Experimental and simulation study of reverse micelles formed by aerosol-OT and water in non-polar solvents.

The formation of reverse micelles by aerosol-OT [sodium bis(2-ethylhexyl) sulfosuccinate] in hydrocarbon solvents, and in the presence of water, is studied using a combination of atomistic molecular-dynamics simulations and small-angle neutron scattering (SANS). There have been many previous studies of aerosol-OT and its self-assembly in both water and non-aqueous solvents, but this work is focused on a combined experimental and simulation study of reverse-micelle formation. The effects of hydration (with water-to-surfactant molar ratios in the range 0-60) and solvent (cyclohexane and -dodecane) are investigated.

Dynamics of magnetization growth and relaxation in ferrofluids.

The dynamics of the growth and relaxation of the magnetization in ferrofluids are determined using theory based on the Fokker-Planck-Brown equation, and Brownian-dynamics simulations. Magnetization growth starting from an equilibrium nonmagnetized state in zero field, and following an instantaneous application of a uniform field of arbitrary strength, is studied with and without interparticle interactions. Similarly, magnetization relaxation is studied starting from an equilibrium magnetized state in a field of arbitrary strength, and following instantaneous removal of the field.

Structure and dynamics in suspensions of magnetic platelets.

In this research, we employ Brownian dynamics simulations, density functional theory, and mean-field theory to explore the profound influence of shape anisotropy of magnetic nanoplatelets on suspension magnetic response. Each platelet is modelled as an oblate cylinder with a longitudinal point dipole, with an emphasis on strong dipolar interactions conducive to self-assembly. We investigate static structural and magnetic properties, characterising the system through pair distribution function, static structure factor, and cluster-size distribution.

Polymeric surfactants at liquid-liquid interfaces: Dependence of structural and thermodynamic properties on copolymer architecture.

Polymeric surfactants are amphiphilic molecules with two or more different types of monomers. If one type of monomer interacts favorably with a liquid, and another type of monomer interacts favorably with another, immiscible liquid, then polymeric surfactants adsorb at the interface between the two liquids and reduce the interfacial tension. The effects of polymer architecture on the structural and thermodynamic properties of the liquid-liquid interface are studied using molecular simulations.

Experimental and simulation study of self-assembly and adsorption of glycerol monooleate in -dodecane with varying water content onto iron oxide.

The self-assembly and surface adsorption of glycerol monooleate (GMO) in -dodecane are studied using a combination of experimental and molecular dynamics simulation techniques. The self-assembly of GMO to form reverse micelles, with and without added water, is studied using small-angle neutron scattering and simulations. A large-scale simulation is also used to investigate the self-assembly kinetics.

Magnetization relaxation dynamics in polydisperse ferrofluids.

When a ferrofluid is magnetized in a strong magnetic field, and then the field is switched off, the magnetization decays from its saturation value to zero. The dynamics of this process are controlled by the rotations of the constituent magnetic nanoparticles, and for the Brownian mechanism, the respective rotation times are strongly influenced by the particle size and the magnetic dipole-dipole interactions between the particles. In this work, the effects of polydispersity and interactions on the magnetic relaxation are studied using a combination of analytical theory and Brownian dynamics simulations.

Measurements of large optical rotary dispersion in the adipose eyelid of Atlantic mackerel ().

Collagen is the most prevalent of Nature's structural proteins, and is found in the extracellular matrices of animals. The structures of collagen molecules and aggregates are chiral, which leads to the rotation of transmitted, plane-polarized light. Here, it is shown that the concentrations of chiral molecules and aggregates in the optically transparent, adipose eyelid of Atlantic mackerel () can be so high, that plane-polarized light in the visible spectrum is rotated by tens to hundreds of degrees, depending on wavelength (the optical rotatory dispersion (ORD)).

Gradient copolymers block copolymers: self-assembly in solution and surface adsorption.

The structures of amphiphilic block and gradient copolymers in solution and adsorbed onto surfaces are surveyed using molecular-dynamics simulations. A bead-spring model is used to identify the general effects of the different architectures: block and gradient copolymers have equal numbers of solvophilic and solvophobic beads, and the gradient copolymer is represented by a linear concentration profile along the chain. Each type of isolated copolymer forms a structure with a globular head of solvophobic beads, and a coil-like tail of solvophilic beads.

How chains and rings affect the dynamic magnetic susceptibility of a highly clustered ferrofluid.

The dynamic magnetic susceptibility, χ(ω), of a model ferrofluid at a very low concentration (volume fraction, approximately 0.05%), and with a range of dipolar coupling constants (1≤λ≤8), is examined using Brownian dynamics simulations. With increasing λ, the structural motifs in the system change from unclustered particles, through chains, to rings.

Influence of size polydispersity on magnetic field tunable structures in magnetic nanofluids containing superparamagnetic nanoparticles.

We probe the influence of particle size polydispersity on field-induced structures and structural transitions in magnetic fluids (ferrofluids) using phase contrast optical microscopy, light scattering and Brownian dynamics simulations. Three different ferrofluids containing superparamagnetic nanoparticles of different polydispersity indices (PDIs) are used. In a ferrofluid with a high PDI (∼0.

Effects of interactions on magnetization relaxation dynamics in ferrofluids.

The dynamics of magnetization relaxation in ferrofluids are studied with statistical-mechanical theory and Brownian dynamics simulations. The particle dipole moments are initially perfectly aligned, and the magnetization is equal to its saturation value. The magnetization is then allowed to decay under zero-field conditions toward its equilibrium value of zero.

Disordered Filaments Mediate the Fibrillogenesis of Type I Collagen in Solution.

Collagen type I is one of the major structural proteins in mammals, providing tissues such as cornea, tendon, bone, skin, and dentin with mechanical stability, strength, and toughness. Collagen fibrils are composed of collagen molecules arranged in a quarter-stagger array that gives rise to a periodicity of 67 nm along the fibril axis, with a 30 nm overlap zone and a 37 nm gap zone. The formation of such highly organized fibrils is a self-assembly process where electrostatic and hydrophobic interactions play a critical role in determining the staggering of the molecules with 67 nm periodicity.

Observation of soft glassy behavior in a magnetic colloid exposed to an external magnetic field.

We provide the first experimental evidence for soft glassy behavior in a sterically stabilized magnetic colloid (ferrofluid) of relatively low volume fraction (φ = 0.037) when a uniform magnetic field is applied at a sufficiently high rate (fast quench). Fast magnetic-field quenches favor structural arrest of field-induced aggregates, owing to insufficient time to settle into lower energy states, thereby pushing the system to a frustrated metastable configuration like a repulsive glass.

Experimental and simulation study of the high-pressure behavior of squalane and poly-α-olefins.

The equation of state, dynamical properties, and molecular-scale structure of squalane and mixtures of poly-α-olefins at room temperature are studied with a combination of state-of-the-art, high-pressure experiments and molecular-dynamics simulations. Diamond-anvil cell experiments indicate that both materials are non-hydrostatic media at pressures above ∼1 GPa. The equation of state does not exhibit any sign of a first-order phase transition.

Static magnetization of immobilized, weakly interacting, superparamagnetic nanoparticles.

The magnetization curve and initial susceptibility of immobilized superparamagnetic nanoparticles are studied using statistical-mechanical theory and Monte Carlo computer simulations. The nanoparticles are considered to be distributed randomly within an implicit solid matrix, but with the easy axes distributed according to particular textures: these are aligned parallel or perpendicular to an external magnetic field, or randomly distributed. The magnetic properties are calculated as functions of the magnetic crystallographic anisotropy barrier (measured with respect to the thermal energy by a parameter σ), and the Langevin susceptibility (related to the dipolar coupling constant and the volume fraction).

Self-assembly and adsorption of cetyltrimethylammonium bromide and didodecyldimethylammonium bromide surfactants at the mica-water interface.

The self-assembly and adsorption of the surfactants cetyltrimethylammonium bromide (CTAB) and didodecyldimethylammonium bromide (DDAB) at the muscovite mica-water interface are studied using molecular-dynamics simulations. Adsorption takes place by an ion-exchange mechanism, in which K+ ions are replaced by the organic alkylammonium cations from the solution. Simulations are performed with and without the surface K+ ions, with pure water, and with the surfactants in aqueous solution.

Interactions between Friction Modifiers and Dispersants in Lubricants: The Case of Glycerol Monooleate and Polyisobutylsuccinimide-Polyamine.

The structural and frictional properties of 10 wt % solutions of the amphiphilic molecules glycerol monooleate (GMO) and polyisobutylsuccinimide-polyamine (PIBSA-PAM) in squalane are studied using molecular dynamics simulations in bulk and under confinement between iron oxide surfaces. GMO is a friction modifier, PIBSA-PAM is a dispersant, and squalane is a good model for typical base oils. A range of liquid compositions and applied pressures is explored, and the formation and stability of reverse micelles are determined under quiescent and shear conditions.

Non-photochemical laser-induced nucleation.

Non-photochemical laser-induced nucleation (NPLIN) is the formation of a new phase from a metastable phase by the action of light on matter. Using millijoule, nanosecond laser pulses at visible and near-infrared wavelengths, it is possible to form the new phase localized in the volume of the beam. In the case of nucleating molecular solids, the laser polarization may have an effect on the particular polymorph that is formed.

Self-assembly and friction of glycerol monooleate and its hydrolysis products in bulk and confined non-aqueous solvents.

Atomistic molecular dynamics simulations are used to study the self-assembly and friction of glycerol monooleate mixed with oleic acid, glycerol, calcium oleate, or water in n-heptane and toluene solvents. The aim is to determine how chemical degradation products of glycerol monooleate could lead to changes in structural and frictional properties. In bulk solution, almost all mixtures studied contain self-assembled reverse micelles.

Modified mean-field theory of the magnetic properties of concentrated, high-susceptibility, polydisperse ferrofluids.

The effects of particle-size polydispersity on the magnetostatic properties of concentrated ferrofluids are studied using theory and computer simulation. The second-order modified mean-field (MMF2) theory of Ivanov and Kuznetsova [Phys. Rev.

Effects of nanoparticle heating on the structure of a concentrated aqueous salt solution.

The effects of a rapidly heated nanoparticle on the structure of a concentrated aqueous salt solution are studied using molecular dynamics simulations. A diamond-like nanoparticle of radius 20 Å is immersed in a sodium-chloride solution at 20% above the experimental saturation concentration and equilibrated at T = 293 K and P = 1 atm. The nanoparticle is then rapidly heated to several thousand degrees Kelvin, and the system is held under isobaric-isoenthalpic conditions.

Molecular Dynamics Simulations of Glycerol Monooleate Confined between Mica Surfaces.

The structure and frictional properties of glycerol monooleate (GMO) in organic solvents, with and without water impurity, confined and sheared between two mica surfaces are examined using molecular dynamics simulations. The structure of the fluid is characterized in various ways, and the differences between systems with nonaggregated GMO and with preformed GMO reverse micelles are examined. Preformed reverse micelles are metastable under static conditions in all systems.

Influence of dipolar interactions on the magnetic susceptibility spectra of ferrofluids.

The frequency-dependent magnetic susceptibility of a ferrofluid is calculated under the assumption that the constituent particles undergo Brownian relaxation only. Brownian-dynamics simulations are carried out in order to test the predictions of a recent theory [A. O.

Sedimentation equilibria in polydisperse ferrofluids: critical comparisons between experiment, theory, and computer simulation.

The sedimentation equilibrium of dipolar particles in a ferrofluid is studied using experiment, theory, and computer simulation. A theory of the particle-concentration profile in a dipolar hard-sphere fluid is developed, based on the local-density approximation and accurate expressions from a recently introduced logarithmic free energy approach. The theory is tested critically against Monte Carlo simulation results for monodisperse and bidisperse dipolar hard-sphere fluids in homogeneous gravitational fields.

Simulations of dipolar fluids using effective many-body isotropic interactions.

The partition function of a system with pairwise-additive anisotropic dipole-dipole interactions is equal to that of a hypothetical system with many-body isotropic interactions [G. Stell, Phys. Rev.