulfidic” network of biologically relevant products

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Summary

INTRODUCTION

Attempts to understand the provenance of life’s building blocks on Earth have led to the study of the innate reactivity of diverse planetary chemical feedstocks. The question of how simple molecules available on the primordial Earth may have interacted to build systems of increasing complexity can be probed by considering the environmental inputs of a nascent Earth and coupling them with material feedstocks to develop scenarios in which molecules of interest implicated by their role in modern biology are formed Refinement of these scenarios is best served by a two-way discourse, by which we consider our knowledge of chemical reactivity and how it might lead us to important biomolecules, and by which we confine ourselves to plausible proposed geochemical scenarios and attempt to discover new chemistries within them to achieve our chemical ends. As the reader progresses, the superficiality of this classification and the inevitable entanglement of the abiotic synthetic chemistry of these classes of molecule becomes increasingly evident, along with the role of photochemistry in linking them

HISTORICAL PERSPECTIVE
PHOTOREDUCTIVE HOMOLOGATION OF HCN AND OTHER NITRILES
PHOTOCHEMICAL NUCLEOSIDE SYNTHESIS
CONDENSATION CHEMISTRY ENABLED BY PHOTOCHEMISTRY
PHOTOCHEMICAL STABILITY AND PHOTOSELECTION
CONCLUSION AND FUTURE PERSPECTIVE
Findings
■ REFERENCES

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