Interfacial Effects during Phase Change in Multiple Levitated Tetrahydrofuran Hydrate Droplets.

Recent strategies developed to examine the nucleation of crystal structures like tetrahydrofuran (THF) hydrates without the effects of a solid interface have included acoustic levitation, where only a liquid-gas interface initially exists. However, the ability now exists to levitate and freeze multiple droplets simultaneously, which could reveal interdroplet effects and provide further insight into interfacial nucleation phenomena. In this study, using direct digital and infrared imaging techniques, the freezing of up to three simultaneous THF hydrate droplets was investigated for the first time. Nucleation was initiated at the aqueous solution-air interface. Two pseudo-heterogeneous mechanisms created additional nucleation interfaces: one from cavitation effects entraining microbubbles and another from subvisible ice particles, also called hydrate-nucleating particles (HNPs), impacting the droplet surface. For systems containing droplets in both the second and third positions, nucleation was statistically simultaneous between all droplets. This effect may have been caused by the high liquid-solid interfacial pressures that developed at nucleation, causing some cracking in the initial hydrate shell around the droplet and releasing additional HNPs (now of hydrate) into the air. During crystallization, the THF hydrate droplets developed a completely white opacity, termed optical clarity loss (OCL). It was suggested that high hydrate growth rates within the droplet resulted in the capture of tiny air bubbles within the solid phase. In turn, light refraction through many smaller bubbles resulted in the OCL. These bubbles created structural inhomogeneities, which may explain how the volumetric expansion of the droplets upon complete solidification was 23.6% compared with 7.4% in pure, stationary THF hydrate systems. Finally, the thermal gradient that developed between the top and bottom of the droplet during melting resulted in a surface tension gradient along the air-liquid interface. In turn, convective cells developed within the droplet, causing it to spin rapidly about the horizontal axis.

Geometry-structure models for liquid crystal interfaces, drops and membranes: wrinkling, shape selection and dissipative shape evolution.

We review our recent contributions to anisotropic soft matter models for liquid crystal interfaces, drops and membranes, emphasizing validations with experimental and biological data, and with related theory and simulation literature. The presentation aims to illustrate and characterize the rich output and future opportunities of using a methodology based on the liquid crystal-membrane shape equation applied to static and dynamic pattern formation phenomena. The geometry of static and kinetic shapes is usually described with dimensional curvatures that co-mingle shape and curvedness. In this review, we systematically show how the application of a novel decoupled shape-curvedness framework to practical and ubiquitous soft matter phenomena, such as the shape of drops and tactoids and bending of evolving membranes, leads to deeper quantitative insights than when using traditional dimensional mean and Gaussian curvatures. The review focuses only on (1) statics of wrinkling and shape selection in liquid crystal interfaces and membranes; (2) kinetics and dissipative dynamics of shape evolution in membranes; and (3) computational methods for shape selection and shape evolution; due to various limitations other important topics are excluded. Finally, the outlook follows a similar structure. The main results include: (1) single and multiple wavelength corrugations in liquid crystal interfaces appear naturally in the presence of surface splay and bend orientation distortions with scaling laws governed by ratios of anchoring-to-isotropic tension energy; adding membrane elasticity to liquid crystal anchoring generates multiple scales wrinkling as in tulips; drops of liquid crystals encapsulates in membranes can adopt, according to the ratios of anchoring/tension/bending, families of shapes as multilobal, tactoidal, and serrated as observed in biological cells. (2) Mapping the liquid crystal director to a membrane unit normal. The dissipative shape evolution model with irreversible thermodynamics for flows dominated by bending rates, yields new insights. The model explains the kinetic stability of cylinders, while spheres and saddles are attractors. The model also adds to the evolving understanding of outer hair cells in the inner ear. (3) Computational soft matter geometry includes solving shape equations, trajectories on energy and orientation landscapes, and shape-curvedness evolutions on entropy production landscape with efficient numerical methods and adaptive approaches.

A coarse-grained molecular model of amyloid fibrils systems.

We report a computational model for amyloid fibrils and discuss its main features and ability to match different experimental morphological characteristics. The model captures the liquid crystalline and cholesteric behaviours in short and rigid amyloid fibrils and shows promising extendibility to more complex colloidal liquid crystals.

All-Atom Molecular Dynamics of Pure Water-Methane Gas Hydrate Systems under Pre-Nucleation Conditions: A Direct Comparison between Experiments and Simulations of Transport Properties for the Tip4p/Ice Water Model.

(1) Background: New technologies involving gas hydrates under pre-nucleation conditions such as gas separations and storage have become more prominent. This has necessitated the characterization and modeling of the transport properties of such systems. (2) Methodology: This work explored methane hydrate systems under pre-nucleation conditions. All-atom molecular dynamics simulations were used to quantify the performance of the TIP4P/2005 and TIP4P/Ice water models to predict the viscosity, diffusivity, and thermal conductivity using various formulations. (3) Results: Molecular simulation equilibrium was robustly demonstrated using various measures. The Green-Kubo estimation of viscosity outperformed other formulations when combined with TIP4P/Ice, and the same combination outperformed all TIP4P/2005 formulations. The Green-Kubo TIP4P/Ice estimation of viscosity overestimates (by 84% on average) the viscosity of methane hydrate systems under pre-nucleation conditions across all pressures considered (0-5 MPag). The presence of methane was found to increase the average number of hydrogen bonds over time (6.7-7.8%). TIP4P/Ice methane systems were also found to have 16-19% longer hydrogen bond lifetimes over pure water systems. (4) Conclusion: An inherent limitation in the current water force field for its application in the context of transport properties estimations for methane gas hydrate systems. A re-parametrization of the current force field is suggested as a starting point. Until then, this work may serve as a characterization of the deviance in viscosity prediction.

From Infrared Spectra to Macroscopic Mechanical Properties of sH Gas Hydrates through Atomistic Calculations.

The vibrational characteristics of gas hydrates are key identifying molecular features of their structure and chemical composition. Density functional theory (DFT)-based IR spectra are one of the efficient tools that can be used to distinguish the vibrational signatures of gas hydrates. In this work, ab initio DFT-based IR technique is applied to analyze the vibrational and mechanical features of structure-H (sH) gas hydrate. IR spectra of different sH hydrates are obtained at 0 K at equilibrium and under applied pressure. Information about the main vibrational modes of sH hydrates and the factors that affect them such as guest type and pressure are revealed. The obtained IR spectra of sH gas hydrates agree with experimental/computational literature values. Hydrogen bond's vibrational frequencies are used to determine the hydrate's Young's modulus which confirms the role of these bonds in defining sH hydrate's elasticity. Vibrational frequencies depend on pressure and hydrate's O···O interatomic distance. OH vibrational frequency shifts are related to the OH covalent bond length and present an indication of sH hydrate's hydrogen bond strength. This work presents a new route to determine mechanical properties for sH hydrate based on IR spectra and contributes to the relatively small database of gas hydrates' physical and vibrational properties.

Rate of Entropy Production in Evolving Interfaces and Membranes under Astigmatic Kinematics: Shape Evolution in Geometric-Dissipation Landscapes.

This paper presents theory and simulation of viscous dissipation in evolving interfaces and membranes under kinematic conditions, known as astigmatic flow, ubiquitous during growth processes in nature. The essential aim is to characterize and explain the underlying connections between curvedness and shape evolution and the rate of entropy production due to viscous bending and torsion rates. The membrane dissipation model used here is known as the Boussinesq-Scriven fluid model. Since the standard approaches in morphological evolution are based on the average, Gaussian and deviatoric curvatures, which comingle shape with curvedness, this paper introduces a novel decoupled approach whereby shape is independent of curvedness. In this curvedness-shape landscape, the entropy production surface under constant homogeneous normal velocity decays with growth but oscillates with shape changes. Saddles and spheres are minima while cylindrical patches are maxima. The astigmatic flow trajectories on the entropy production surface, show that only cylinders and spheres grow under the constant shape. Small deviations from cylindrical shapes evolve towards spheres or saddles depending on the initial condition, where dissipation rates decrease. Taken together the results and analysis provide novel and significant relations between shape evolution and viscous dissipation in deforming viscous membrane and surfaces.

Thermodynamic modelling of acidic collagenous solutions: from free energy contributions to phase diagrams.

Tropocollagen is considered one of the main precursors in the fabrication of collagen-based biomaterials. Triple helix acidic solutions of collagen I have been shown experimentally to lead to chiral plywood architectures found in bone and "cornea" like tissues. As these plywoods are solid analogues of liquid crystal architectures, bio-inspired processing and fabrication platforms based on liquid crystal physics and thermodynamics will continue to play an essential role. For tissue engineering applications, it has been shown that dilute isotropic collagen solutions need to be flow processed first and then dehydrated. Thus, a complete fundamental understanding of the thermodynamics and free energy contributions in acidic collagen aqueous solutions is necessary to avoid expensive trial-and-error fabrication. To achieve this goal, we analyze the microscopic mechanisms of ordering and interactions in solutions of triple helix collagen, namely mixing, attraction, excluded-volume and chirality. To capture the mentioned physics, we then incorporate and integrate the Flory-Huggins, Maier-Saupe, Onsager and Frank theories. Nonetheless, they together are incapable of providing an acceptable mesophasic description in acidic collagenous solutions because tropocollagen biomacromolecules are positively charged. We then explore a simple and accurate electrostatic mean-field potential. Our results on collagen are in good agreement with experiments and include phase diagrams, phase transition thresholds, and critical isotropic/cholesteric order parameters. The present extended theory is shown to properly converge to classical liquid crystal models and is used to express the phenomenological Landau-de Gennes parameters with more fundamental quantities. This study provides a platform to derive accurate process models for the fabrication of collagen-based materials, considering and benefitting from the full range of underlying interactions.

Extracting shape from curvature evolution in moving surfaces.

Shape is a crucial geometric property of surfaces, interfaces, and membranes in biology, colloidal and interface science, and many areas of physics. This paper presents theory, simulation and scaling of local shape and curvedness changes in moving surfaces and interfaces, under uniform normal motion, as in phase ordering transitions in liquid crystals. Previously presented measures of shape and curvedness are introduced in quantities and equations used in colloidal science and interfacial transport phenomena to separate shape effects from those of curvedness. Considering in parallel the new shape formalism with the classical curvature formalism, this paper sheds new light on what effects originate only from shape. The new shape evolution equations are solved under uniform normal surface flow. It is found that the solutions obey the so-called "astigmatism equation" fixing the linear relation between the radii of curvature. Astigmatic trajectories in the shape-curvedness phase plane, can be clearly classified into two modes: (i) constant shape evolution, and (ii) variable shape-variable curvedness. Shapes between spheres and cylinders follow the former mode for large curvedness and transition at smaller curvedness into the latter. Shapes' transitions between cylinder and saddles only follow the second mode. Under geometry-driven stagnation (i.e. zero normal velocity) shapes can be frozen. Evolving spheres and cylinders freeze into the same original shape, but perturbed cylinders can freeze into a variety of shapes including saddles. The results provide a useful complementary view on how to describe and control shape evolution in surfaces and interfaces, of wide interest in soft matter materials.

Morphology of elastic nematic liquid crystal membranes.

Liquid crystalline phases found in many biological materials, such as actin, DNA, cellulose, and collagen can be responsible for the deformation of cell membranes. In this paper, cell membrane deformation is investigated through the coupling between liquid crystal anisotropy and membrane bending elasticity. The generalized shape equation for anisotropic interfaces, which resort to the Cahn-Hoffman capillarity vector, the Rapini-Papoular anchoring energy, and the Helfrich elastic energy, is applied to gain insight into the deformation of closed liquid crystal membranes. This study presents a general morphological phase diagram of membrane surface patterns, in which two characteristic regimes of membrane shapes can be classified with respect to the most dominant factor between liquid crystal anisotropy and bending elasticity. To that end, we consider a 2D nematic liquid crystal droplet immersed in a isotropic phase in the presence of an interfacial layer of surfactants, which leads to an additional elastic contribution to the free energy of the system. The presented results indicate that, depending on the bending elasticity of the cell membrane, the liquid crystal might be able to deform the cell, thereby resulting in anisotropic asymmetric shapes. As liquid crystal anisotropy dominates the bending elasticity, spindle-like or tactoid shapes, which are extensively observed in experiments, can be formed. The findings provide a foundational framework to better understand membrane topologies in living soft matters. Furthermore, the coupling between order and curvature of membranes shed new light into the design of novel functional soft materials.

Biological plywood film formation from para-nematic liquid crystalline organization.

In vitro non-equilibrium chiral phase ordering processes of biomacromolecular solutions offer a systematic and reproducible way of generating material architectures found in Nature, such as biological plywoods. Accelerated progress in biomimetic engineering of mesoscopic plywoods and other fibrous structures requires a fundamental understanding of processing and transport principles. In this work we focus on collagen I based materials and structures to find processing conditions that lead to defect-free collagen films displaying the helicoidal plywood architecture. Here we report experimentally-guided theory and simulations of the chiral phase ordering of collagen molecules through water solvent evaporation of pre-aligned dilute collagen solutions. We develop, implement and a posteriori validate an integrated liquid crystal chiral phase ordering-water transport model that captures the essential features of spatio-temporal chiral structure formation in shrinking film domains due to directed water loss. Three microstructural (texture) modes are identified depending on the particular value of the time-scale ratio defined by collagen rotational diffusion to water translational diffusion. The magnitude of the time scale ratio provides the conditions for the synchronization of the helical axis morphogenesis with the increase in the mesogen concentration due to water loss. Slower than critical water removal rates leads to internal multiaxial cellular patterns, reminiscent of the classical columnar-equiaxed metallurgical casting structures. Excessive water removal rates lead to destabilization of the chiral axis and multidomain defected films. The predictions of the integrated model are in qualitative agreement with experimental results and can potentially guide solution processing of other bio-related mesogenic solutions that seek to mimic the architecture of biological fibrous composites.

Theory and Simulation of Cholesteric Film Formation Flows of Dilute Collagen Solutions.

Dilute isotropic collagen solutions are usually flow processed into monodomain chiral nematic thin films for obtaining highly ordered materials by a multistep process that starts with complex inhomogeneous flow kinematics. Here we present rigorous theory and simulation of the initial precursors during flow steps in cholesteric collagen film formation. We first extract the molecular shape parameter and rotational diffusivity from previously reported simple shear data of dilute collagen solutions, where the former leads the reactive parameter (tumbling function) which determines the net effect of vorticity and strain rate on the average orientation and where the latter establishes the intensity of strain required for flow-birefringence, both crucial quantities for controlled film formation flow. We find that the tumbling function is similar to those of rod-like lyotropic liquid crystalline polymers and hence it is predicted that they would tumble in the ordered high concentration state leading to flow-induced texturing. The previously reported experimental data is well fitted with rotational diffusivities whose order of magnitude is consistent to those of other biomacromolecules. We then investigate the response of the tensor order parameter to complex flow kinematics, ranging from pure vorticity, through simple shear, to extensional flow, as may arise in typical flow casting and film flows. The chosen control variable to produce precursor cholesteric films is the director or average orientation, since the nematic order is set close to typical values found in concentrated cholesteric type I collagen solutions. Using the efficient four-roll mill kinematics, we summarize the para-nematic structure-flow process diagram in terms of the director orientation and flow type. Using analysis and computation, we provide a parametric envelope that is necessary to eventually produce well-aligned cholesteric films. We conclude that extensional flow is an essential ingredient of well-ordered film precursors with required Deborah numbers on the order of unity.

Geometric reconstruction of biological orthogonal plywoods.

In this paper we focus on the structural determination of biological orthogonal plywoods, fiber-like composite analogues of liquid crystalline phases, where the fibrils of the building blocks show sharp 90° orientation jumps between fibers in adjacent domains. We present an original geometric and computational modelling that allows us to determine the fibrillary orientation in biological plywoods from periodic herringbone patterns commonly observed in cross-sections. Although herringbone patterns were long reported, the specific and quantitative relationships between herringbones and the orthogonal plywoods were absent or at best incomplete. Here we provide an efficient and new procedure to perform an inverse problem that connects two specific features of the herringbone patterns (aperture angle and wavelength) with the 3D morphology of the structure, whose accuracy and validity were ascertained through in silico simulations and also with real specimens ("Eremosphaera viridis"). This contribution extends significantly the better known characterization methods of 2D cross sections, such as the arced patterns observed in biological helicoidal plywoods, and with the present proposed methodology it adds another characterization tool for a variety of biological fibrous composites that form cornea-like tissues.

Nano-scale surface wrinkling in chiral liquid crystals and plant-based plywoods.

We present theoretical scaling and computational analysis of nanostructured free surfaces formed in chiral liquid crystals (LC) and plant-based twisted plywoods. A nemato-capillary model is used to derive a generalized equation that governs the shape of cholesteric free surfaces. It is shown that the shape equation includes three distinct contributions to the capillary pressure: area dilation, area rotation, and director curvature. To analyse the origin of periodic reliefs in plywood surfaces, these three pressure contributions and corresponding surface energies are systematically investigated. It is found that for weak homeotropic surface anchoring, the nano-wrinkling is driven by the director curvature pressure mechanism. Consequently, the model predicts that for a planar surface with a uniform tangential helix vector, no surface nano-scale wrinkling can be observed because the director curvature pressure is zero. Scaling is used to derive the explicit relation between the wrinkling's amplitude to the wavelength ratio as a function of the anisotropic surface tension, which is then validated with experimental values. These new findings can be used to characterize plant-based twisted plywoods, as well as to inspire the design of biomimetic chiro-optical devices.

Disclination elastica model of loop collision and growth in confined nematic liquid crystals.

Theory and modeling are used to characterize disclination loop-loop interactions in nematic liquid crystals under capillary confinement with strong homeotropic anchoring. This defect process arises when a mesogen in the isotropic phase is quenched into the stable nematic state. The texture evolution starts with +1/2 disclination loops that merge into a single loop through a process that involves collision, pinching and relaxation. The process is characterized with a combined Rouse-Frank model that incorporates the tension and bending elasticity of disclinations and the rotational viscosity of nematics. The Frank model of disclinations follows the Euler elastica model, whose non-periodic solution, known as Poleni's curve, is shown to locally describe the loop-loop collision and to shed light on why loop-loop merging results in a disclination intersection angle of approximately 60°. Additional Poleni invariants demonstrate how tension and bending pinch the two loops into a single +1/2 disclination ring. The Rouse model of disclination relaxation yields a Cahn-Hilliard equation whose time constant combines the confinement, tension/bending stiffness ratio and disclination diffusivity. Based on predictions made using this three stage process, a practical procedure is proposed to find viscoelastic parameters from defect geometry and defect dynamics. These findings contribute to the evolving understanding of textural transformations in nematic liquid crystals under confinement using the disclination elastica methodology.

Computational study of the elastic properties of Rheum rhabarbarum tissues via surrogate models of tissue geometry.

Plant petioles and stems are hierarchical cellular structures, displaying geometrical features defined at multiple length scales. One or more of the intermediate hierarchical levels consists of tissues in which the cellular distribution is quasi-random, a factor that affects the elastic properties of the tissues. The current work focuses on the finite element analysis (FEA) of the constituent tissues of the plant Rheum rhabarbarum (rhubarb). The geometric model is generated via a recently introduced method: the finite edge centroidal Voronoi tessellation (FECVT), which is capable to capture the gradients of cellularity and diversified pattern of cellular materials, as opposed to current approaches in literature. The effective stiffness of the tissues is obtained by using an accurate numerical homogenization technique via detailed finite element analysis of the models of sub-regions of the tissues. As opposed to a large-scale representative volume element (RVE), statistical volume elements (SVE) are considered in this work to model tissue microstructures that are highly random. 2D finite element analyses demonstrate that the distribution of cells in collenchyma and parenchyma tissue make them stiffer in two different directions, while the overall effect of the combined tissues results in approximately equal stiffness in both directions. The rhubarb tissues, on the other hand, are more compliant than periodic and quasi-uniform random cellular materials by a factor of up to 47% and 44%, respectively. The variations of the stiffness shows the stiffening role that cell shape, size, and graded cellular distribution play in the mechanics of the rhubarb tissue.

Stress-sensor device based on flexoelectric liquid crystalline membranes.

Membrane flexoelectricity is an electromechanical coupling process that describes membrane bending and membrane electrical polarization caused by bending under electric fields. In this paper we propose, formulate, and characterize a stress-sensor device for mechanically loaded solids, consisting of a soft flexoelectric thin membrane attached to the loaded deformed solid. Because the curvature of the deformed solid is transferred to the attached flexoelectric membrane, the electromechanical transduction of the latter produces a charge that is proportional to the stress of the solid. The model of the stress-sensor device is based on the integration of the thermodynamics of polarizable membranes with isotropic solid elasticity, leading to a transfer function that identifies the elastic, electromechanical, and geometrical parameters involved in electrical-signal generation. The model is applied to representative normal bending and then to more complex off-axis bending of elastic bars. In all cases, a common transfer function shows the generic material and its geometric contributions. The sensor sensitivity increases linearly with flexoelectricity and the membrane-solid interface, and the sensitivity decreases with increasing membrane thickness and Young's modulus of the solid. The theoretical results contribute to ongoing experimental efforts towards the development of anisotropic soft-matter-based stress-sensor devices through solid-membrane interactions and electromechanical transduction.

Dynamic wetting model for the isotropic-to-nematic transition over a flat substrate.

Phase ordering over solid substrates is a ubiquitous and important soft material transformation process whose description incorporates wetting, anchoring and phase transition kinetics. In this paper the kinetics of the isotropic-to-nematic isothermal phase transition over a flat solid surface in a growing spherical drop is analyzed based on the Landau-de Gennes Q-tensor order parameter equations. The model, based on a previously derived interface force balance and a newly derived contact line force balance, is shown to be consistent with the generic model of conservative interface and contact line motions. The advancing dynamic contact angle equation is extracted from kinematic compatibility between the moving isotropic-nematic interface and contact line. A tractable surface phase transition kinetic model obtained by focusing on the dominant phase transition and wetting driving forces yields: (i) the constant advancing dynamic contact angle θ, and (ii) the contact line speed as a function of undercooling ΔT. It is shown that as undercooling increases, the surface phase transition mode approaches the bulk phase transition mode, such that θ approaches π. The elastic and wetting parameters that control the phase transformation process are identified and experiments for their determination are defined. These dynamic wetting and surface phase transition results significantly expand existing characterization methods of LC-substrate interfaces based on static phase transition droplet methods.

Structure characterisation method for ideal and non-ideal twisted plywoods.

The twisted plywood architecture, known as the Bouligand structure, is a ubiquitous biological and synthetic fibrous composite structure, analogous to that of cholesteric liquid crystals. Twisted plywoods can show ideal or non-ideal structures and are formed via equilibrium or non-equilibrium liquid crystal self-assembly processes. A key to the structure characterisation of plywood films is the specification of the local and global helix vector h(x) and pitch p(x) of the cholesteric order. Previous extensive work demonstrated that oblique cuts of the plywood give rise to arc-patterns that depend both on the unknown incision angle α and the unknown pitch p(x), thus making the precise 3D cholesteric reconstruction ambiguous. In this paper we present an efficient method based on geometric modelling and new visualization software that determines unambiguously the cholesteric pitch under spatially homogeneous and heterogeneous conditions. The method is applied to films that display two-pitch and spatially non-homogenous structures, as sometimes observed under equilibrium and non-equilibrium self-assembly. The method can be extended to other biological materials such as cornea-like, cylindrical, and various cuticle plywoods.

Mechanisms and shape predictions of nematic disclination branching under conical confinement.

Liquid crystals (LCs) are self-organizing anisotropic viscoelastic soft materials that flow like viscous liquids and display anisotropies like crystals. When a nematic liquid crystal is confined to a capillary tube with strong anchoring conditions, disclination defects of higher (+1) and lower (+1/2) topological charges can coexist, connected through a defect branch point. The shape of the +1/2 disclination lines emanating from the branch point are functions of confinement and bulk elasticity. Previous work shows that nematic liquid crystals under cylindrical confinement display a radial (one +1 line)-to-planar polar (two +1/2 lines) defect texture transition through the nucleation and uniform motion of a disclination branch point. Here we present analysis, scaling and modeling based on a non-linear non-local nematic elastic equation that shows that a branch point also can be generated from disclinations in a liquid crystal confined to different conical geometries with homeotropic anchoring conditions. The cone aperture increases the bending stiffness but decreases the curvature of the disclination. These competing effects lead to a decrease in the total disclination curvature, increase in elastic energy and volume of the branching region. The results are summarized into power laws and integrated into a shape/energy diagram that reveals the effects of confinement and its gradient (cone angle) on disclination shape selection. These new findings are useful to assess the Frank elasticity of new nematic liquid crystals and to predict novel defect structures in complex confinement, including biological microfluidics and mesophase fiber spinning.

A molecular and thermodynamic view of the assembly of gold nanoparticles in nematic liquid crystal.

The molecular interactions driving the assembly of gold nanoparticles (AuNPs) in a nematic liquid crystal (LC) are directly detected by nuclear magnetic resonance (NMR) spectroscopy and thermodynamically analyzed. The orientational orders of the selectively deuterated LC matrix and AuNP ligands, each separately followed by variable temperature (2)H NMR as a function of particle concentration, were observed to be strongly correlated. The mechanism of the reversible formation of long-range, quasi-periodic nanoparticle structures is attributed to the coupling of the AuNP ligands to the LC matrix, inducing an isotropic-nematic biphasic state. Experimentally validated thermodynamic modeling shows that, in contrast to colloidal nematics that are dominated by elastic forces, nematic dispersions of nanoparticles self-organize through a subtle balance of entropic forces and excluded volume, interface-mediated mesogen and nanoparticle molecular interactions, and couplings between conserved and nonconserved order parameters. Fine-tuning of these interactions through ligand and mesogen chemistry, together with mesoscale modeling, provides a route for materials innovations by merging structured fluid physics and nanoscience.