No abstract

In this review article, we analyze recent progress in the application of liquid crystal-assisted advanced functional materials for sensing biological and chemical analytes. Multiple research groups demonstrate substantial interest in liquid crystal (LC) sensing platforms, generating an increasing number of scientific articles. We review trends in implementing LC sensing techniques and identify common problems related to the stability and reliability of the sensing materials as well as to experimental set-ups. Finally, we suggest possible means of bridging scientific findings to viable and attractive LC sensor platforms.

Highly stretchable liquid crystal core–elastomer sheath fibres are spun using a microfluidic wet spinning approach.

Nematic liquid crystals (NLCs) of achiral molecules and racemic mixtures of chiral ones form flat films and show uniform textures between circular polarizers when suspended in sub-millimeter size grids and immersed in water. On addition of chiral dopants to the liquid crystal, the films exhibit optical textures with concentric ring patterns and radial variation of the birefringence color. Both are related to a biconvex shape of the chiral liquid crystal film; the rings are due to interference. The curvature radii of the biconvex lens array are in the range of a few millimeters. This curvature leads to a radial variation of the optical axis along the plane of the film. Such a Pancharatnam-type phase lens dominates the imaging and explains the measured focal length of about one millimeter. To our knowledge, these are the first spontaneously formed Pancharatnam devices. The unwinding of the helical structure at the grid walls drives the lens shape. The relation between the lens curvature and material properties such as helical pitch, the twist elastic constant, and the interfacial tensions, is derived. This simple, novel method for spontaneously forming microlens arrays can also be used for various sensors.

Liquid crystal (LC) phases typically show anisotropic alignment-dependent properties, such as viscosity and dielectric permittivity, so it stands to reason that LCs also have anisotropic interfacial tensions. Measuring the interfacial tension γ of an LC with conventional methods, such as pendant drops, can be challenging, however, especially when we need to know γ for different LC aligning conditions, as is the case when we seek Δγ, the interfacial tension anisotropy. Here, we present measurements of Δγ of the common synthetic nematic LC compound 5CB against water using a microfluidic droplet aspiration technique. To ensure tangential and normal alignment, respectively, we add poly(vinyl alcohol) (PVA) and sodium dodecylsulfate (SDS), respectively, as a stabilizer and measure γ for different concentrations of stabilizer. By fitting the Szyszkowski equation to the data, we can extrapolate to zero-stabilizer concentration, obtaining the γ of 5CB to pure water for each alignment. For normal alignment, we find γ⊥=31.9±0.8 mN·m−1, on the order of 1 mN·m−1 greater than γ||=30.8±5 mN·m−1 for tangential alignment. This resonates with the empirical knowledge that 5CB aligns tangentially to an interface with pure water. The main uncertainty arises from the use of polymeric PVA as tangential-promoting stabilizer. Future improvements in accuracy may be expected if PVA can be replaced by a low molar mass stabilizer that ensures tangential alignment.

Biosensing using liquid crystals has a tremendous potential by coupling the high degree of sensitivity of their alignment to their surroundings with clear optical feedback. Many existing setups use birefringence of nematic liquid crystals, which severely limits straightforward and frugal implementation into a sensing platform due to the sophisticated optical set-ups required. In this work, we instead utilize chiral nematic liquid crystal microdroplets, which show strongly reflected structural color, as sensing platforms for surface active agents. We systematically quantify the optical response of closely related biological amphiphiles and find unique optical signatures for each species. We detect signatures across a wide range of concentrations (from micromolar to millimolar), with fast response times (from seconds to minutes). The striking optical response is a function of the adsorption of surfactants in a nonhomogeneous manner and the topology of the chiral nematic liquid crystal orientation at the interface requiring a scattering, multidomain structure. We show that the surface interactions, in particular, the surface packing density, to be a function of both headgroup and tail and thus unique to each surfactant species. We show lab-ona-chip capability of our method by drying droplets in high-density two-dimensional arrays and simply hydrating the chip to detect dissolved analytes. Finally, we show proof-of-principle in vivo biosensing in the healthy as well as inflamed intestinal tracts of live zebrafish larvae, demonstrating CLC droplets show a clear optical response specifically when exposed to the gut environment rich in amphiphiles. Our unique approach shows clear potential in developing on-site detection platforms and detecting biological amphiphiles in living organisms.

The interfacial tension between two immiscible fluids is of critical importance for understanding many natural phenomena as well as in industrial production processes; however, it can be challenging to measure this parameter with high accuracy. Most commonly used techniques have significant shortcomings because of their reliance on other data such as density or viscosity. To overcome these issues, we devise a technique that works with very small sample quantities and does not require any data about either fluid, based on micropipette aspiration techniques. The method facilitates the generation of a droplet of one fluid inside of the other, followed by immediate in situ aspiration of the droplet into a constricted channel. A modified Young–Laplace equation is then used to relate the pressure needed to produce a given deformation of the droplet’s radius to the interfacial tension. We demonstrate this technique on different systems with interfacial tensions ranging from sub-millinewton per meter to several hundred millinewton per meter, thus over 4 orders of magnitude, obtaining precise results in agreement with the literature solely from experimental observations of the droplet deformation.

Electrospinning of polymer solutions is a multifaceted process that depends on the careful balancing of many parameters to achieve a desired outcome, in many cases including mixtures of multiple solvents. A systematic study of how the solution viscosity 𝜼-a good probe of solvent-polymer interactions-and the electrospinnability change when poly(acrylic acid) (PAA) is dissolved in ethanol-water mixtures at varying mixing ratio is carried out. A pronounced maximum is found in 𝜼 at a water-to-ethanol molar ratio of about 2:1, where the solvent mixture deviates maximally from ideal mixing behavior and partial deprotonation of carboxyl groups by water coincides synergistically with dissolution of the uncharged protonated PAA fraction by ethanol. The PAA concentration is tuned as a function of water-ethanol ratio to obtain a common value of 𝜼 for all solvent mixtures that is suitable for electrospinning. For high PAA content, the Taylor cone grows in volume over time despite minimum solution flow rate, even experiencing surface gelation for ethanol-rich solutions. This is attributed to the hygroscopic nature of PAA, drawing excess water into the Taylor cone from the air during spinning.