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At high concentration, long Watson/Crick (WC) double-helixed DNA forms columnar crystal or liquid crystal phases of linear, parallel duplex chains packed on periodic lattices. This can also be a structural motif of short NA oligomers such as the 5’-GTAC-3’ studied here, which makes four-base WC duplexes having hydrophobic blunt ends. End-to-end aggregation then assembles these duplexes into columns and columnar phases are stabilized, in spite of breaks in the double helix every four bases. But the new degrees of freedom introduced by such breaks also enable opportunities for a more diverse palette of self-assembly modes, producing striking self-assemblies of DNA that would not be achievable with contiguous polymers. These include recently reported three-dimensional (3D) periodic low-density nanoscale networks of GCCG, and the twist grain boundary (TGB) phase presented here. In the TGB, columns of GTAC pairs assemble into monolayer sheets in which the duplex columns are mutually parallel. However, unlike in the columnar crystals, these sheets stack in helical fashion into lamellar arrays in which the column axis of each layer is rotated through a 60° angle with respect to the columns in neighboring layers. This assembly of DNA is unique in that it the fills a 3D volume wherein the major grooves of columns in each layer mutually enter and interlock with the major grooves of columns in neighboring layers. This locking is optimized by small adjustments in structure enabled by the breaks in the duplex backbones. 

Nucleic acids (NAs) in modern biology accomplish a variety of tasks, and the emergence of primitive nucleic acids is broadly recognized as a crucial step for the emergence of life. While modern NAs have been optimized by evolution to accomplish various biological functions, such as catalysis or transmission of genetic information, primitive NAs could have emerged and been selected based on more rudimental chemical–physical properties, such as their propensity to self-assemble into supramolecular structures. One such supramolecular structure available to primitive NAs are liquid crystal (LC) phases, which are the outcome of the collective behavior of short DNA or RNA oligomers or monomers that self-assemble into linear aggregates by combinations of pairing and stacking. Formation of NA LCs could have provided many essential advantages for a primitive evolving system, including the selection of potential genetic polymers based on structure, protection by compartmentalization, elongation, and recombination by enhanced abiotic ligation. Here, we review recent studies on NA LC assembly, structure, and functions with potential prebiotic relevance. Finally, we discuss environmental or geological conditions on early Earth that could have promoted (or inhibited) primitive NA LC formation and highlight future investigation axes essential to further understanding of how LCs could have contributed to the emergence of life. 

Understanding of the pairing statistics in solutions populated by a large number of distinct solute species with mutual interactions is a challenging topic, relevant in modeling the complexity of real biological systems. Here we describe, both experimentally and theoretically, the formation of duplexes in a solution of random-sequence DNA (rsDNA) oligomers of lengthL= 8, 12, 20 nucleotides. rsDNA solutions are formed by 4^Ldistinct molecular species, leading to a variety of pairing motifs that depend on sequence complementarity and range from strongly bound, fully paired defectless helices to weakly interacting mismatched duplexes. Experiments and theory coherently combine revealing a hybridization statistics characterized by a prevalence of partially defected duplexes, with a distribution of type and number of pairing errors that depends on temperature. We find that despite the enormous multitude of inter-strand interactions, defectless duplexes are formed, involving a fraction up to 15% of the rsDNA chains at the lowest temperatures. Experiments and theory are limited here to equilibrium conditions. 

Although its mesomorphic properties have been studied for many years, only recently has the molecule of life begun to reveal the true range of its rich liquid crystalline behavior. End-to-end interactions between concentrated, ultrashort DNA duplexes—driving the self-assembly of aggregates that organize into liquid crystal phases—and the incorporation of flexible single-stranded “gaps” in otherwise fully paired duplexes—producing clear evidence of an elementary lamellar (smectic-A) phase in DNA solutions—are two exciting developments that have opened avenues for discovery. Here, we report on a wider investigation of the nature and temperature dependence of smectic ordering in concentrated solutions of various “gapped” DNA (GDNA) constructs. We examine symmetric GDNA constructs consisting of two 48-base pair duplex segments bridged by a single-stranded sequence of 2 to 20 thymine bases. Two distinct smectic layer structures are observed for DNA concentration in the range $\sim 230\text{to}\sim 280$mg/mL. One exhibits an interlayer periodicity comparable with two-duplex lengths (“bilayer” structure), and the other has a period similar to a single-duplex length (“monolayer” structure). The bilayer structure is observed for gap length ≳10 bases and melts into the cholesteric phase at a temperature between 30 °C and 35 °C. The monolayer structure predominates for gap length ≲10 bases and persists to $>40\hspace{0.17em}°$C. We discuss models for the two layer structures and mechanisms for their stability. We also report results for asymmetric gapped constructs and for constructs with terminal overhangs, which further support the model layer structures.