Phase transitions of fluorotelomer alcohols at the water|alkane interface studied via molecular dynamics simulation.

Fluorosurfactants are long-lasting environmental pollutants that accumulate at interfaces ranging from aerosol droplet surfaces to cell membranes. Modeling of adsorption-based removal technologies for fluorosurfactants requires accurate simulation methods which can predict their adsorption isotherm and monolayer structure. Fluorotelomer alcohols with one or two methylene groups adjacent to the alcohol (7 : 1 FTOH and 6 : 2 FTOH, respectively) are investigated using the OPLS-AA force field at the water|hexane interface, varying the interfacial area per surfactant. The acquired interfacial pressure isotherms and monolayer phase behavior are compared with previous experimental results. The results are consistent with the experimental data inasmuch as, at realistic adsorption densities, only 7 : 1 FTOH shows a phase transition between liquid-expanded (LE) and 2D crystalline phases. Structures of the LE and crystalline phases are in good agreement with the sticky disc and Langmuir defective crystal models, respectively, used previously to interpret experimental data. Interfacial pressure of the LE phase agrees well with experiment, and sticky disc interaction parameters indicate no 2D LE-gas transition is present for either molecule. Conformation analysis reveals 7 : 1 FTOH favors conformers where the OH dipole is perpendicular to the molecular backbone, such that the crystalline phase is stabilized when these dipoles align.

Interfacial Layer Breaker: A Violation of Stokes' Law in High-Speed Atomic Force Microscope Flows.

Structured water near surfaces is important in nonclassical crystallization, biomineralization, and restructuring of cellular membranes. In addition to equilibrium structures, studied by atomic force microscopy (AFM), high-speed AFM (H-S AFM) can now detect piconewton forces in microseconds. With increasing speeds and decreasing tip diameters, there is a danger that continuum water models will not hold, and molecular dynamic (MD) simulations would be needed for accurate predictions. MD simulations, however, can only evolve over tens of nanoseconds due to memory and computational efficiency/speed limitations, so new methods are needed to bridge the gap. Here, we report a hybrid, multiscale simulation method, which can bridge the size and time scale gaps to existing experiments. Structured water is studied between a moving silica AFM colloidal tip and a cleaved mica surface. The computational domain includes 1,472,766 atoms. To mimic the effect of long-range hydrodynamic forces occurring in water, when moving the AFM tip at speeds from 5 × 10-7 to 30 m/s, a hybrid multiscale method with local atomistic resolution is used, which serves as an effective open-domain boundary condition. The multiscale simulation is thus equivalent to using a macroscopically large computational domain with equilibrium boundary conditions. Quantification of the drag force shows the breaking of continuum behavior. Nonmonotonic dependence on both the tip speed and distance from the surface implies breaking of the hydration layer around the moving tip at time scales smaller than water cluster formation and strong water compressibility effects at the highest speeds.

Minimum surfactant concentration required for inducing self-shaping of oil droplets and competitive adsorption effects.

Surfactant choice is key in starting the phenomena of artificial morphogenesis, the bottom-up growth of geometric particles from cooled emulsion droplets, as well as the bottom-up self-assembly of rechargeable microswimmer robots from similar droplets. The choice of surfactant is crucial for the formation of a plastic phase at the oil-water interface, for the kinetics, and for the onset temperature of these processes. But further details are needed to control these processes for bottom-up manufacturing and understand their molecular mechanisms. Still unknown are the minimum concentration of the surfactant necessary to induce the processes, or competing effects in a mixture of surfactants when only one is capable of inducing shapes. Here we systematically study the effect of surfactant nature and concentration on the shape-inducing behaviour of hexadecane-in-water emulsions with both cationic (CTAB) and non-ionic (Tween, Brij) surfactants over up to five orders of magnitude of concentration. The minimum effective concentration is found approximately equal to the critical micelle concentration (CMC), or the solubility limit below the Krafft point of the surfactant. However, the emulsions show low stability at the vicinity of CMC. In a mixed surfactant experiment (Tween 60 and Tween 20), where only one (Tween 60) can induce shapes we elucidate the role of competition at the interface during mixed surfactant adsorption by varying the composition. We find that a lower bound of ∼75% surface coverage of the shape-inducing surfactant with C14 or longer chain length is necessary for self-shaping to occur. The resulting technique produces a clear visual readout of otherwise difficult to investigate molecular events. These basic requirements (minimum concentration and % surface coverage to induce oil self-shaping) and the related experimental techniques are expected to guide academic and industrial scientists to formulations with complex surfactant mixtures and behaviour.

Self-shaping of oil droplets via the formation of intermediate rotator phases upon cooling.

Revealing the chemical and physical mechanisms underlying symmetry breaking and shape transformations is key to understanding morphogenesis. If we are to synthesize artificial structures with similar control and complexity to biological systems, we need energy- and material-efficient bottom-up processes to create building blocks of various shapes that can further assemble into hierarchical structures. Lithographic top-down processing allows a high level of structural control in microparticle production but at the expense of limited productivity. Conversely, bottom-up particle syntheses have higher material and energy efficiency, but are more limited in the shapes achievable. Linear hydrocarbons are known to pass through a series of metastable plastic rotator phases before freezing. Here we show that by using appropriate cooling protocols, we can harness these phase transitions to control the deformation of liquid hydrocarbon droplets and then freeze them into solid particles, permanently preserving their shape. Upon cooling, the droplets spontaneously break their shape symmetry several times, morphing through a series of complex regular shapes owing to the internal phase-transition processes. In this way we produce particles including micrometre-sized octahedra, various polygonal platelets, O-shapes, and fibres of submicrometre diameter, which can be selectively frozen into the corresponding solid particles. This mechanism offers insights into achieving complex morphogenesis from a system with a minimal number of molecular components.

Highly Porous Magnetic Janus Microparticles with Asymmetric Surface Topology.

Monodispersed magnetic Janus particles composed of a porous polystyrene portion and a nonporous poly(vinyl acetate) portion with embedded oleic acid-coated magnetic nanoparticles were generated using microfluidic emulsification followed by two distinct phase separation events triggered by solvent evaporation. The template droplets were composed of 2 wt % polystyrene, 2 wt % poly(vinyl acetate), and 0.5-2 wt % n-heptane-based magnetic fluid dissolved in dichloromethane (DCM). The porosity of polystyrene compartments was the result of phase separation between a nonvolatile nonsolvent (n-heptane) and a volatile solvent (DCM) within polystyrene-rich phase. The focused ion beam cross-sectioning and scanning electron microscopy (SEM) imaging revealed high surface porosity of polystyrene compartments with negligible porosity of poly(vinyl acetate) parts, which can be exploited to increase the wettability contrast between the two polymers and enhance bubble generation in bubble-driven micromotors. The porosity of the polystyrene portion was controlled by varying the fraction of n-heptane in the dispersed phase. The particle composition was confirmed by scanning electron microscopy-energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, and differential scanning calorimetry. The fabricated particles were successfully magnetized when subjected to an external magnetic field, which led to their aggregation into regular 2D assemblies. The particle clusters composed of two to four individual particles could be rotated with a rotating magnetic field. Microfluidic generation of highly porous Janus particles with compositional, topological, and magnetic asymmetry provides a cost-effective, easy-to-implement yet highly robust and versatile strategy for the manufacturing of multifunctional smart particles.

Multilayer Formation in Self-Shaping Emulsion Droplets.

In several recent studies, we showed that micrometer-sized oil-in-water emulsion droplets from alkanes, alkenes, alcohols, triglycerides, or mixtures of these components can spontaneously "self-shape" upon cooling into various regular shapes, such as regular polyhedrons, platelets, rods, and fibers ( Denkov , N. , Nature 2015 , 528 , 392 ; Cholakova , D. , Adv. Colloid Interface Sci. 2016 , 235 , 90 ). These drop-shape transformations were explained by assuming that intermediate plastic rotator phase, composed of ordered multilayers of oily molecules, is formed beneath the drop surface around the oil-freezing temperature. An alternative explanation was proposed ( Guttman , S. , Proc. Natl. Acad. Sci. USA 2016 113 , 493 ; Guttman , S. , Langmuir 2017 , 33 , 1305 ), which is based on the assumption that the oil-water interfacial tension decreases to very low values upon emulsion cooling. Here, we present new results, obtained by differential scanning calorimetry (DSC), which quantify the enthalpy effects accompanying the drop-shape transformations. Using optical microscopy, we related the peaks in the DSC thermograms to the specific changes in the drop shape. Furthermore, from the enthalpies measured by DSC, we determined the fraction of the intermediate phase involved in the processes of drop deformation. The obtained results support the explanation that the drop-shape transformations are intimately related to the formation of ordered multilayers of alkane molecules with thickness varying between several and dozens of layers of alkane molecules, depending on the specific system. The new results provide the basis for a rational approach to the mechanistic explanation and to the fine control of this fascinating and industrially relevant phenomenon.

Light-induced actuating nanotransducers.

Nanoactuators and nanomachines have long been sought after, but key bottlenecks remain. Forces at submicrometer scales are weak and slow, control is hard to achieve, and power cannot be reliably supplied. Despite the increasing complexity of nanodevices such as DNA origami and molecular machines, rapid mechanical operations are not yet possible. Here, we bind temperature-responsive polymers to charged Au nanoparticles, storing elastic energy that can be rapidly released under light control for repeatable isotropic nanoactuation. Optically heating above a critical temperature [Formula: see text] = 32 °C using plasmonic absorption of an incident laser causes the coatings to expel water and collapse within a microsecond to the nanoscale, millions of times faster than the base polymer. This triggers a controllable number of nanoparticles to tightly bind in clusters. Surprisingly, by cooling below [Formula: see text] their strong van der Waals attraction is overcome as the polymer expands, exerting nanoscale forces of several nN. This large force depends on van der Waals attractions between Au cores being very large in the collapsed polymer state, setting up a tightly compressed polymer spring which can be triggered into the inflated state. Our insights lead toward rational design of diverse colloidal nanomachines.

Bottom-up Formation of Carbon-Based Structures with Multilevel Hierarchy from MOF-Guest Polyhedra.

Three-dimensional carbon-based structures have proven useful for tailoring material properties in structural mechanical and energy storage applications. One approach to obtain them has been by carbonization of selected metal-organic frameworks (MOFs) with catalytic metals, but this is not applicable to most common MOF structures. Here, we present a strategy to transform common MOFs, by guest inclusions and high-temperature MOF-guest interactions, into complex carbon-based, diatom-like, hierarchical structures (named for the morphological similarities with the naturally existing diatomaceous species). As an example, we introduce metal salt guests into HKUST-1-type MOFs to generate a family of carbon-based nano-diatoms with two to four levels of structural hierarchy. We report control of the morphology by simple changes in the chemistry of the MOF and guest, with implications for the formation mechanisms. We demonstrate that one of these structures has unique advantages as a fast-charging lithium-ion battery anode. The tunability of composition should enable further studies of reaction mechanisms and result in the growth of a myriad of unprecedented carbon-based structures from the enormous variety of currently available MOF-guest candidates.

Tuning of Structural Colors Like a Chameleon Enabled by Shape-Memory Polymers.

Nature often uses structuring of materials for coloration rather than incorporating dye molecules, since single-construction materials are capable of producing any vivid visible color in plants and insects. By precisely engineering features that diffract or scatter light, more recently, humans have created similarly intense non-fading colors. Stretchable polymer opals have emerged as a single material which can dynamically shift across the whole visible spectrum using structural colors, by temporary stretching or compression. For energy efficiency and practical considerations, however, it is necessary to fix semi-permanently desired colors without continuous stretching or application of other stimuli or energy. Here, a polymer opal incorporating a shape-memory polymer embedded in its matrix can keep a particular color fixed without the application of external forces, yet can be reprogrammed to a different fixed color on demand. The influence of the material composition on its optical appearance, shape-fixity, and shape recovery abilities in controlled stretch experiments is quantified. High-speed printing-compatible localized compression pattern imprinting is shown to generate stable but easily erasable color patterns. This opens up the potential for durable and energy-efficient yet reusable and reconfigurable displays, wearables, or packaging and security labeling based on such polymeric film materials.

Theory of Shape-Shifting Droplets.

Recent studies of cooled oil emulsion droplets uncovered transformations into a host of flattened shapes with straight edges and sharp corners, driven by a partial phase transition of the bulk liquid phase. Here, we explore theoretically the simplest geometric competition between this phase transition and surface tension in planar polygons and recover the observed sequence of shapes and their statistics in qualitative agreement with experiments. Extending the model to capture some of the three-dimensional structure of the droplets, we analyze the evolution of protrusions sprouting from the vertices of the platelets and the topological transition of a puncturing planar polygon.

Mechanisms and Control of Self-Emulsification upon Freezing and Melting of Dispersed Alkane Drops.

Emulsification requires drop breakage and creation of a large interfacial area between immiscible liquid phases. Usually, high-shear or high-pressure emulsification devices that generate heat and increase the emulsion temperature are used to obtain emulsions with micrometer and submicrometer droplets. Recently, we reported a new, efficient procedure of self-emulsification (Tcholakova et al. Nat. Commun. 2017, 8, 15012), which consists of one to several cycles of freezing and melting of predispersed alkane drops in a coarse oil-in-water emulsion. Within these freeze-thaw cycles of the dispersed drops, the latter burst spontaneously into hundreds and thousands of smaller droplets without using any mechanical agitation. Here, we clarify the main factors and mechanisms, which drive this self-emulsification process, by exploring systematically the effects of the oil and surfactant types, the cooling rate, and the initial drop size. We show that the typical size of the droplets, generated by this method, is controlled by the size of the structural domains formed in the cooling-freezing stage of the procedure. Depending on the leading mechanism, these could be the diameter of the fibers formed upon drop self-shaping or the size of the crystal domains formed at the moment of drop-freezing. Generally, surfactant tails that are 0-2 carbon atoms longer than the oil molecules are most appropriate to observe efficient self-emulsification. The specific requirements for the realization of different mechanisms are clarified and discussed. The relative efficiencies of the three different mechanisms, as a function of the droplet size and cooling procedure, are compared in controlled experiments to provide guidance for understanding and further optimization and scale-up of this self-emulsification process.

"Self-Shaping" of Multicomponent Drops.

In our recent study we showed that single-component emulsion drops, stabilized by proper surfactants, can spontaneously break symmetry and transform into various polygonal shapes during cooling [ Denkov Nature 2015 , 528 , 392 - 395 ]. This process involves the formation of a plastic rotator phase of self-assembled oil molecules beneath the drop surface. The plastic phase spontaneously forms a frame of plastic rods at the oil drop perimeter which supports the polygonal shapes. However, most of the common substances used in industry appear as mixtures of molecules rather than pure substances. Here we present a systematic study of the ability of multicomponent emulsion drops to deform upon cooling. The observed trends can be summarized as follows: (1) The general drop-shape evolution for multicomponent drops during cooling is the same as with single-component drops; however, some additional shapes are observed. (2) Preservation of the particle shape upon freezing is possible for alkane mixtures with chain length difference Δn ≤ 4; for greater Δn, phase separation within the droplet is observed. (3) Multicomponent particles prepared from alkanes with Δn ≤ 4 plastify upon cooling due to the formation of a bulk rotator phase within the particles. (4) If a compound, which cannot induce self-shaping when pure, is mixed with a certain amount of a compound which induces self-shaping, then drops prepared from this mixture can also self-shape upon cooling. (5) Self-emulsification phenomena are also observed for multicomponent drops. In addition to the three recently reported mechanisms of self-emulsification [ Tcholakova Nat. Commun. 2017 , ( 8 ), 15012 ], a new (fourth) mechanism is observed upon freezing for alkane mixtures with Δn > 4. It involves disintegration of the particles due to a phase separation of alkanes upon freezing.

On the Mechanism of Drop Self-Shaping in Cooled Emulsions.

Two recent studies (Denkov et al., Nature 2015, 528, 392 and Guttman et al. Proc. Natl. Acad. Sci. U.S.A.2016, 113, 493) demonstrated that micrometer-sized n-alkane drops, dispersed in aqueous surfactant solutions, can break their spherical symmetry upon cooling and self-shape into a variety of regular shapes, such as fluid polyhedra, platelet-shaped hexagons, triangles, rhomboids, toroids, and submicrometer-diameter fibers. In the first study, the observed phenomenon was explained by a mechanism involving the formation of interfacial multilayer of self-assembled alkane molecules in the so-called rotator phases, templated by the frozen surfactant adsorption layer. Such phases are known to form in alkane droplets under similar conditions and are sufficiently strong to deform the droplets against the capillary pressure of a finite interfacial tension of several mN/m. The authors of the second study proposed a different explanation, namely, that the oil-water interfacial tension becomes ultralow upon cooling, which allows for surface extension and drop deformation at negligible energy penalty. To reveal which of these mechanisms is operative, we measure in the current study the temperature dependence of the interfacial tensions of several systems undergoing such drop-shape transitions. Our results unambiguously show that drop self-shaping is not related to ultralow oil-water interfacial tension, as proposed by Guttmann et al. These results support the mechanism proposed by Denkov et al., which implies that the large bending moment, required to deform an oil-water interface with an interfacial tension of 5 to 10 mN/m, is generated by an interfacial multilayer of self-assembled alkane molecules.

A 3-dimensional fibre scaffold as an investigative tool for studying the morphogenesis of isolated plant pells.

BACKGROUND: Cell culture methods allow the detailed observations of individual plant cells and their internal processes. Whereas cultured cells are more amenable to microscopy, they have had limited use when studying the complex interactions between cell populations and responses to external signals associated with tissue and whole plant development. Such interactions result in the diverse range of cell shapes observed in planta compared to the simple polygonal or ovoid shapes in vitro. Microfluidic devices can isolate the dynamics of single plant cells but have restricted use for providing a tissue-like and fibrous extracellular environment for cells to interact. A gap exists, therefore, in the understanding of spatiotemporal interactions of single plant cells interacting with their three-dimensional (3D) environment. A model system is needed to bridge this gap. For this purpose we have borrowed a tool, a 3D nano- and microfibre tissue scaffold, recently used in biomedical engineering of animal and human tissue physiology and pathophysiology in vitro. RESULTS: We have developed a method of 3D cell culture for plants, which mimics the plant tissue environment, using biocompatible scaffolds similar to those used in mammalian tissue engineering. The scaffolds provide both developmental cues and structural stability to isolated callus-derived cells grown in liquid culture. The protocol is rapid, compared to the growth and preparation of whole plants for microscopy, and provides detailed subcellular information on cells interacting with their local environment. We observe cell shapes never observed for individual cultured cells. Rather than exhibiting only spheroid or ellipsoidal shapes, the cells adapt their shape to fit the local space and are capable of growing past each other, taking on growth and morphological characteristics with greater complexity than observed even in whole plants. Confocal imaging of transgenic Arabidopsis thaliana lines containing fluorescent microtubule and actin reporters enables further study of the effects of interactions and complex morphologies upon cytoskeletal organisation both in 3D and in time (4D). CONCLUSIONS: The 3D culture within the fibre scaffolds permits cells to grow freely within a matrix containing both large and small spaces, a technique that is expected to add to current lithographic technologies, where growth is carefully controlled and constricted. The cells, once seeded in the scaffolds, can adopt a variety of morphologies, demonstrating that they do not need to be part of a tightly packed tissue to form complex shapes. This points to a role of the immediate nano- and micro-topography in plant cell morphogenesis. This work defines a new suite of techniques for exploring cell-environment interactions.

Anisotropic colloidal micromuscles from liquid crystal elastomers.

Monodomain liquid crystal elastomers (LCEs) are new materials uniquely suitable for artificial muscles, as they undergo large reversible uniaxial shape changes, with strains of 20-500% and stresses of 10-100 kPa, falling exactly into the dynamic range of a muscle. LCEs exhibit little to no fatigue over thousands of actuation cycles. Their practical use has been limited, however, owing to the difficulty of synthesizing components, achieving consistent alignment during cross-linking across the whole material and often a high nematic-isotropic phase transition temperature. The most widely studied method for LC alignment involves mechanical stretching of the material during one of two cross-linking steps, which makes fabrication difficult to control and lends itself mainly to samples that can be easily grasped (with sizes of the order of mm). In this article, we describe a method of adapting the LCE synthesis to microscale objects, achieving monodomain alignment with a single cross-linking step, and lowering the cycling temperature. LCE precursor droplets are embedded in and then stretched in a polymer matrix at high temperature. Confinement of the uniaxially stretched droplets maintains the alignment achieved during stretching and allows us to eliminate one of the cross-linking steps and the variability associated with it. Adding a comonomer during the polymerization leads to lowering of the nematic-to-isotropic transition temperature (58 °C), significantly expanding the range of potential applications for these micromuscles. We demonstrate reversible thermal switching of the micromuscles in line with the largest strain changes observed for side-chain LCEs and a differential scanning calorimetry characterization of the material phase transitions. The method demonstrates the parallel fabrication of many microscale actuators and is amenable to further scale-up and manufacturing.

Stability and viscoelasticity of magneto-Pickering foams.

We have developed a new class of bistable Pickering foams, which can remain intact for weeks at room temperature but can be destroyed rapidly and on-demand with the use of a magnetic field. Such responsive foam systems can find application in various industrial and environmental processes that require controlled defoaming. These foams are stabilized by particles of hypromellose phthalate (HP-55) and contain oleic acid-coated carbonyl iron particles embedded in the HP-55 matrix. The complex behavior of these foams arises from several factors: a robust anisotropic particle matrix, the capacity to retain a high amount of water, as well as an age-dependent response to an external field. We report how the structure and viscoelastic properties of the foams change with time and affect their collapse characteristics. The evolution of foam properties is quantified by measuring the rate of liquid drainage from the foam as well as the rate of bubble growth in the foam with respect to time elapsed (in the absence of a magnetic field). We also evaluate the time necessary for foam collapse in magnetic fields as a function of magnetic particle content. A decreasing liquid volume fraction in the foam during aging leads to an increase in the elasticity and rigidity of the foam structure. These data allow us to identify a transition time separating two distinct stages of foam development in the absence of field. We propose different mechanisms which control foam collapse for each stage in a magnetic field. The stiffening of foam films between air bubbles with age plays a key role in distinguishing between the two destabilization regimes.

Extension of the TraPPE Force Field for Battery Electrolyte Solvents.

Optimizing electrolyte formulations is key to improving performance of Li-/Na-ion batteries, where transport properties (diffusion coefficient, viscosity) and permittivity need to be predicted as functions of temperature, salt concentration and solvent composition. More efficient and reliable simulation models are urgently needed, owing to the high cost of experimental methods and the lack of united-atom molecular dynamics force fields validated for electrolyte solvents. Here the computationally efficient TraPPE united-atom force field is extended to be compatible with carbonate solvents, optimizing the charges and dihedral potential. Computing the properties of electrolyte solvents, ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and dimethoxyethane (DME), we observe that the average absolute errors in the density, self-diffusion coefficient, permittivity, viscosity, and surface tension are approximately 15% of the corresponding experimental values. Results compare favorably to all-atom CHARMM and OPLS-AA force fields, offering computational performance improvement of at least 80%. We further use TraPPE to predict the structure and properties of LiPF6 salt in these solvents and their mixtures. EC and PC form complete solvation shells around Li+ ions, while the salt in DMC forms chain-like structures. In the poorest solvent, DME, LiPF6 forms globular clusters despite DME's higher permittivity than DMC.

Measuring the Adsorption of Electrolytes on Lipid Monolayers.

The interactions between ions and lipid monolayers have captivated the attention of biologists and chemists alike for almost a century. In the absence of experimentally accessible concentration profiles, the electrolyte adsorption remains the most informative quantitative characteristic of the ion-lipid interactions. However, there is no established procedure to obtain the electrolyte adsorption on spread lipid monolayers. As a result, in the literature, the ion-lipid monolayer interactions are discussed qualitatively, based on the electrolyte effect on more easily accessible variables, e.g., surface tension. In this letter, we demonstrate how the electrolyte adsorption on lipid monolayers can be obtained experimentally. The procedure requires combining surface pressure versus molecular area compression isotherms with spreading pressure data. For the first time, we report an adsorption isotherm of NaCl on a lipid monolayer as a function of the density of the monolayer. The leading interactions seem to be the osmotic effect from the lipid head groups in the surface layer and ion-lipid association.

Structure of the Hexadecane Rotator Phase: Combination of X-ray Spectra and Molecular Dynamics Simulation.

Rotator phases are rotationally disordered plastic crystals, some of which can form upon freezing of alkane at alkane-water interfaces. Existing X-ray diffraction studies show only partial unit cell information for rotator phases of some alkanes. This includes the rotator phase of n-hexadecane, which is a transient metastable phase in pure alkane systems, but shows remarkable stability at interfaces when mediated by a surfactant. Here, we combine synchrotron X-ray diffraction data and molecular dynamics (MD) simulations, reporting clear evidence of the face-centered orthorhombic RI rotator phase from spectra for two hexadecane emulsions, one stabilized by Brij C10 and another by Tween 40 surfactants. MD simulations of pure hexadecane use the recently developed Williams 7B force field, which is capable of reproducing crystal-to-rotator phase transitions, and it also predicts the crystal structure of the RI phase. Full unit cell information is obtained by combining unit cell dimensions from synchrotron data and molecular orientations from MD simulations. A unit cell model of the RI phase is produced in the crystallographic information file (CIF) format, with each molecule represented by a superposition of four rotational positions, each with 25% occupancy. Powder diffraction spectra computed using this model are in good agreement with the experimental spectra.