Deep Eutectic Solvents (DESs) and their applications [forthcoming]

Deep Eutectic Solvents (DESs) and Their Application

Abiotic ligation of DNA oligomers templated by their liquid crystal ordering

It has been observed that concentrated solutions of short DNA oligomers develop liquid crystal ordering as the result of a hierarchically structured supramolecular self-assembly. In mixtures of oligomers with various degree of complementarity, liquid crystal microdomains are formed via the selective aggregation of those oligomers that have a sufficient degree of duplexing and propensity for physical polymerization. Here we show that such domains act as fluid and permeable microreactors in which the order-stabilized molecular contacts between duplex terminals serve as physical templates for their chemical ligation. In the presence of abiotic condensing agents, liquid crystal ordering markedly enhances ligation efficacy, thereby enhancing its own phase stability. The coupling between order-templated ligation and selectivity provided by supramolecular ordering enables an autocatalytic cycle favouring the growth of DNA chains, up to biologically relevant lengths, from few-base long oligomers. This finding suggests a novel scenario for the abiotic origin of nucleic acids

Salts of HCN‐Cyanide Aggregates: [CN(HCN) 2

Although pure hydrogen cyanide can spontaneously polymerize or even explode, when initiated by small amounts of bases (e.g. CN−), the reaction of liquid HCN with [WCC]CN (WCC=weakly coordinating cation=Ph4P, Ph3PNPPh3=PNP) was investigated. Depending on the cation, it was possible to extract salts containing the formal dihydrogen tricyanide [CN(HCN)2]− and trihydrogen tetracyanide ions [CN(HCN)3]− from liquid HCN when a fast crystallization was carried out at low temperatures. X-ray structure elucidation revealed hydrogen-bridged linear [CN(HCN)2]− and Y-shaped [CN(HCN)3]− molecular ions in the crystal. Both anions can be considered members of highly labile cyanide-HCN solvates of the type [CN(HCN)n]− (n=1, 2, 3 …) as well as formal polypseudohalide ions. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA