Two-wavelength wrinkling patterns in helicoidal plywood surfaces: imprinting energy landscapes onto geometric landscapes.

We present a model to investigate the formation of two-length scale surface patterns in biological and synthetic anisotropic soft matter materials through the high order interaction of anisotropic interfacial tension and capillarity at their free surfaces. The unique pattern-formation mechanism emerging from the presented model is based on the interaction between lower and higher order anchoring modes. Analytical and numerical solutions are used to shed light on why and how simple anisotropic anchoring generates two-lengthscale wrinkles whose amplitudes are given in terms of anchoring coefficients. The novel finding is that the surface energy landscape with its maxima and minima can be imprinted onto the surface geometric landscape. Symmetry relations and scaling laws are used to provide the explicit relations between the anchoring constants and surface profile of the two length scale wrinkles. These new findings establish a new paradigm for characterizing surface wrinkling in biological liquid crystals, and inspire the design of novel functional surface structures.

Multiple-wavelength surface patterns in models of biological chiral liquid crystal membranes.

We present a model to investigate the formation of surface patterns in biological materials through the interaction of anisotropic interfacial tension, bending elasticity, and capillarity at their free surfaces. Focusing on the cholesteric liquid crystal (CLC) material model, the generalized shape equation for anisotropic interfaces using the Rapini-Papoular anchoring and Helfrich free energies is applied to understand the formation of multi-length scale patterns, such as those found in floral petals. The chiral liquid crystal-membrane model is shown to be analogous to a driven pendulum, a connection that enables generic pattern classification as a function of bending elasticity, liquid crystal chirality and anchoring strength. The unique pattern-formation mechanism emerging from the model here presented is based on the nonlinear interaction between bending-driven folding and anchoring-driven creasing. The predictions are shown to capture accurately the two-scale wrinkling of certain tulips. These new findings enable not only to establish a new paradigm for characterizing surface wrinkling in biological liquid crystals, but also to inspire the design of functional surface structures.

Ab initio modelling of methane hydrate thermophysical properties.

The key thermophysical properties of methane hydrate were determined using ab initio modelling. Using density functional theory, the second-order elastic constants, heat capacity, compressibility, and thermal expansion coefficient were calculated. A wide and relevant range of pressure-temperature conditions were considered, and the structures were assessed for stability using the mean square displacement and radial distribution functions. Methane hydrate was found to be elastically isotropic with a linear dependence of the bulk modulus on pressure. Equally significant, multi-body interactions were found to be important in hydrates, and water-water interactions appear to strongly influence compressibility like in ice Ih. While the heat capacity of hydrate was found to be higher than that of ice, the thermal expansion coefficient was significantly lower, most likely due to the lower rigidity of hydrates. The mean square displacement gave important insight into stability, heat capacity, and elastic moduli, and the radial distribution functions further confirmed stability. The presented results provide a much needed atomistic thermoelastic characterization of methane hydrates and are essential input for the large-scale applications of hydrate detection and production.

Tunable nano-wrinkling of chiral surfaces: Structure and diffraction optics.

Periodic surface nano-wrinkling is found throughout biological liquid crystalline materials, such as collagen films, spider silk gland ducts, exoskeleton of beetles, and flower petals. These surface ultrastructures are responsible for structural colors observed in some beetles and plants that can dynamically respond to external conditions, such as humidity and temperature. In this paper, the formation of the surface undulations is investigated through the interaction of anisotropic interfacial tension, swelling through hydration, and capillarity at free surfaces. Focusing on the cellulosic cholesteric liquid crystal (CCLC) material model, the generalized shape equation for anisotropic interfaces using the Cahn-Hoffman capillarity vector and the Rapini-Papoular anchoring energy are applied to analyze periodic nano-wrinkling in plant-based plywood free surfaces with water-induced cholesteric pitch gradients. Scaling is used to derive the explicit relations between the undulations' amplitude expressed as a function of the anchoring strength and the spatially varying pitch. The optical responses of the periodic nano-structured surfaces are studied through finite difference time domain simulations indicating that CCLC surfaces with spatially varying pitch reflect light in a wavelength higher than that of a CCLC's surface with constant pitch. This structural color change is controlled by the pitch gradient through hydration. All these findings provide a foundation to understand structural color phenomena in nature and for the design of optical sensor devices.

Electroviscous sphere-wall interactions.

A theoretical analysis is presented to determine the forces of interaction between an electrically charged spherical particle and a charged plane wall when the particle translates parallel to the wall and rotates around its axis in a symmetric electrolyte solution at rest. The electroviscous effects, arising from the coupling between the electrical and hydrodynamic equations, are determined as a solution of three partial differential equations, derived from Cox's general theory [R.G. Cox, J. Fluid Mech. 338 (1997) 1], for electroviscous ion concentration, electroviscous potential and electroviscous flow field. It is a priori assumed that the double layer thickness surrounding each charged surfaces is much smaller than the particle size. Using the matched asymptotic expansion technique, the electroviscous forces experienced by the sphere are explicitly determined analytically for small particle-wall distances, but low and intermediate Peclet numbers.

Electroviscous cylinder-wall interactions.

A theoretical analysis is presented to determine the forces of interaction between an electrically charged cylindrical particle and a charged plane boundary wall when the particle translates parallel to the wall and rotates around its axis in a symmetric electrolyte solution at rest. The electroviscous effects, arising from the coupling between the electrical and hydrodynamic equations, are determined as a solution of three partial differential equations, derived from R.G. Cox's general theory [J. Fluid Mech. 338 (1997) 1], for electroviscous ion concentration, electroviscous potential, and electroviscous flow field. It is assumed a priori that the double layer thickness surrounding each charged surface is much smaller than the length scale of the problem. Using the matched asymptotic expansion technique, the electroviscous forces experienced by the cylinder are explicitly determined analytically for small particle-wall distances for low and intermediate Peclet numbers. It is found that the tangential force usually increases the drag above the purely hydrodynamic drag, although for certain conditions the drag can be reduced. Similarly the normal force is usually repulsive, i.e., it is an electrokinetic lift force, but under certain conditions the normal force can be attractive.

Assessing flow alignment of nematic liquid crystals through linear viscoelasticity.

Shear alignment of rodlike nematic liquid crystals is found when the reactive parameter lambda>1. Measurements of lambda usually require complex experiments. This paper presents a method based on the nematodynamic theory of Leslie and Ericksen that assesses flow alignment through small amplitude oscillatory flow. The method is based on the fact that the effect of lambda on the storage modulus G' of linear viscoelasticity, when the director is along the flow direction, is directly proportional to lambda-1. Thus the alignment-nonalignment transition for increasing lambda is a reentrant viscoelastic transition: viscoelastic (lambda<1) -->purely viscous (lambda=0) -->viscoelastic (lambda>1) that is reflected in the storage modulus G' and in the "loss angle" delta= tan(-1) (G"/G'). The methodology is demonstrated by analyzing the Leslie-Ericksen equations for small-amplitude oscillatory Poiseuille flow of (4-n-octyl- 4' -cyanobiphenyl) (8CB) using analytical and scaling methods. Since linear viscoelastic moduli are easily accessible, the proposed methodology is an additional useful and economical tool for nematodynamicists.

Monodomain and polydomain helicoids in chiral liquid-crystalline phases and their biological analogues.

Many natural composites exhibit an architecture known as twisted plywood which imparts to them a superior set of physical properties. The origin of this structure is complex and not yet understood. However, it is thought to involve a lyotropic chiral nematic liquid-crystalline mesophase. Indeed, striking structural similarities have been observed and reported between biological fibrous composites and ordered fluids. In this work, a mathematical model based on the Landau-de Gennes theory has been developed to investigate the role played by constraining surfaces in the structural development of a composite material that experiences a liquid-crystalline state during the early steps of its morphogenesis. The goal of this study is to verify the need for an initial constraining surface in the formation of monodomain twisted plywoods as hypothesized by Neville (Tissue & Cell 20, 133 (1988); Biology of Fibrous Composites (Cambridge University Press, 1993)). The numerical simulations qualitatively confirm this theory and highlight the important role that modelling of liquid-crystalline self-assembly plays in the study of tissue morphogenesis.

Texture formation in carbonaceous mesophase fibers.

Carbonaceous mesophases are discotic nematic liquid crystals that are spun into high performance carbon fibers using the melt spinning process. The spinning process produces a wide range of different fiber textures. Planar polar (PP) and planar radial (PR) textures are two ubiquitous ones. This paper presents theory and simulation of the texture formation process using the Landau-de Gennes mesoscopic theory for discotic liquid crystals. The computed PP and PR textures phase diagram, given in terms of temperature and fiber radius, is presented to establish the processing conditions and geometric factors that lead to the selection of these textures. Thin fibers adopt the PR texture, while thicker fibers and higher temperatures adopt the PP texture. The influence of elastic anisotropy to the formation of textures and structure is thoroughly characterized.

Temperature effects on capillary instabilities in a thin nematic liquid crystalline fiber embedded in a viscous matrix.

Linear stability analysis of capillary instabilities in a thin nematic liquid crystalline cylindrical fiber embedded in an immiscible viscous matrix is performed by formulating and solving the governing nemato-capillary equations, that include the effect of temperature on the nematic ordering as well as the effect of the nematic orientation. A representative axial nematic orientation texture with the planar easy axis at the fiber surface is studied. The surface disturbance is expressed in normal modes, which include the azimuthal wave number m to take into account non-axisymmetric modes. Capillary instabilities in nematic fibers reflect the anisotropic nature of liquid crystals, such as the ordering and orientation contributions to the surface elasticity and surface normal and bending stresses. Surface gradients of normal and bending stresses provide additional anisotropic contributions to the capillary pressure that may renormalize the classical displacement and curvature forces that exist in any fluid fiber. The exact nature (stabilizing and destabilizing) and magnitude of the renormalization of the displacement and curvature forces depend on the nematic ordering and orientation, i.e. the anisotropic contribution to the surface energy, and accordingly capillary instabilities may be axisymmetric or non-axisymmetric. In addition, when the interface curvature effects are accounted for as contributions of the work of interfacial bending and torsion to the total energy of the system, the higher-order bending moment contribution to the surface stress tensor is critical in stabilizing the fiber instabilities. For the planar easy axis, the nematic ordering contribution to the surface energy, which renormalizes the effect of the fiber shape, plays a crucial role to determine the instability mechanisms. Moreover, the unstable modes, which are most likely observed, can be driven by the dependence of surface energy on the surface area. Low-ordering fibers display the classical axisymmetric mode, since the surface energy decreases by decreasing the surface area. Decreasing temperature gives rise to the encounter with a local maximum or to monotonic increase of the characteristic length of the axisymmetric mode. Meanwhile, in the presence of high surface ordering, non-axisymmetric finite wavelength instabilities emerge, with higher modes growing faster since the surface energy decreases by increasing the surface area. As temperature decreases, the pitches of the chiral microstructures become smaller. However, this non-axisymmetric instability mechanism can be regulated by taking account of the surface bending moment, which contains higher order variations in the interface curvatures. More and more non-axisymmetric modes emerge as temperature decreases, but, at constant temperature, only a finite number of non-axisymmetric modes are unstable and a single fastest growing mode emerges with lower and higher unstable modes growing slower. For nematic fibers, the classical fiber-to-droplet transformation is one of several possible instability pathways, while others include chiral microstructures. The capillary instabilities' growth rate of a thin nematic fiber in a viscous matrix is suppressed by increasing either the fiber or matrix viscosity, but the estimated droplet sizes after fiber breakup in axisymmetric instabilities decrease with increasing the matrix viscosity.

Capillary instabilities in thin nematic liquid crystalline fibers.

A complete identification and characterization of three distinct capillary instabilities in nematic liquid crystal fibers is presented. Linear stability analysis of capillary instabilities in thin nematic liquid crystalline cylindrical fibers is performed by formulating and solving the governing nematocapillary equations. A representative axial nematic orientation texture is studied. The surface disturbance is expressed in normal modes, which include the azimuthal wavenumber m to take into account nonaxisymmetric modes of the disturbance. Capillary instabilities in nematic fibers reflect the anisotropic nature of liquid crystals, such as the orientation contribution to the surface elasticity and surface bending stresses. Surface gradients of bending stresses provide additional anisotropic contributions to the capillary pressure that may renormalize the classical displacement and curvature forces that exist in any fluid fiber. The exact nature (stabilizing and destabilizing) and magnitude of the renormalization of the displacement and curvature forces depend on the nematic orientation and the anisotropic contribution to the surface energy, and accordingly capillary instabilities may be axisymmetric or nonaxisymmetric, with finite or unbounded wavelengths. Thus, the classical fiber-to-droplet transformation is one of several possible instability pathways while others include surface fibrillation.

Saddle-splay elasticity and interfacial nematostatics.

This Brief Report drives the generalized force balance equations of interfacial statics between nematic liquid crystals (NLC) and isotropic fluids (I), using the classical equations of liquid crystal physics, taking into account an important class of gradient surface elasticity, known as saddle-splay elasticity. The objective is to identify the exact nature of the saddle-splay contributions to the fundamental interfacial force balance equations, known as the Laplace-Young equation and the Marangoni force equation. General expressions for the dynamic generalization of these two equations were given by Shih, Mann, and Brown [Mol. Cryst. Liq. Cryst. 98, 47 (1983)], but the specific form of the static terms appearing in these two equations were missing in the literature, and are now given in this paper. It is found that the tensorial order and functional form of the contributions of saddle-splay elasticity to the two force balance equations are congruent with those arising from the interfacial tension. Therefore, to generalize the interfacial equations of nematostatics by including saddle-splay energy, the interfacial tension must be renormalized with the saddle-splay energy contribution. In addition, saddle splay gives rise to distortion stresses, the two-dimensional analog to the bulk Ericksen stresses, which contribute to the tangential Marangoni force. Exact expressions for pressure jumps across NLC/I interfaces and for the tangential Marangoni force are derived and analyzed. These generalized results are expected to be useful in the characterization of nematocapillarity phenomena, such as wetting, spreading, and the mechanics of thin nematic films.

Tension gradients and Marangoni flows in nematic interfaces.

This brief report (i) presents equations that govern the balance of tangential forces in interfaces between isotropic viscous fluids and nematic liquid crystals, and (ii) establishes the physical origin of nematic Marangoni flows. It is shown that surface gradients in the orientation dependent surface free energy gives rise to tangential nematic Marangoni forces. Tangential nematic Marangoni forces are caused by surface gradients of the nematic tensor order parameter, and the kinetic coefficient characterizing this interfacial phenomenon is proportional to nematic elastic storage. Expressions of the Marangoni forces using a classical constitutive equation for the surface free energy are given for general and uniaxial nematic ordering states. Nematic Marangoni flows or nematocapillarity augments the class of Marangoni flows present in electrocapillarity, diffusocapillarity, and thermocapillarity.

Bilateral metastatic endophthalmitis in diabetics.

A case of bilateral metastatic endophthalmitis in a diabetic patient is presented. Most cases from the literature are secondary to fungal sepsis, but few cases of metastatic bacterial endophthalmitis have been reported. In this diabetic patient urine and blood cultures were negative for fungi and positive for Escherichia Coli. The outcome was disappointing, the enucleation of both globes being necessary. The aim of the report is to outline that metastatic endophthalmitis should be counted among the possible complications of bacterial sepsis, especially in diabetics because of their susceptibility to infection.

Neuroendocrine, sympathetic and metabolic responses induced by interleukin-1.

Effects on turnover of vasopressin (AVP) in the hypothalamus and on secretion of pituitary hormones, catecholamines and insulin after intraperitoneal injection of recombinant interleukin-1 (beta) (IL-1) were investigated in male wistar rats. Intraperitoneal administration of IL-1 in a dose (1 microgram) that maximally activated pituitary-adrenal activity failed to alter plasma concentrations of prolactin, luteinizing hormone and melanocyte-stimulating hormone. Rats chronically cannulated in the right jugular veins showed a time-related increase in plasma corticosterone concentrations in response to intraperitoneal administration of IL-1 that lasted up to 4 h. In the same rats, plasma epinephrine (E) and norepinephrine (NE) concentrations were only slightly elevated (2-fold increase) at 30 min and at 1 h after IL-1 administration. Unlike in endotoxin-resistant C3H/HeJ mice, where IL-1 induces hypoglycemia, IL-1 did not affect plasma concentrations of glucose and insulin in Wistar rats. In the zona externa of the median eminence, IL-1 stimulated corticotropin-releasing factor (CRF) turnover at an approximate rate of 15%/h, but did not cause a concomitant change in AVP turnover as can be observed after insulin-induced hypoglycemia. Since half of the hypothalamic CRF neurons have been shown to costore AVP, the data favor the view of a selective effect of IL-1 on a subtype of CRF neurons. We conclude that pituitary-adrenal activation in response to Il-1 is caused by CRF secretion from a subtype of CRF neurons (not storing AVP) in the rat hypothalamus.(ABSTRACT TRUNCATED AT 250 WORDS)