Dielectric Properties of a Ferroelectric Nematic Material: Quantitative Test of the Polarization-Capacitance Goldstone Mode.

The recently discovered ferroelectric nematic (N_{F}) liquid crystals (LC) have been reported to show an extraordinarily large value of the real part of the dielectric constant (ϵ^{'}>10^{3}) at low frequencies. However, it was argued by Clark et al. in Phys. Rev. Res. 6, 013195 (2024)PPRHAI2643-156410.1103/PhysRevResearch.6.013195 that what was measured was the capacitance of the insulating layer at LC or electrode surface and not that of the liquid crystal. Here we describe the results of dielectric spectroscopy measurements of an N_{F} material in cells with variable thickness of the insulating layers. Our measurements quantitatively verify the model by Clark et al. Additionally, our measurements in cells with bare conducting indium tin oxide surface provide a crude estimate of ϵ_{⊥}∼10^{2} in the N_{F} phase.

Impact of Divalent Cations on In-Layer Positional Order of DNA-Based Liquid Crystals: Implications for DNA Condensation.

The layered liquid crystalline phases formed by DNA molecules, which include rigid and flexible segments ("gapped DNA"), enable the study of both end-to-end stacking and side-to-side (helix-to-helix) lateral interactions, forming a model system to study such interactions at physiologically relevant DNA and ion concentrations. The observed layer structure exhibits long-range interlayer and in-layer positional correlations. In particular, the in-layer order has implications for DNA condensation, as it reflects whether these normally repulsive interactions become attractive under certain ionic conditions. Using synchrotron small-angle X-ray scattering measurements, we investigate the impact of divalent Mg2+ cations (in addition to a constant 150 mM Na+) on the stability of the inter- and in-layer DNA ordering as a function of temperature between 5 and 65 °C. DNA constructs with different terminal base pairings were created to mediate the strength of the attractive end-to-end stacking interactions between the blunt ends of the gapped DNA constructs. We demonstrate that the stabilities at a fixed DNA concentration of both interlayer and in-layer order are significantly enhanced even at a few mM Mg2+ concentration. The stabilities are even higher at 30 mM Mg2+; however, a marked decrease is observed at 100 mM Mg2+, suggesting a change in the nature of side-by-side interactions within this Mg2+ concentration range. We discuss the implications of these results in terms of counterion-mediated DNA-DNA attraction and DNA condensation.

Mono- and bilayer smectic liquid crystal ordering in dense solutions of "gapped" DNA duplexes.

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 [Formula: see text] 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 [Formula: see text]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.

Stability of End-to-End Base Stacking Interactions in Highly Concentrated DNA Solutions.

Positionally ordered bilayer liquid crystalline nanostructures formed by gapped DNA (GDNA) constructs provide a practical window into DNA-DNA interactions at physiologically relevant DNA concentrations; concentrations several orders of magnitude greater than those in commonly used biophysical assays. The bilayer structure of these states of matter is stabilized by end-to-end base stacking interactions; moreover, such interactions also promote in-plane positional ordering of duplexes that are separated from each other by less than twice the duplex diameter. The end-to-end stacked as well as in-plane ordered duplexes exhibit distinct signatures when studied via small-angle X-ray scattering (SAXS). This enables analysis of the thermal stability of both the end-to-end and side-by-side interactions. We performed synchrotron SAXS experiments over a temperature range of 5-65 °C on GDNA constructs that differ only by the terminal base-pairs at the blunt duplex ends, resulting in identical side-by-side interactions, while end-to-end base stacking interactions are varied. Our key finding is that bilayers formed by constructs with GC termination transition into the monolayer state at temperatures as much as 30 °C higher than for those with AT termination, while mixed (AT/GC) terminations have intermediate stability. By modeling the bilayer melting in terms of a temperature-dependent reduction in the average fraction of end-to-end paired duplexes, we estimate the stacking free energies in DNA solutions of physiologically relevant concentrations. The free-energies thereby determined are generally smaller than those reported in single-molecule studies, which might reflect the elevated DNA concentrations in our studies.

Ferroelectric nematic droplets in their isotropic melt.

The isotropic to ferroelectric nematic liquid transition was theoretically studied over one hundred years ago, but its experimental studies are rare. Here we present experimental results and theoretical considerations of novel electromechanical effects of ferroelectric nematic liquid crystal droplets coexisting with the isotropic melt. We find that the droplets have flat pancake-like shapes that are thinner than the sample thickness as long as there is room to increase the lateral droplet size. In the center of the droplets a wing-shaped defect with low birefringence is present that moves perpendicular to a weak in-plane electric field, and then extends and splits in two at higher fields. Parallel to the defect motion and extension, the entire droplet drifts along the electric field with a speed that is independent of the size of the droplet and is proportional to the amplitude of the electric field. After the field is increased above 1 mV µm-1 the entire droplet gets deformed and oscillates with the field. These observations led us to determine the polarization field and revealed the presence of a pair of positive and negative bound electric charges due to divergences of polarization around the defect volume.

Distinct differences in the nanoscale behaviors of the twist-bend liquid crystal phase of a flexible linear trimer and homologous dimer.

We synthesized the liquid crystal dimer and trimer members of a series of flexible linear oligomers and characterized their microscopic and nanoscopic properties using resonant soft X-ray scattering and a number of other experimental techniques. On the microscopic scale, the twist-bend phases of the dimer and trimer appear essentially identical. However, while the liquid crystal dimer exhibits a temperature-dependent variation of its twist-bend helical pitch varying from 100 to 170 Å on heating, the trimer exhibits an essentially temperature-independent pitch of 66 Å, significantly shorter than those reported for other twist-bend forming materials in the literature. We attribute this to a specific combination of intrinsic conformational bend of the trimer molecules and a sterically favorable intercalation of the trimers over a commensurate fraction (two-thirds) of the molecular length. We develop a geometric model of the twist-bend phase for these materials with the molecules arranging into helical chain structures, and we fully determine their respective geometric parameters.

Flexo-Ionic Effect of Ionic Liquid Crystal Elastomers.

The first study of the flexo-ionic effect, i.e., mechanical deformation-induced electric signal, of the recently discovered ionic liquid crystal elastomers (iLCEs) is reported. The measured flexo-ionic coefficients were found to strongly depend on the director alignment of the iLCE films and can be over 200 µC/m. This value is orders of magnitude higher than the flexo-electric coefficient found in insulating liquid crystals and is comparable to the well-developed ionic polymers (iEAPs). The shortest response times, i.e., the largest bandwidth of the flexo-ionic responses, is achieved in planar alignment, when the director is uniformly parallel to the substrates. These results render high potential for iLCE-based devices for applications in sensors and wearable micropower generators.

Missing Link between Helical Nano- and Microfilaments in B4 Phase Bent-Core Liquid Crystals, and Deciphering which Chiral Center Controls the Filament Handedness.

The range of possible morphologies for bent-core B4 phase liquid crystals has recently expanded from helical nanofilaments (HNFs) and modulated HNFs to dual modulated HNFs, helical microfilaments, and heliconical-layered nanocylinders. These new morphologies are observed when one or both aliphatic side chains contain a chiral center. Here, the following questions are addressed: which of these two chiral centers controls the handedness (helicity) and which morphology of the nanofilaments is formed by bent-core liquid crystals with tris-biphenyl diester core flanked by two chiral 2-octyloxy side chains? The combined results reveal that the longer arm of these nonsymmetric bent-core liquid crystals controls the handedness of the resulting dual modulated HNFs. These derivatives with opposite configuration of the two chiral side chains now feature twice as large dimensions compared to the homochiral derivatives with identical configuration. These results are supported by density functional theory calculations and stochastic dynamic atomistic simulations, which reveal that the relative difference between the para- and meta-sides of the described series of compounds drives the variation in morphology. Finally, X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy (AFM) data also uncover the new morphology for B4 phases featuring p2/m symmetry within the filaments and less pronounced crystalline character.

Poly(ethylene glycol) Diacrylate Based Electro-Active Ionic Elastomer.

Preparation and low voltage induced bending (converse flexoelectricity) of crosslinked poly(ethylene glycol) diacrylate (PEGDA), modified with thiosiloxane (TS) and ionic liquid (1-hexyl-3-methylimidazolium hexafluorophosphate) (IL) are reported. In between 2µm PEDOT:PSS electrodes at 1 V, it provides durable (95% retention under 5000 cycles) and relatively fast (2 s switching time) actuation with the second largest strain observed so far in ionic electro-active polymers (iEAPs). In between 40 nm gold electrodes under 8 V DC voltage, the film can be completely curled up (270° bending angle) with 6% strain that, to the best of the knowledge, is unpreceded among iEAPs. These results render great potential for the TS/PEGDA/IL based electro-active actuators for soft robotic applications.

Polarization-Modulated Bent-Core Liquid Crystal Thin Films without Layer Undulation.

Spatial confinement is known to affect molecular organizations of soft matter. We present an important manifestation of this statement for thin films of bent-core smectic liquid crystals. Prior freeze-fracture transmission electron microscopy (FFTEM) studies carried out on nitro-substituted bent-core mesogens (n-OPIMB-NO_{2}) revealed an undulated smectic layer structure with an undulation periodicity of ∼8 nm. We report cryogenic TEM measurements on ∼100 nm thick 8-OPIMB-NO_{2} films. In contrast to FFTEM results, our studies show only density modulation with periodicity b=16.2 nm, and no smectic layer undulation. We show that the discrepancy between the FFTEM and cryogenic transmission electron microscopy (cryo-TEM) results can be attributed to the different sample thicknesses used in the experiments. FFTEM monitors cracked surfaces of a relatively thick (5-10 µm) frozen sample, whereas cryo-TEM visualizes the volume of a thin (0.1 µm) film that was quenched from its partially fluid phase. These results have importance in possible photovoltaics and organic electronics applications where submicron thin films are used.

Spherical-cap droplets of a photo-responsive bent liquid crystal dimer.

Using a photo-responsive dimer exhibiting the transition between nematic (N) and twist-bend nematic (NTB) phases, we prepared spherical cap-shaped droplets on solid substrates exposed to air. The internal director structures of these droplets vary depending on the phase and on the imposed boundary conditions. The structural switching between the N and NTB phases was successfully performed either by temperature control or by UV light-irradiation. The N phase is characterized by an extremely small bend elastic constant K3, and surprisingly, we found that the droplet-air interface induces a planar alignment, in contrast to that seen for typical calamitic liquid crystals. As a consequence, the director configuration was stabilized in a structure substantially different from that normally found in conventional nematic liquid crystalline droplets. In the twist-bend nematic droplets characteristic structures with macroscopic length scales were formed, and they were well controlled by the droplet size. These results indicated that a continuum theory is effective in describing the stabilization mechanism of the macroscopic structure even in the twist-bend nematic liquid crystal droplets exhibiting director modulations on a scale of several molecular lengths.

Indication of a twist-grain-boundary-twist-bend phase of flexible core bent-shape chiral dimers.

The effect of the molecular chirality of chiral additives on the nanostructure of the twist-bend nematic (NTB) liquid crystal phase with ambidextrous chirality and nanoscale pitch due to spontaneous symmetry breaking is studied. It is found that the ambidextrous nanoscale pitch of the NTB phase increases by 50% due to 3% chiral additive, and the chiral transfer among the biphenyl groups disappears in the NTB* phase. Most significantly, a twist-grain boundary (TGB) type phase is found at c > 1.5 wt% chiral additive concentrations below the usual N* phase and above the non-CD active NTB* phase. In such a TGB type phase, the adjacent blocks of pseudo-layers of the nanoscale pitch rotate across the grain boundaries.

Electroresponsive Ionic Liquid Crystal Elastomers.

This paper describes the preparation, physical properties, and electric bending actuation of a new class of active materials-ionic liquid crystal elastomers (iLCEs). It is demonstrated that iLCEs can be actuated by low-frequency AC or DC voltages of less than 1 V. The bending strains of the unoptimized first iLCEs are already comparable to the well-developed ionic electroactive polymers. Additionally, iLCEs exhibit several novel and superior features, such as the alignment that increases the performance of actuation, the possibility of preprogrammed actuation patterns at the level of the cross-linking process, and dual (thermal and electric) actuations in hybrid samples. Since liquid crystal elastomers are also sensitive to magnetic fields and can also be light sensitive, iLCEs have far-reaching potentials toward multiresponsive actuations that may have so far unmatched properties in soft robotics, sensing, and biomedical applications.

Pretransitional behavior of viscoelastic parameters at the nematic to twist-bend nematic phase transition in flexible n-mers.

We report dynamic light scattering measurements of the orientational (Frank) elastic constants and associated viscosities among a homologous series of a liquid crystalline dimer, trimer, and tetramer exhibiting a uniaxial nematic (N) to twist-bend nematic (NTB) phase transition. The elastic constants for director splay (K11), twist (K22) and bend (K33) exhibit the relations K11 > K22 > K33 and K11/K22 > 2 over the bulk of the N phase. Their behavior near the N-NTB transition shows dependency on the parity of the number (n) of the rigid mesomorphic units in the flexible n-mers. Namely, the bend constant K33 in the dimer and tetramer turns upward and starts increasing close to the transition, following a monotonic decrease through most of the N phases. In contrast, K33 for the trimer flattens off just above the transition and shows no pretransitional enhancement. The twist constant K22 increases pretransitionally in both even and odd n-mers, but more weakly so in the trimer, while K11 increases steadily on cooling without evidence of pretransitional behavior in any n-mer. The viscosities associated with pure splay, twist-dominated twist-bend, and pure bend fluctuations in the N phase are comparable in magnitude to those of rod-like monomers. All three viscosities increase with decreasing temperature, but the bend viscosity in particular grows sharply near the N-NTB transition. The N-NTB pretransitional behavior is shown to be in qualitative agreement with the predictions of a coarse-grained theory, which models the NTB phase as a "pseudo-layered" structure with the symmetry (but not the mass density wave) of a smectic-A* phase.

Bending nematic liquid crystal membranes with phospholipids.

The interactions of phospholipids with liquid crystals have formed the basis for attractive biosensor technologies, but many questions remain concerning the basic physics and chemistry of these interactions. Phospholipids such as 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC), at sufficiently high (∼1 µM) concentrations and/or sufficiently long times, turn the liquid crystal director perpendicular to the LC/water interface. If the other side of the LC film is in contact with a surface that prefers perpendicular alignment, the LC film appears completely dark between crossed polarizers. Recently, however, Popov et al. (J. Mater. Chem. B, 2017, 5, 5061) noted that at even higher (∼10 µM) DLPC concentrations, the liquid crystal texture brightens again between crossed polarizers. To explain this surprising observation, it was suggested that the LC interface might bend. In this paper we show by optical surface profiler measurements that indeed the interface of the LC film of 4-cyano-4'-octylbiphenyl (8CB) suspended in a transmission electron microscopy (TEM) grid with openings of ∼0.5 mm in diameter bends towards the lipid-coated interface. We demonstrate that where the bending occurs, the bent interface exhibits extreme sensitivity to air pressure variations, producing an optical response with acoustic stimulation. Finally, we suggest a physical mechanism for this astonishing result.

Smart biomimetic micro/nanostructures based on liquid crystal elastomers and networks.

A plethora of living organisms are equipped with smart functionalities that are usually rooted in their surface micro/nanostructures or underlying muscle tissues. Inspired by nature, extensive research efforts have been devoted to the development of novel biomimetic functional micro/nanostructured systems. Despite all the accomplishments, the emulation of biological adaptation and stimuli responsive actuation has been a longstanding challenge. The use of liquid crystal elastomers (LCEs) and networks (LCNs) for the fabrication of smart biomimetic micro/nanostructures has recently drawn extensive scientific attention and has become a growing field of research with promising prospects for emerging technologies. In this study, we review the recent progress in this field and portray the current challenges as well as the outlook of this field of research.

A Dual Modulated Homochiral Helical Nanofilament Phase with Local Columnar Ordering Formed by Bent Core Liquid Crystals: Effects of Molecular Chirality.

Helical nanofilament (HNF) phases form as a result of an intralayer mismatch between top and bottom molecular halves in bent-core liquid crystals (BC-LCs) that is relieved by local saddle-splay geometry. HNFs are immensely attractive for photovoltaic and chiral separation applications and as templates for the chiral spatial assembly of guest molecules. Here, the synthesis and characterization of two unichiral BC-LCs and one racemic mixture with tris-biphenyl-diester cores featuring chiral (R,R) and (S,S) or racemic 2-octyloxy aliphatic side chains are presented. In comparison to the achiral compound with linear side chains forming an intralayer modulated HNF phase (HNFmod ), synchrotron small angle X-ray diffraction indicates that the unichiral derivatives form a dual modulated HNF phase with intra- as well as interlayer modulations (HNFmod2 ) suggesting a columnar local structure of the nanofilaments. Transmission electron microscopy and circular dichroism spectropolarimetry confirm that the unichiral materials exclusively form homochiral HNFs with a twist sense-matching secondary twist. A contact preparation provides the first example of two identical chiral liquid crystal phases only differing in their handedness that do not mix and form an achiral liquid crystal phase with an entirely different structure in the contact zone.

Morphology Tuning of Electrospun Liquid Crystal/Polymer Fibers.

This paper elucidates the means to control precisely the morphology of electrospun liquid crystal/polymer fibers formed by phase separation. The relative humidity, solution parameters (concentration, solvent), and the process parameter (feed rate) were varied systematically. We show that the morphology of the phase-separated liquid crystal can be continuously tuned from capsules to uniform fibers with systematic formation of beads-on-a-string structured fibers in the intermediate ranges. In all cases, the polymer forms a sheath around a liquid-crystal (LC) core. The width of the polymer sheath and the diameter of the LC core increase with increasing feed rates. This is similar to the results obtained by coaxial electrospinning. Because these fibers retain the responsive properties of liquid crystals and because of their large surface area, they have potential applications as thermo-, chemo-, and biosensors. Because the size and shape of the liquid-crystal domains will have a profound effect on the performance of the fibers, our ability to precisely control morphology will be crucial in developing these applications.

Airbrush Formation of Liquid Crystal/Polymer Fibers.

A homogeneous solution of a low-molecular-weight liquid crystal and a polymer spontaneously phase separates during airbrushing to form uniform fibers with a fluid liquid-crystal core surrounded by a solid polymer sheath. This structure forms because it effectively minimizes the interfacial energy of the phase-separated components while minimizing the elastic energy of the liquid-crystal core. These fibers incorporate the sensitive stimuli response of liquid crystals while maintaining the structural integrity, flexibility, and large surface-area-to-volume ratios inherent in fibers. We demonstrate the electro- and thermo-optical response of the resulting fibers. They may find use as biological and chemical sensors. The resulting fibers have the potential to shape the future of flexible/wearable electronics and sensors.

Nanostructures of nematic materials of laterally branched molecules.

The synthesis and small-angle X-ray scattering (SAXS) characterization is reported for 20 laterally branched mesogenic molecules, which are derived from the common rod-shaped 2,5-bis([4-(octyloxy)phenyl]carbonyloxy) benzoic acid unit. These compounds have a varying degree of flexibility, in that their lateral branch is formed upon conversion of the acid to either an ester or an amide, and most laterally branched molecules exhibit relatively wide nematic liquid-crystal phases with a direct nematic-to-crystal transition at lower temperatures. SAXS studies reveal the presence of smectic-like nanostructures (clusters) with short-range order in the nematic phase, with characteristic correlation lengths from 3 to over 10 nm. The smectic layers that are contained in these clusters are tilted with respect to the nematic director by angles ranging from 0° (i.e. untilted) to 55°. In some compounds, the intensity of the SAXS peak corresponding to the smectic layer spacing depends strongly on temperature. The main features of the nanostructures can be understood based on the molecular structure; therefore, guiding future synthetic work towards more precisely controlled and technologically useful nanostructures in nematics.