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The extraordinary responsiveness and large diversity of self-assembled structures of liquid crystals are well documented and they have been extensively used in devices like displays. For long, this application route strongly influenced academic research, which frequently focused on the performance of liquid crystals in display-like geometries, typically between flat, rigid substrates of glass or similar solids. Today a new trend is clearly visible, where liquid crystals confined within curved, often soft and flexible, interfaces are in focus. Innovation in microfluidic technology has opened for high-throughput production of liquid crystal droplets or shells with exquisite monodispersity, and modern characterization methods allow detailed analysis of complex director arrangements. The introduction of electrospinning in liquid crystal research has enabled encapsulation in optically transparent polymeric cylinders with very small radius, allowing studies of confinement effects that were not easily accessible before. It also opened the prospect of functionalizing textile fibers with liquid crystals in the core, triggering activities that target wearable devices with true textile form factor for seamless integration in clothing. Together, these developments have brought issues center stage that might previously have been considered esoteric, like the interaction of topological defects on spherical surfaces, saddle-splay curvature-induced spontaneous chiral symmetry breaking, or the non-trivial shape changes of curved liquid crystal elastomers with non-uniform director fields that undergo a phase transition to an isotropic state. The new research thrusts are motivated equally by the intriguing soft matter physics showcased by liquid crystals in these unconventional geometries, and by the many novel application opportunities that arise when we can reproducibly manufacture these systems on a commercial scale. This review attempts to summarize the current understanding of liquid crystals in spherical and cylindrical geometry, the state of the art of producing such samples, as well as the perspectives for innovative applications that have been put forward.

By photopolymerizing liquid crystal shells, their rich variety of self-assembled structures can be rendered permanent and the lifetime extended from days to months, without removing the characteristic responsiveness. If polymerization is carried out close to either boundary of the nematic phase, the process triggers the transition into the adjacent phase, to higher or to lower degree of order., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Helical liquid crystal self-assembly in suspensions of cellulose nanocrystals (CNCs), bioderived nanorods exhibiting excellent mechanical and optical properties, opens attractive routes to sustainable production of advanced functional materials. For convenience, in most studies until now, the CNCs were suspended in water, leaving a knowledge gap concerning the influence of the solvent. Using a novel approach for aggregation-free solvent exchange in CNC suspensions, here we show that protic solvents with a high dielectric permittivity εr significantly speed up self-assembly (from days to hours) at high CNC mass fraction and reduce the concentration dependence of the helix period (variation reducing from more than 30 μm to less than 1 μm). Moreover, our computer simulations indicate that the degree of order at constant CNC content increases with increasing εr, leading to a shorter pitch and a reduced threshold for liquid crystallinity. In low-εr solvents, the onset of long-range orientational order is coupled to kinetic arrest, preventing the formation of a helical superstructure. Our results show that the choice of solvent is a powerful parameter for tuning the behavior of CNC suspensions, enhancing our ability to control the self-assembly and thereby harvesting valuable novel cellulose-based materials.

Monodisperse cholesteric liquid crystal microspheres exhibit spherically symmetric Bragg reflection, generating, via photonic cross communication, dynamically tuneable multi-coloured patterns. These patterns, uniquely defined by the particular sphere arrangement, could render cholesteric microspheres very useful in countless security applications, as tags to identify and authenticate their carriers, mainly physical objects or persons. However, the optical quality of the cholesteric droplets studied so far is unsatisfactory, especially after polymerisation, a step required for obtaining durable samples that can be used for object identification. We show that a transition from droplets to shells solves all key problems, giving rise to sharp patterns and excellent optical quality even after polymerisation, the polymerised shells sustaining considerable mechanical deformation. Moreover, we demonstrate that, counter to prior expectation, cross communication takes place even between non-identical shells. This opens additional communication channels that add significantly to the complexity and unique character of the generated patterns.

We investigate the nematic-isotropic (N-I) transition in shells of the liquid crystal 5CB, surrounded by aqueous phases that conventionally are considered to be immiscible with 5CB. The aqueous phases contain either sodium dodecyl sulfate (SDS) or polyvinyl alcohol (PVA) as stabiliser, the former additionally promoting homeotropic director alignment. For all shell configurations we find a depression of the clearing point compared to pure 5CB, indicating that a non-negligible fraction of the constituents of the surrounding phases enter the shell, predominantly water. In hybrid-aligned shells, with planar outer and homeotropic inner boundary (or vice versa), the N-I transition splits into two steps, with a consequent three-step textural transformation. We explain this as a result of the order-enhancing effect of a monolayer of radially aligned SDS molecules adsorbed at the homeotropic interface.

The realization of long, aligned molecular wires is a great challenge, and a variety of approaches have been proposed. Interestingly, hexapentyloxytriphenylene (HAT5) discotic liquid crystal molecules, a model system of molecules with flat and aromatic cores, can spontaneously form well-aligned, micrometer long, yet only tens of nanometers thick, nanowires on solid surfaces. We have investigated the formation mechanism of these wires using different solvents with selected characteristics, including chemical structure, boiling point, vapor pressure, and surface tension. When casting from toluene and benzene solutions, atomic force microscopy reveals that the discotics spontaneously form very long and thin wires, self-aligning along a common orientation. If instead dodecane or heptane are used, different and in general thicker structures are obtained. The chemical structure of the solvent appears to have a key role, coupling to the liquid crystal self-assembly by allowing solvent molecules to enter the ordered structure if their design matches the core of HAT5 molecules, thereby guiding the assembly. However, other aspects are also relevant in the assembly, including the nature of the substrate and the rate of solvent evaporation, and these can favor or interfere with the self-assembly into long structures. The use of solvents with aromatic structure is advantageous not only because it affects the geometry of the assembly, promoting long wire formation, but it is also compatible with good quality of the intermolecular order, as suggested by a high anisotropy of the Raman spectra of the nanowires formed from these solvents. Finally, the electrical properties of ordered systems show a clearly higher electrical conductivity compared to the disorganized aggregates.

The packing of cellulose nanocrystals (CNC) in the anisotropic chiral nematic phase has been investigated over a wide concentration range by small-angle X-ray scattering (SAXS) and laser diffraction. The average separation distance between the CNCs and the average pitch of the chiral nematic phase have been determined over the entire isotropic-anisotropic biphasic region. The average separation distances range from 51 nm, at the onset of the anisotropic phase formation, to 25 nm above 6 vol % (fully liquid crystalline phase) whereas the average pitch varies from ≈15 μm down to ≈2 μm as ϕ increases from 2.5 up to 6.5 vol %. Using the cholesteric order, we determine that the twist angle between neighboring CNCs increases from about 1° up to 4° as ϕ increases from 2.5 up to 6.5 vol %. The dependence of the twisting on the volume fraction was related to the increase in the magnitude of the repulsive interactions between the charged rods as the average separation distance decreases.

Coaxial electrospinning allows easy and cost-effective realization of composite fibers at the nano- and microscales. Different multifunctional materials can be incorporated with distinct localization to specific regimes of the fiber cross section and extended internal interfaces. However, the final composite properties are affected by variations in internal structure, morphology, and material separation, and thus, nanoscale control is mandatory for high-performance application in devices. Here, we present an analysis with unprecedented detail of the cross section of liquid core-functionalized fibers, yielding information that is difficult to reveal. This is based on focused ion beam (FIB) lift-out and allowing HR-TEM imaging of the fibers together with nanoscale resolution chemical analysis using energy dispersive X-ray spectroscopy (EDS). Unexpectedly, core material escapes during spinning and ends up coating the fiber exterior and target substrate. For high core injection rate, a dramatic difference in fiber morphology is found, depending on whether the surface on which the fibers are deposited is hydrophobic or hydrophilic. The latter enhances postspinning extraction of core fluid, resulting in the loss of the functional material and collapsed fiber morphology. Finally, in situ produced TiO2 nanoparticles dispersed in the polymer appear strikingly different when the core fluid is present compared to when the polymer solution is spun on its own.

The intrinsic ability of cellulose nanocrystals (CNCs) to self-organize into films and bulk materials with helical order in a cholesteric liquid crystal is scientifically intriguing and potentially important for the production of renewable multifunctional materials with attractive optical properties. A major obstacle, however, has been the lack of control of helix direction, which results in a defect-rich, mosaic-like domain structure. Herein, a method for guiding the helix during film formation is introduced, which yields dramatically improved uniformity, as confirmed by using polarizing optical and scanning electron microscopy. By raising the CNC concentration in the initial suspension to the fully liquid crystalline range, a vertical helix orientation is promoted, as directed by the macroscopic phase boundaries. Further control of the helix orientation is achieved by subjecting the suspension to a circular shear flow during drying., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Thin liquid crystalline shells surrounding and surrounded by aqueous phases can be conveniently produced using a nested capillary microfluidic system, as was first demonstrated by Fernandez-Nieves et al. in 2007. By choosing particular combinations of stabilizers in the internal and external phases, different types of alignment, uniform or hybrid, can be ensured within the shell. Here, we investigate shells in the nematic and smectic phases under varying boundary conditions, focusing in particular on textural transformations during phase transitions, on the interaction between topological defects in the director field and inclusions in the liquid crystal (LC), and on the possibility to relocate defects within the shell by rotating the shell in the gravitational field. We demonstrate that inclusions in a shell can seed defects that cannot form in a pristine shell, adding a further means of tuning the defect configuration, and that shells in which the internal aqueous phase is not density matched with the LC will gently rearrange the internal structure upon a rotation that changes the influence of gravity. Because the defects can act as anchor points for added linker molecules, allowing self-assembly of adjacent shells, the various arrangements of defects developing in these shells and the possibility of tuning the result by modifying boundary conditions, LC phase, thickness and diameter of the shell or applying external forces make this new LC configuration very attractive.

We investigated the electrolyte effects on the stability of nematic and lamellar lyotropic liquid crystalline (LLC) phases formed by the simple anionic surfactant cesium pentadecafluorooctanoate (CsPFO) in water. To the lyotropic guest phase, at the constant CsPFO-mass fraction of 0.55, the series of electrolytes LiCl, NaCl, KCl, CsCl, CsI, and Cs(2)SO(4), respectively, was added at concentrations ranging from 0.5 to 2.5 mol %. With increasing electrolyte concentration two substantially different effects were observed. At low concentrations all added electrolytes caused an increase of the thermal stability of the LLC phases, favoring the lamellar phase over the nematic phase. This behavior is, at least qualitatively, understood within the packing parameter model. The extent of the stabilization clearly depends on the chemical nature of the added cation. For a given cation, however, the effect is colligative, i.e., independent of the chemical nature of the added anion. At higher salt concentrations a salting-out-like phase separation was induced. This effect is clearly ion-specific as the salting-out concentration varied for each cation following the order of the Hofmeister series for cations.

Liquid crystal containing composite fibres were produced via coaxial electrospinning, demonstrating that this technique can be used for producing new functional fibres and/or to study the impact of extreme confinement on liquid crystal phases.

We develop a molecular-statistical theory of the smectic-A-smectic-C transition which is described as a transition of the order-disorder type. The theory is based on a general expansion of the effective interaction potential and employs a complete set of orientational order parameters. All the order parameters of the smectic-C phase including the tilt angle are calculated numerically as functions of temperature for a number of systems which correspond to different transition scenario. The effective interaction potential and the parameters of the transition are also calculated for specific molecular models based on electrostatic and induction interaction between molecular dipoles. The theory successfully reproduces the main properties of both conventional and so-called "de Vries-type" smectic liquid crystals, clarifies the origin of the anomalously weak layer contraction and describes the tricritical behavior at the smectic-A-smectic-C transition. The "de Vries behavior," i.e., anomalously weak layer contraction is also obtained for a particular molecular model based on interaction between longitudinal molecular dipoles. A simple phenomenological model is presented enabling one to obtain explicit expressions for the layer spacing and the tilt angle which are used to fit the experimental data for a number of materials.

We develop both phenomenological and molecular-statistical theory of smectic- A -smectic- C phase transition with anomalously weak smectic layer contraction. Using a general mean-field molecular model, we demonstrate that a relatively simple interaction potential suffices to describe the transition both in conventional and de Vries type smectics. The theoretical results are in excellent agreement with experimental data. The approach can be used to describe tilting transitions in other soft matter systems.

Interest in the smectic liquid-crystalline state of matter received a substantial boost with the discovery by Meyer in the mid-1970s that a chiral smectic C (SmC*) phase exhibits a spontaneous electric polarization, and with the subsequent demonstration by Clark and Lagerwall of the surface-stabilized SmC* ferroelectric liquid crystal at the beginning of the 1980s. Since then, chiral smectic phases and their plethora of polar effects have dominated the research in this field, which today has reached a mature state where the first commercial microdisplay applications are now shipping in millions-per-year quantities. In this Review we discuss some of the topics of highest interest in current smectic liquid crystal research, and address application-relevant research (de Vries-type tilting transitions without defect generation and high-tilt antiferroelectric liquid crystals with perfect dark state) as well as more curiosity-driven research (the nature and origin of the chiral smectic C subphases and their intermediate frustrated states between ferro- and antiferroelectricity).

We study the effects of mixing ferroelectric and antiferroelectric liquid-crystal compounds (FLCs and AFLCs) when the former are strictly synclinic and the latter strictly anticlinic, i.e. one mixture component exhibits only SmC* and the other only SmC(a)* as tilted phase. Three different paths between syn- and anticlinicity were detected: transition directly between SmC* and SmC(a)*, transition via the SmC(beta)* and SmC(gamma)* subphases, or by "escaping" the clinicity frustration by reducing the tilt to zero, i.e. the SmA* phase is extended downwards in temperature, separating SmC* from SmC(a)* in the phase diagram. The most common path is the one via the subphases, demonstrating that these phases appear as a result of frustration between syn- and anticlinic and, consequently, between syn- and antipolar order. For assessing the role of chirality, we also replaced the FLC with non-chiral synclinics. With one of the AFLCs, the route via supbhases was detected even in this case, suggesting that chirality--although necessary--does not have quite the importance that has previously been attributed to the appearance of the subphases. The path chosen in the mixture study seemed to be determined mainly by the synclinic component, the subphase induction occurring only when the SmA*-SmC* transition was second order.

We show that the helical superstructure in chiral smectic-C-type liquid crystal phases can, if the pitch is short enough, give rise to the tristate switching characteristic of antiferroelectrics even if the local commensurate order is synpolar as in the ordinary Sm-C* phase. Since the field-induced helix unwinding exhibits a distinct threshold, in contrast to mere helix distortion, two unwinding / rewinding peaks per half cycle of an applied triangular wave voltage can be seen in the current response. By considering this antiferroelectric aspect of the helical modulation we give a simple explanation of why the ultrashort-pitch Sm-C*alpha phase exhibits antiferroelectric switching although its dielectric spectroscopy response is qualitatively identical to that of the synpolar Sm-C* phase. Using data from the compound MHPOCBC we show that the Sm-C*alpha dielectric response is well described by continuum theory. We also demonstrate that, if the pitch is very short as in MHPOCBC, helix unwinding/rewinding leave characteristic traces in the electrooptic response even in the commensurately antiferroelectric (antipolar) Sm-C*(a) phase, distinguishable from the switching between the antipolar and synpolar states of this phase.

By mixing the achiral liquid crystal HOAB, exhibiting a nematic (N)-smectic-C (SmC) mesophase sequence, with the chiral antiferroelectric liquid crystal (AFLC) (S,S)-M7BBM7, forming the antiferroelectric SmC(a)(*) phase, at least seven different mesophases have been induced which neither component forms on its own: a twist-grain-boundary (TGB(*)) phase, two or three blue phases, the untilted SmA(*) phase, as well as all three chiral smectic-C-type "subphases," SmC(alpha)(*), SmC(beta)(*), and SmC(gamma)(*). The nature of the induced phases and the transitions between them were determined by means of optical and electro-optical investigations, dielectric spectroscopy, and differential scanning calorimetry. The induced phases can to a large extent be understood as a result of frustration, TGB(*) at the border between nematic and smectic, the subphases between syn and anticlinic tilted smectic organization. X ray scattering experiments reveal that the smectic layer spacing as well as the degree of smectic order is relatively constant in the whole mixture composition range in which AFLC behavior prevails, whereas both these parameters rapidly decrease as the amount of HOAB is increased to such an extent that no other smectic-C-type phase than SmC/SmC(*) exists. By tailoring the composition we are able to produce liquid crystal mixtures exhibiting unusual phase sequences, e.g., with a direct isotropic-SmC(a)(*) transition or a temperature range of the SmC(beta)(*) subphase of about 50 K.

We describe an analog electro-optic (EO) switching mechanism occurring in thin cells filled with a low-polarization ferroelectric liquid crystal mixture with positive dielectric anisotropy. The mixture is composed of an achiral nonpolar smectic-C (Sm-C) host doped with a small amount of a commercially available unichiral compound. The switching mechanism provides analog EO behavior, and thus could be attractive for information display applications. The process is polarization-driven for weak fields, while for higher field strength the dielectric coupling dominates the process.

The optic, electro-optic, and dielectric properties of antiferroelectric liquid crystals (AFLCs) are analyzed and discussed in terms of the local tilt plane orientation. We show that the so-called pretransitional effect is a combination of two different electro-optic modes: the field-induced antiphase distortion of the antiferroelectric structure and the field-induced reorientation of the tilt plane. In the presence of a helix, the latter corresponds to a field-induced distortion of the helix. Both electro-optic modes are active only when the electric field has a component along the tilt plane. Thus, by assuring a horizontal surface-stabilized condition, where the helix is unwound by surface action and the tilt plane is everywhere parallel to the cell plates, the pretransitional effect should be suppressed. We also discuss the dielectrically active modes in AFLCs and under which circumstances they contribute to the measured dielectric permittivity.

We report results of x-ray, optic, electro-optic, and dielectric investigations on an antiferroelectric liquid-crystal mixture exhibiting a direct second-order phase transition between the Sm-A* and Sm-C(*)(a) phases with virtually no shrinkage in the smectic layer spacing. The birefringence measurements and texture observations suggest that the phase transition follows the diffuse cone model of Adrian de Vries, which explains the constant layer spacing. The antiferroelectric nature of the tilted phase is verified by the presence of twin polarization reversal peaks in the current response and by the absence of strong absorptions in the dielectric spectrum. The threshold for switching this phase to the synclinic, ferroelectric state is sharp and occurs at a very low voltage.

A non-layer-shrinkage fluorinated ferroelectric liquid crystal compound, 8422[2F3], has been characterized by means of optical, x-ray, and calorimetric methods. The orientational distribution within macroscopic volumes, determined through wide-angle x-ray scattering and birefringence measurements, was found to be identical in the Sm-A* and helical Sm-C* phases. Together with the absence of layer shrinkage, this constitutes strong evidence that the second-order Sm-A*-Sm-C* transition in this material is well described by the diffuse cone model of de Vries. The absolute values of the layer spacing show that the molecules aggregate to antiparallel pairs. The molecular interaction across the layer boundaries will then occur only between fluorine atoms, leading to unusually weak interlayer tilt direction correlation. This explains the experimental observations of a very easily disturbed Sm-C* helix and a peculiar surface-stabilized texture. Tilt angle and birefringence values as a function of field and temperature have been evaluated in the Sm-A* and Sm-C* phases and the results corroborate the conclusions from the x-ray investigations.