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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. 

We have structurally characterized the liquid crystal (LC) phase that can appear as an intermediate state when a dielectric nematic, having polar disorder of its molecular dipoles, transitions to the almost perfectly polar-ordered ferroelectric nematic. This intermediate phase, which fills a 100-y-old void in the taxonomy of smectic LCs and which we term the “smectic Z A ,” is antiferroelectric, with the nematic director and polarization oriented parallel to smectic layer planes, and the polarization alternating in sign from layer to layer with a 180 Å period. A Landau free energy, originally derived from the Ising model of ferromagnetic ordering of spins in the presence of dipole–dipole interactions, and applied to model incommensurate antiferroelectricity in crystals, describes the key features of the nematic–SmZ A –ferroelectric nematic phase sequence. 

In high-resolution adiabatic scanning calorimetry (ASC) experiments, data for the temperature dependence of the specific enthalpy, h(T), and of the specific heat capacity, c(p)(T), are simultaneously obtained, from which the order of the phase transition and critical behaviour can be evaluated. ASC was applied to study the nematic to ferroelectric nematic phase transition (N-N-F) in the liquid crystal molecule 4-[(4-nitrophenoxy)carbonyl]phenyl 2,4-dimethoxybenzoate (RM734). The N-N-F was found to be very weakly first order with a latent heat Delta h = 0.115 +/- 0.005 J/g. The pretransitional specific heat capacity behaviour is substantially larger in the high-temperature N phase than in the low-temperature N-F phase. In both phases the power-law analysis of c(p)(T) resulted in a critical exponent alpha = 0.50 +/- 0.05 and amplitude ratio A(NF)/A(N) = 0.42 +/- 0.03. The very small latent heat and the value of alpha indicate that the N-N-F transition is close to a tricritical point. This is confirmed by a value of the order parameter exponent beta approximate to 0.25, recently obtained from electric polarisation measurements. Invoking two-scale-factor universality, it follows from the low value of A(NF)/A(N) ratio that the size of the critical fluctuations is much larger in the N-F phase than in the N phase. 

We report the observation of the smectic A F , a liquid crystal phase of the ferroelectric nematic realm. The smectic A F is a phase of small polar, rod-shaped molecules that form two-dimensional fluid layers spaced by approximately the mean molecular length. The phase is uniaxial, with the molecular director, the local average long-axis orientation, normal to the layer planes, and ferroelectric, with a spontaneous electric polarization parallel to the director. Polarization measurements indicate almost complete polar ordering of the ∼10 Debye longitudinal molecular dipoles, and hysteretic polarization reversal with a coercive field ∼2 × 10 5 V / m is observed. The SmA F phase appears upon cooling in two binary mixtures of partially fluorinated mesogens: 2N/DIO, exhibiting a nematic (N)–smectic Z A (SmZ A )–ferroelectric nematic (N F )–SmA F phase sequence, and 7N/DIO, exhibiting an N–SmZ A –SmA F phase sequence. The latter presents an opportunity to study a transition between two smectic phases having orthogonal systems of layers. 

The success of nematic liquid crystals in displays and optical applications is due to the combination of their optical uniaxiality, fluidity, elasticity, responsiveness to electric fields and controllable coupling of the molecular orientation at the interface with solid surfaces. The discovery of a polar nematic phase opens new possibilities for liquid crystal-based applications, but also requires a new study of how this phase couples with surfaces. Here we explore the surface alignment of the ferroelectric nematic phase by testing different rubbed and unrubbed substrates that differ in coupling strength and anchoring orientation and find a variety of behaviors – in terms of nematic orientation, topological defects and electric field response – that are specific to the ferroelectric nematic phase and can be understood as a consequence of the polar symmetry breaking. In particular, we show that by using rubbed polymer surfaces it is easy to produce cells with a planar polar preferential alignment and that cell electrostatics ( e.g. grounding the electrodes) has a remarkable effect on the overall homogeneity of the ferroelectric ordering.