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Understanding how soft matter deforms in response to mechanical interactions is central to the design of functional synthetic materials as well as elucidation of the behaviors of biological assemblies. Here we explore how cycles of thermally induced transitions between nematic (N) and isotropic (I) phases can be used to exert cyclical elastic stresses on dispersions of giant unilamellar vesicles (GUVs) and thereby evolve GUV shape and properties. The measurements were enabled by the finding that I–N–I phase transitions of the lyotropic chromonic liquid crystal disodium cromoglycate, when conducted via an intermediate columnar (M) phase, minimized transport of GUVs on phase fronts to confining surfaces. Whereas I to N phase transitions strained spherical GUVs into spindle-like shapes, with an efflux of GUV internal volume, subsequent N to I transitions generated a range of complex GUV shapes, including stomatocyte, pear- and dumbbell-like shapes that depended on the extent of strain in the N phase. The highest strained GUVs were observed to form buds (daughter vesicles) that we show, via a cycle of I–N–I–N phase transitions, are connected via a neck to the parent vesicle. Additional experiments established that changes in elasticity of the phase surrounding the GUVs and not thermal expansion of membranes were responsible for the shape transitions, and that I–N–I transformations that generate stomatocytes can be understood from the Bilayer-Coupling model of GUV shapes. Overall, these observations advance our understanding of how LC elastic stresses can be regulated to evolve the shapes of soft biological assemblies as well as provide new approaches for engineering synthetic soft matter. 

Soft matter that undergoes programmed macroscopic responses to molecular analytes has potential utility in a range of health and safety-related contexts. In this study, we report the design of a nematic liquid crystal (LC) composition that forms through dimerization of carboxylic acids and responds to the presence of vapors of organoamines by undergoing a visually distinct phase transition to an isotropic phase. Specifically, we screened mixtures of two carboxylic acids, 4-butylbenzoic acid and trans-4-pentylcyclohexanecarboxylic acid, and found select compositions that exhibited a nematic phase from 30.6 to 111.7 °C during heating and 110.6 to 3.1 °C during cooling. The metastable nematic phase formed at ambient temperatures was found to be long-lived (>5 days), thus enabling the use of the LC as a chemoresponsive optical material. By comparing experimental infrared (IR) spectra of the LC phase with vibrational frequencies calculated using density functional theory (DFT), we show that it is possible to distinguish between the presence of monomers, homodimers and heterodimers in the mixture, leading us to conclude that a one-to-one heterodimer is the dominant species within this LC composition. Further support for this conclusion is obtained by using differential scanning calorimetry. Exposure of the LC to 12 ppm triethylamine (TEA) triggers a phase transition to an isotropic phase, which we show by IR spectroscopy to be driven by an acid-base reaction, leading to the formation of ammonium carboxylate salts. We characterized the dynamics of the phase transition and found that it proceeds via a characteristic spatiotemporal pathway involving the nucleation, growth, and coalescence of isotropic domains, thus amplifying the atomic-scale acid-base reaction into an information-rich optical output. In contrast to TEA, we determined via both experiment and computation that neither hydrogen bonding donor or acceptor molecules, such as water, dimethyl methylphosphonate, ethylene oxide or formaldehyde, disrupt the heterodimers formed in the LC, hinting that the phase transition (including spatial-temporal characteristics of the pathway) induced in this class of hydrogen bonded LC may offer the basis of a facile and chemically selective way of reporting the presence of volatile amines. This proposal is supported by exploratory experiments in which we show that it is possible to trigger a phase transition in the LC by exposure to volatile amines emitted from rotting fish. Overall, these results provide new principles for the design of chemoresponsive soft matter based on hydrogen bonded LCs that may find use as the basis of low-cost visual indicators of chemical environments. 

Mammalian cells are soft, and correct functioning requires that cells undergo dynamic shape changes in vivo. Although a range of diseases are associated with stiffening of red blood cells (RBCs; e.g., sickle cell anemia or malaria), the mechanical properties and thus shape responses of cells to complex viscoelastic environments are poorly understood. We use vapor pressure measurements to identify aqueous liquid crystals (LCs) that are in osmotic equilibrium with RBCs and explore mechanical coupling between RBCs and LCs. When transferred from an isotropic aqueous phase into a LC, RBCs exhibit complex yet reversible shape transformations, from initially biconcave disks to elongated and folded geometries with noncircular cross-sections. Importantly, whereas the shapes of RBCs are similar in isotropic fluids, when strained by LC, a large variance in shape response is measured, thus unmasking cell-to-cell variation in mechanical properties. Numerical modeling of LC and cell mechanics reveals that RBC shape responses occur at constant cell membrane area but with membrane shear moduli that vary between cells from 2 to 16 × 10⁻⁶N/m. Temperature-dependent LC elasticity permits continuous tuning of RBC strains, and chemical cross-linking of RBCs, a model for diseased cells, leads to striking changes in shape responses of the RBCs. Overall, these results provide insight into the coupling of strain between soft mammalian cells and synthetic LCs, and hint at new methods for rapidly characterizing mechanical properties of single mammalian cells in a population and thus cell-to-cell variance.

 

Liquid crystals (LCs) are fluids within which molecules exhibit long-range orientational order, leading to anisotropic properties such as optical birefringence and curvature elasticity. Because the ordering of molecules within LCs can be altered by weak external stimuli, LCs have been widely used to create soft matter systems that respond optically to electric fields (LC display), temperature (LC thermometer) or molecular adsorbates (LC chemical sensor). More recent studies, however, have moved beyond investigations of optical responses of LCs to explore the design of complex LC-based soft matter systems that offer the potential to realize more sophisticated functions ( e.g. , autonomous, self-regulating chemical responses to mechanical stimuli) by directing the interactions of small molecules, synthetic colloids and living cells dispersed within the bulk of LCs or at their interfaces. These studies are also increasingly focusing on LC systems driven beyond equilibrium states. This review presents one perspective on these advances, with an emphasis on the discovery of fundamental phenomena that may enable new technologies. Three areas of progress are highlighted; (i) directed assembly of amphiphilic molecules either within topological defects of LCs or at aqueous interfaces of LCs, (ii) templated polymerization in LCs via chemical vapor deposition, an approach that overcomes fundamental challenges related to control of LC phase behavior during polymerization, and (iii) studies of colloids in LCs, including chiral colloids, soft colloids that are strained by LCs, and active colloids that are driven into organized states by dissipation of energy ( e.g. bacteria). These examples, and key unresolved issues discussed at the end of this perspective, serve to convey the message that soft matter systems that integrate ideas from LC, surfactant, polymer and colloid sciences define fertile territory for fundamental studies and creation of future transformative technologies. 

Mesoscale chiral materials are prepared by lithographic methods, assembly of chiral building blocks, and through syntheses in the presence of polarized light. Typically, these processes result in micrometer‐sized structures, require complex top–down manipulation, or rely on tedious asymmetric separation. Chemical vapor deposition (CVD) polymerization of chiral precursors into supported films of liquid crystals (LCs) are discovered to result in superhierarchical arrangements of enantiomorphically pure nanofibers. Depending on the molecular chirality of the 1‐hydroxyethyl [2.2]paracyclophane precursor, extended arrays of enantiomorphic nanohelices are formed from achiral nematic templates. Arrays of chiral nanohelices extend over hundreds of micrometers and consistently display enantiomorphic micropatterns. The pitch of individual nanohelices depends on the enantiomeric excess and the purity of the chiral precursor, consistent with the theoretical model of a doubly twisted LC director configuration. During CVD of chiral precursors into cholesteric LC films, aspects of molecular and mesoscale asymmetry combine constructively to form regularly twisted nanohelices. Enantiomorphic surfaces permit the tailoring of a wide range of functional properties, such as the asymmetric induction of weak chiral systems.

 

The development of stimuli‐responsive materials suitable for use in wearable sensors is a key unresolved challenge. Liquid crystals (LCs) are particularly promising, as they do not require power, are light‐weight, and can be tuned to respond to a range of targeted chemical stimuli. Here, an advance is reported in the design of LCs for chemical sensors with the discovery of LCs that assume parallel orientations at free surfaces and yet retain their chemoresponsiveness. The resulting LC‐based sensors are more sensitive and exhibit faster responses than previous LC sensor designs.

 

Surface‐supported liquid crystals (LCs) that exhibit orientational and thus optical responses upon exposure to ppb concentrations of Cl₂gas are reported. Computations identified Mn cations as candidate surface binding sites that undergo redox‐triggered changes in the strength of binding to nitrogen‐based LCs upon exposure to Cl₂gas. Guided by these predictions, μm‐thick films of nitrile‐ or pyridine‐containing LCs were prepared on surfaces decorated with Mn²⁺binding sites as perchlorate salts. Following exposure to Cl₂, formation of Mn⁴⁺(in the form of MnO₂microparticles) was confirmed and an accompanying change in the orientation and optical appearance of the supported LC films was measured. In unoptimized systems, the LC orientational transitions provided the sensitivity and response times needed for monitoring human exposure to Cl₂gas. The response was also selective to Cl₂over other oxidizing agents such as air or NO₂and other chemical targets such as organophosphonates.