Base-pairing of uracil and 2,6-diaminopurine: from cocrystals to photoreactivity

Highlights•Base-pairing in reaction conditions of different water availability and temperatures•Crystal structures solved from electron and single-crystal X-ray diffraction data•Photodegradation of base-pair under UV irradiationSummaryWe show that the non-canonical nucleobase 2,6-diaminopurine (D) spontaneously base pairs with uracil (U) in water and the solid state without the need to be attached to the ribose-phosphate backbone. Depending on the reaction conditions, D and U assemble in thermodynamically stable hydrated and anhydrated D-U base-paired cocrystals. Under UV irradiation, an aqueous solution of D-U base-pair undergoes photochemical degradation, while a pure aqueous solution of U does not. Our simulations suggest that D may trigger the U photodimerization and show that complementary base-pairing modifies the photochemical properties of nucleobases, which might have implications for prebiotic chemistry.