Electrophoretic propulsion of matchstick-shaped magnetodielectric particles in the presence of external magnetic fields in a nematic liquid crystal.

Synthesis of micro- and nanoparticles of pre-designed shape and surface properties is an integral part of soft and synthetic active matter. We report synthesis of matchstick-shaped (MS) magnetodielectric particles and demonstrate their potential as active agents with field-controllable trajectories in a nematic liquid crystal (NLC). The MS particles with homeotropic anchoring in NLCs align either parallel or perpendicular to the director depending on the dipolar or quadrupolar director distortions. When subjected to transverse electric and magnetic fields, the particles experience electric and magnetic torques trying to align them in the respective field directions. At equilibrium, the long axis is tilted at an angle with respect to the director. The change in orientation alters the surrounding elastic distortion, which results in unbalanced electroosmotic flows. These flows provide the necessary impetus for propelling the particles in various directions with different velocities depending on their orientations.

Effect of small amounts of akaganeite (ß-FeOOH) nanorods on the gelation, phase behaviour and injectability of thermoresponsive Pluronic F127.

Pluronic F127 (PF127) is a copolymer with an amphiphilic nature and can self-assemble to form micelles and, beyond 20% (w/v), form a thermoresponsive physical gel state. However, they are mechanically weak and easily dissolve in physiological environments, which limits their use in load-bearing in specific biomedical applications. Therefore, we propose a pluronic-based hydrogel with enhanced stability by incorporating small amounts of paramagnetic nanorods, akaganeite (ß-FeOOH) nanorods (NRs) of aspect ratio ∼7, with PF127. Due to their weak magnetic properties, ß-FeOOH NRs have been used as a precursor for preparing stable iron-oxide states (e.g., hematite and magnetite), and the studies on ß-FeOOH NRs to be used as a primary component in hydrogels are at the nascent stage. Here we report a method to synthesize ß-FeOOH NRs on a gram scale using a simple sol-gel process and characterize the NRs with various techniques. A phase diagram and thermoresponsive behaviour based on rheological experiments and visual observations are proposed for 20% (w/v) PF127 with low concentrations (0.1-1.0% (w/v)) of ß-FeOOH NRs. We observe a unique non-monotonous behaviour in the gel network represented by various rheological parameters like storage modulus, yield stress, fragility, high-frequency modulus plateau, and characteristic relaxation time as a function of nanorod concentration. A plausible physical mechanism is proposed to fundamentally understand the observed phase behaviour in the composite gels. These gels show thermoresponsiveness and enhanced injectability, and could find applications in tissue engineering and drug delivery.

Rheology and microstructure of thermoresponsive composite gels of hematite pseudocubes and Pluronic F127.

Stimuli-responsive materials or smart materials are designed materials whose properties can be changed significantly by applying external stimuli, such as stress, electric or magnetic fields, light, temperature, and pH. We report the linear and nonlinear rheological properties of thermoresponsive composite gels based on submicron-sized hematite pseudocube-shaped particles and a triblock copolymer Pluronic F127 (PF127). These novel composites form hard gels at an elevated temperature of 37 °C. For certain concentrations (<20 w/v. %) of hematite pseudocubes in 17.5 w/v. % of PF127, the gel strength is enhanced and the brittleness of the gels decreases. Higher concentrations (>20 w/v. %) of hematite pseudocubes in PF127 result in weaker and fragile gels. We develop an extensive rheological fingerprint using linear and nonlinear rheological studies. Adsorption of PF127 copolymer molecules on the hematite cube surfaces would further assist the formation of particle clusters along with magnetic interactions to be held effectively in the PF127 micellar network at elevated temperatures. The microscopic structure of these composite gels is visualized through a confocal microscope. Our experiments show that addition of hematite cubes up to 20 w/v. % does not change the rapid thermal gelation of PF127 solutions; hence, the hematite-PF127 composite, which transforms into a hard gel near human body temperature of 37 °C, could be suitable for use in smart drug delivery systems.

Nontrivial electrophoresis of silica nano and microrods in a nematic liquid crystal.

We study DC and AC electrophoresis of silica nano and microrods in a thin film of a nematic liquid crystal. These particles induce virtual topological defects and demonstrate nontrivial electrophoresis. We measure several electrophoretic mobility coefficients and compare with those calculated theoretically. We demonstrate a competing effect of elastic and electrostatic torques that arises due to tilting of the rods in the liquid crystal. A simple theory describing this effect allows us to measure the effective polarisability of the rods. Our approach is simple and applicable to a wide variety of asymmetric and polarisable particles.

Mandelic acid appended chiral gels as efficient templates for multicolour circularly polarized luminescence.

Mandelic acid is a medicinally important chiral molecule that is widely used as a vital component in antibiotics, antiseptics and cosmetics. While the medicinal properties of mandelic acid are well known, its aggregation and gelation characteristics, which are crucial to finding applications as cosmetics and ointments, are least explored. We have designed and synthesized a pair of mandelic acid derivatives and investigated their aggregation properties in binary solvent mixtures. The compounds undergo self-assembly through various noncovalent interactions, leading to the formation of robust chiral gels. Strong birefringence could be visualised from the individual structures constituting the gel. The large rod-like chiral structures are utilized as efficient templates for the assembly of ultra-small luminescent achiral carbon nanodots. The transfer of optical activity from the chiral host matrix to the fluorescent guest nanoparticles resulted in the generation of circularly polarized luminescence signals from the hybrid nanocomposites. The use of blue, green and red-emitting nanodots led to the fabrication of multicolour chiral light-emitting materials capable of covering the entire visible range. Considering the numerous medicinal benefits offered by mandelic acid and carbon nanodots, the materials constituting the nanocomposites, the distinct dimensions presented in the current work open new avenues for chiral light emitting materials to be used in biomedical research.

Interactions of charged microrods in chiral nematic liquid crystals.

We study the pair interaction of charged silica microrods in chiral nematic liquid crystals and show that the microrods with homeotropic surface anchoring form a bound state due to the competing effect of electrostatic (Coulomb) and elastic interactions. The robustness of the bound state is demonstrated by applying external electrical and mechanical forces that perturbs their equilibrium position as well as orientation. In the bound state we have measured the correlated thermal fluctuations of the position, using two-particle cross-correlation spectroscopy that uncovers their hydrodynamic interaction. These findings reveal unexplored aspects of liquid-crystal dispersions which are important for understanding the assembly and dynamics of nano- and microparticles in chiral nematic liquid crystals.

Microrheology to probe smectic clusters in bent-core nematic liquid crystals.

Many bent-core nematic liquid crystals exhibit unusual physical properties due to the presence of smectic clusters, known as "cybotactic" clusters, in the nematic phase. Here, we investigate the effect of these clusters on the complex shear modulus (G*(ω)) of two asymmetric bent-core liquid crystals using a microrheological technique. The compound with a shorter hydrocarbon chain (8OCH3) exhibits only a nematic (N) phase whereas the compound with a longer chain (16OCH3) exhibits both nematic (N) and smectic-A (SmA) phases. The rheological results are correlated with the measurements of curvature elastic constants. Our results show that the directional shear modulus of 16OCH3, just above the SmA to N phase transition temperature, is strikingly different than that of 8OCH3, owing to the smectic clusters. An approximate size of the clusters is estimated using a simple model. Therefore, microrheological studies on bent-core nematic liquid crystals are very useful in extracting information about underlying smectic clusters.

Evaporation of Inclined Drops: Formation of Asymmetric Ring Patterns.

Evaporation of colloidal drops on horizontal surfaces deposits the contained particles at the drop-edge producing radially symmetric ring-like stains. The symmetry in the particle deposition is broken when the drop is placed on a tilted surface due to the influence of gravity on the suspended particles and the drop itself. Using extremely small drops generated by electrospray, we explore cases where different mechanisms of particle transport dominate. We show that the asymmetric residues are formed as the gravity-induced effects compete with the capillary flow. Our results give a broad insight into the pattern formation of evaporating inclined drops.

Hierarchical self-assembly, spongy architecture, liquid crystalline behaviour and phase diagram of Laponite nanoplatelets in alcohol-water binary solvents.

Hydrophobicity and solvation of different charged species are among the various key factors that regulate the self-assembly of colloids, and macromolecules in their suspensions. In this paper, we demonstrate a method to tune the interaction potential and the resulting phase behaviour and microstructure of the states that form by using a combination of Laponite nanoplatelets and alcohols in water. This allows us to exquisitely control the self-assembly process of Laponite nanoplatelets. A new class of soft materials, called nanoclay-organogels, is studied systematically for their aging behaviour, microscopic structure and mechanical properties. Real space imaging techniques depicted spongy architecture with nano and micron size pores inside the gel matrix indicating the hierarchical self-assembly of the nanoplatelets in the aqueous solutions of polar organics. We have extensively examined the dispersion stability, aggregation, gelation and liquid crystalline behaviour of Laponite nanoplatelets in different alcohol (methanol, ethanol, 1-proponaol and ethylene glycol, and glycerol)-water binary solvents, thereby proposing a generalized description of nanoclay in alcoholic solutions, which is poorly probed and marginally understood in the literature. A phase diagram of Laponite® in alcohol solutions is proposed, which clearly demarcates regions of isotropic sol, unstable sol, isotropic gel, nematic/birefringent gel, glass, flocculated sedimentation and liquid crystalline structures.

Colloidal analogues of polymer chains, ribbons and 2D crystals employing orientations and interactions of nano-rods dispersed in a nematic liquid crystal.

Robust control over the position, orientation and self-assembly of nonspherical colloids facilitate the creation of new materials with complex architecture that are important from technological and fundamental perspectives. We study orientation, elastic interaction and co-assembly of surface functionalized silica nano-rods in thin films of nematic liquid crystal. With homeotropic boundary condition, the nano-rods are predominantly oriented perpendicular to the nematic director which is different than the mostly parallel orientation of the micro-rods. The percentage of perpendicular nano-rods are significantly larger than the parallel nano-rods. The perpendicular nano-rods create very weak elastic deformation and exhibit unusual, out-of-plane, attractive interaction. On the other hand, the nano-rods oriented parallel to the director create strong elastic deformation and shows anisotropic, in-plane, dipolar interaction. In both orientations, the induced defects reside in the nano-rods. With the help of a dynamic laser tweezers and using nano-rods as building blocks we demonstrate colloidal analogues of linear polymer chains, ribbons and two-dimensional binary crystals.

Shaping Silica Rods by Tuning Hydrolysis and Condensation of Silica Precursors.

We present the synthesis of colloidal silica particles with new shapes by manipulating the growth conditions of rods that are growing from polyvinylpyrrolidone-loaded water-rich droplets containing ammonia and ethanol. The silica rods grow by ammonia-catalyzed hydrolysis and condensation of tetraethoxysilane (TEOS). The lengthwise growth of these silica rods gives us the opportunity to change the conditions at any time during the reaction. In this work, we vary the availability of hydrolyzed monomers as a function of time and study how the change in balance between the hydrolysis and condensation reactions affects a typical synthesis (as described in more detail by our group earlier1). First, we show that in a "standard" synthesis, there are two silica growth processes occurring; one in the oil phase and one in the droplet. The growth process in the water droplet causes the lengthwise growth of the rods. The growth process in the oil phase produces a thin silica layer around the rods, but also causes the nucleation of 70 nm silica spheres. During a typical rod growth, silica formation mainly takes place in the droplet. The addition of partially hydrolyzed TEOS or tetramethoxysilane (TMOS) to the growth mixture results in a change in balance between the hydrolysis and condensation reaction. As a result, the growth also starts to take place on the surface of the water droplet and thus from the oil phase, not only from inside the droplet onto a silica rod sticking out of the droplet. Carefully tuning the growth from the droplet and the growth from the oil phase allowed us to create nanospheres, hollow silica rods, hollow sphere rod systems (colloidal matchsticks), and bent silica rods.

In-situ Observation of Hierarchical Self-Assembly Driven by Bicontinuous Gelation in Mixed Nanodisc Dispersions.

The search for new functional soft materials with precise and reconfigurable structures at the nano and meso-scale is a major challenge as well as objective of the current science. Patchy colloids of different shapes and functionalities are considered important new building blocks of a bottom-up approach towards rational design of new soft materials largely governed by anisotropic interactions. Herein, we investigate the self-assembly, growth of hierarchical microstructures and aging dynamics of 2D nano-platelets of two different aspect ratios (Laponite ~25 and Montmorillonite ~250) which form gels with different porosity that is achieved by tuning their mixing ratios. Qualitative in situ real-space studies are carried out, including fluorescent confocal microscopy imaging of the bicontinuous gelation process or final states, which provides dynamic visualization of the self-organization. The bicontinuous gels exhibit a foam-like morphology having pores of a few micrometers in size that can be tuned by varying the mixing ratio of nanoplatelets. It is shown that this new class of clay gels has unique and tunable physical properties that will find potential applications in the development of low cost lithium ion batteries, nanocomposites and nuclear waste management.

Kinetics of anisotropic ordering in Laponite dispersions induced by a water-air interface.

In this work, we report the kinetics of ordering occurring at the water-air interface of Laponite dispersions. Propagation of such ordering into the bulk and its relaxation dynamics were systematically studied through light scattering measurements. Depolarization ratio D(p), which accounted for the optical anisotropy, was measured as a function of depth from the interface and aging of the samples. The extent of spatial ordering was found to be several decades larger than the typical particle size. Spatial ordering originated from the interface and percolated into the bulk with aging time t(w). Growth in D(p) with waiting time was found to follow power-law behavior given as D(p)~t(w)(n), with n increasing from 0.1 to 4 as one moved away from the interface into the bulk. D(p) decreased exponentially with depth h given as D(p)~e(-(h/h(0))), where h(0) is the decay length, increasing from 0.4 to 0.75 mm with aging time. Dynamic structure factor measurements performed on the samples at various aging times, depths, and temperatures yielded two distinct relaxation times: one fast mode followed by a slow mode. The fast mode remained invariant while slow mode relaxation time followed an exponential decay with depth. This study indicated that the arrested phase nucleated from the interface and propagated into the bulk, which was not observed when the surface was insulated with a layer of hydrophobic liquid. Dilution of the concentrated samples destroyed the aforesaid ordering and made the dispersion homogeneous implying the ordered state was a glass.

Unified scaling behavior of physical properties of clays in alcohol solutions.

This paper reports observation of universal scaling of physical properties of clay particles, Laponite (aspect ratio=30) (L) and Na Montmorillonite (MMT, aspect ratio=200), in aqueous alcohol solutions (methanol, ethanol and 1-propanol) with solvent polarity, defined through reaction field factor f(OH)(ɛ(0),n)=[(ɛ(0) - 1/ɛ(0) + 2) - (n(2) - 1/n(2) + 2)], at room temperature (20°C). Here, ɛ(0) and n are the static dielectric constant and refractive index of the solvent concerned. Physical properties (Z) such as zeta potential, effective aggregate size, viscosity and surface tension scaled with the relative solvent polarity as Z∼δf(α); δf=(f(w)(ɛ(0),n) - f(OH)(ɛ(0),n)), where f(w)(ɛ(0),n) is the reaction field factor for water, Z is the normalized physical property, and α is its characteristic scaling exponent. The value of this exponent was found to be invariant of aspect ratio of the clay but dependent on the solvent polarity only.

Landau theory description of observed isotropic to anisotropic phase transition in mixed clay gels.

A characteristic new cooperative dehydration transition, in 1:1 Laponite-MMT cogel, was observed at T(c) ≈ 60 °C, a temperature at which the storage modulus (G(')) and depolarization ratio (D(p)) showed sharp increase, and the isotropic cogel turned into an anisotropic one. The dehydration dynamics could be described through power-law relations: G(') ∼ (T(c)-T)(-γ) and D(p) ∼ (T(c)-T)(-ß) with γ ≈ ß = 0.40 ± 0.05. The x-ray diffraction data revealed that the crystallite size decreased from 17 nm (at 20 °C) to 10 nm (at 80 °C) implying loss of free and inter-planar water. When this cogel was spontaneously cooled below T(c), it exhibited much larger storage modulii values which implied the existence of several metastable states in this system. This phase transition could be modeled through Landau theory, where the depolarization ratio was used as experimental order parameter (ψ). This parameter was found to scale with temperature, as ψ ∼ (T(c)-T)(-α), with power-law exponent α = 0.40 ± 0.05; interestingly, we found α ≈ ß ≈ γ.

Universal sol state behavior and gelation kinetics in mixed clay dispersions.

Sol and gel state behavior, in aqueous salt free dispersions, of clays Laponite (L) and Na montmorillonite (MMT) was studied at various mixing ratios (L:MMT = r = 1:0.5, 1:1, and 1:2). In the sol state, the zeta potential and gelation concentration of L-MMT obeyed the universal relation, X(L-MMT) = (rX(L) + X(MMT))/(1 + r), where X is zeta potential or gelation concentration (c(g)), implying that these properties are linear combinations of the same of their individual components. The low frequency storage modulus (G(0)'), relative viscosity (η(r)), and apparent cluster size (R) could be universally described by the power-law, G(0)' ∼ ((c/c(g)) - 1)(t) (c > c(g)), and η(r), R ∼ (1 - (c/c(g)))(-k,ν) (c < c(g)), with t = 1.5, k = 1.1, and υ = 0.8 close to the gelation concentration, for r = 1:1 cogel, consistent with the percolation model description of gelation. Interestingly, the hyperscaling relation δ = t/(k + t) yielded δ = 0.56 not too different from the predicted value ∼0.7, while the experimental value of δ obtained from G''(ω) ∼ ω(δ) close to c ≈ c(g) yielded δ = 1.5, which was at variance with the hyperscaling result. The experimental data, on hand, mostly supported percolation type gelation mechanism. As the cogels were slowly heated, at a characteristic temperature, T(g), a sharp increase in G' value was noticed, implying a transition to gel hardening (a new phase state). The temperature-dependent behavior followed the power-law description, G' ∼ (T(g) - T)(-γ) (T < T(g)), with γ = 0.40 ± 0.05 invariant of composition of the cogel, whereas for MMT and Laponite, γ = 0.25 and 0.55, respectively. It has been shown that the cogel has significantly enhanced mechanical (G(0) increased by 10 times for r = 1:1 cogel) and thermal properties (T(g) increased by 13 °C for 1:1 cogel) that can be exploited to design customized soft materials.