Probing the Interior of Self-Assembled Caffeine Dimer at Various Temperatures

The self-assembly of non-toxic well-consumed small caffeine molecules into well-defined structures has important implications for future medical applications seeking to target the transport of small drugs in human body. Particularly, the solvation of the microenvironments of the self assembly ultimately dictates the interaction with the drug molecules and their therapeutic efficacy. We present femtosecond-resolved studies of the dynamics of aqueous solvation within self-assembled dimeric structure of caffeine molecules. We have placed small hydrophobic probes 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl) 4H-pyran (DCM), coumarin 500 (C500) into the caffeine dimer to enable spectroscopic examinations of the interior. While molecular modeling and NMR studies of the probes in the caffeine dimers reveal a well-defined location (stacked in between two caffeine molecules), dynamical light scattering (DLS), Fourier transform infrared (FTIR) spectroscopy, densimetric and sonometric experiments explore the structural evolution of the dimer upon complexation with the probes. We have extended our studies in various temperatures in order to explore structural evolution of the self assembled structure and consequently the dynamics of solvation in the interior of the dimer. Picoseconds/femtosecond resolved dynamics and the polarization gated spectroscopic studies unravel the hydration and energetics associated with activated viscous flow of the confined probes. Our studies indicate that the interior of the caffeine dimer is well-solvated; however, the dynamics of solvation is retarted significantly compared to that in bulk water, clearly revealing the dimers maintain some ordered water molecules. We have also explored the consequence of the retarded dynamics of solvation on the photo-induced electron transfer (ET) reaction of a model probe, 2-(p-toluidino) naphthalene-6-sulfonate (TNS) encapsulated in the dimer.     

Nonlinearities in tilt and layer displacements of planar lipid bilayers

A novel continuum model is proposed to describe the deformations of a planar lipid bilayer suspended across a circular pore. The model is derived within a new theoretical framework for smectic A liquid crystals in which the usual director n , which defines the average orientation of the molecules, is not constrained to be normal to the layers. The free energy is defined by considering the elastic splay of the director, the bending and compression of the lipid bilayer, the cost of tilting the director with respect to the layer normal, the surface tension, and the weak anchoring of the director. Variational methods are used to derive the equilibrium equations and boundary conditions. The resulting boundary value problem is then solved numerically to compute the fully nonlinear displacement of the layers and tilt of the lipid molecules. A parametric study shows that an increase in surface tension produces a decrease in the deformation of the lipid bilayers while an opposite effect is obtained when increasing the anchoring strength.     

Branching of colloidal chains in capillary-confined nematics

We report on the observation of colloidal chain assembly and branching inside capillaries filled with a nematic liquid crystal. Because of the homeotropic anchoring of liquid crystalline molecules on the capillary and colloidal droplet surfaces, the assembly of droplets along the capillary axis is expected, producing a transformation of the nematic director field from an escape-radial to quasiradial configuration. However, the subsequent over time branching of the straight colloidal chains is counterintuitive. By numerical simulations, we demonstrate that chain branching can occur by overcoming an energy barrier and can at least dwell as a metastable configuration. Moreover, manipulation of colloidal chains by electric fields and their gradients demonstrates various regimes of chain behavior in electric fields.     

Orientational dynamics in nematic liquid crystals

We examine the behaviour of single-particle orientational time correlation functions in nematic liquid crystals. As well as the expected dynamics involving oscillation in a mean-field potential, and occasional jumps between orientations parallel and antiparallel to the director, we provide the first simulation evidence of long-time tails characteristic of coupling to director fluctuations.     

The holographic investigation of diffusion of azo-dye in liquid crystals host

The diffusion of azo-dye (DR-1) in a planar liquid crystals host (5CB) at various temperatures has been investigated by laser-induced holographic grating relaxation technique. The decay of the diffraction intensity provides information about the diffusion of photoexcited azo-dye molecules. The relaxation time constants can be derived from the time dependence of the diffraction intensity fitted by a single exponential function. Thus, the diffusion coefficients parallel and perpendicular to the director of liquid crystals at various temperatures can be obtained from the plots of the reciprocal of the relaxation time versus the square of the grating vector. From the analysis of the holographic grating relaxation, the diffusion is faster along the molecular director than for the perpendicular case, and the diffusion increases with rising temperature either parallel or perpendicular to the nematic director of liquid crystals. PACS 42.40.Eq; 42.40.Lx     

Transport properties of cholesteric liquid crystals studied by molecular dynamics simulation

We have studied the transport properties of a cholesteric liquid crystal by molecular dynamics simulation. The molecules consist of six soft ellipsoids of revolution, the axes of which are perpendicular to the line connecting their centres of symmetry. The angle between the symmetry axes of two adjacent ellipsoids is 7.5°, so the molecules are twisted. At high densities they form a cholesteric phase where their twist axes are oriented around the cholesteric axis and the symmetry axes of the ellipsoids are approximately parallel to the local director. We have been particularly interested in thermomechanical coupling or the Lehmann effect, which arises when a temperature gradient parallel to the cholesteric axis induces a torque that rotates the director. The converse is also possible: rotation of the director can drive a heat current. The thermal conductivity, the twist viscosity, the cross-coupling coefficient between the temperature gradient and the torque, and the cross-coupling coefficient between the director angular velocity and the heat current have been calculated by non-equilibrium molecular dynamics simulation methods (NEMD) and by evaluation of the Green-Kubo relations from equilibrium simulations. Two ensembles have been utilized: the ordinary canonical ensemble and another ensemble where the director angular velocity is constrained to be a constant of motion. All the methods give consistent results for the twist viscosity and the thermal conductivity. The NEMD estimates of the cross-coupling coefficients agree within a relative error of 20%. This is consistent with the Onsager reciprocity relations that state that the two cross-coupling coefficients should be equal. The relative error of the Green-Kubo estimates is about 100% even though the order of magnitude is the same as that of the NEMD estimates.     

Solvation force in hard ellipsoid fluids with HNW interaction

In present work, using density functional theory and extended restricted orientation model, the one particle density of hard Gaussian overlap fluid near the colloid walls is calculated. The hard needle–wall interaction between molecules and colloids are considered. Using non-linear equation, proposed by Grimson–Rickyazen, the solvation force of hard ellipsoidal molecular fluid with hard Gaussian overlap interaction is calculated. We could not find the exact or simulation results for comparison. The results in the case k = 2.0 are compared with the solvation force of one-dimensional hard rod fluids. The results are corresponded, qualitatively.     

Rotational reorientation of the director in twisted nematic liquid-crystal cells

The orientational relaxation of the director to its equilibrium orientation under electric, elastic, and viscous torques arising in twisted nematic liquid-crystal cells is investigated. It is shown that the relaxation time of the director depends strongly on the external electric field strength and weakly on the energy of anchoring of liquid-crystal molecules to the surfaces of the cell. The relaxation time of the director anomalously increases in electric fields close to the Fréedericksz threshold. It is established that, at specific strengths of the external electric field, the relaxation can occur in the form of traveling waves propagating from one edge to the other edge of the twisted nematic liquid-crystal cell. The calculations of the relaxation processes in the vicinity of the nematic-smectic A phase transition temperature demonstrate that the distortion of the director field is uniform over the entire cross section of the liquid-crystal cell and does not depend on the strength of anchoring of the liquid-crystal molecules to the surfaces of the cell.     

Nonlinear molecular deformations and solitons in a nematic liquid crystal

We studied nonlinear molecular deformations in a nematic liquid crystal with homeotropically aligned molecules and hard boundaries. As the basic dynamical equation for the director axis of the liquid crystal resembles the Landau-Lifshitz equation representing spin dynamics in a one dimensional classical continuum isotropic Heisenberg ferromagnetic spin chain, we invoke here the space curve formalism and the stereographic projection technique used in the case of the Heisenberg spin chain. Under space curve mapping, the director dynamics with elastic deformation is found to be governed by a perturbed nonlinear Schrödinger equation. A multiple-scale perturbation analysis brings out perturbed solitons to represent molecular deformations in the nematic liquid crystal. However, when a constant electric field is applied, the director dynamics is expressed under stereographic projection and the molecular deformations are found to be governed by periodic and localized static planar director configurations. A linear stability analysis on the static planar configurations shows that the system exhibits stable deformations.     

Nanoscale molecular superfluidity of hydrogen

We present a microscopic quantum theoretical analysis of the nanoscale superfluid properties of solvating clusters of para-H2 around the linear OCS molecule. Path-integral calculations with N=17 para-H2 molecules, constituting a full solvation shell, show the appearance of a significant superfluid response to rotation around the molecular axis at T=0.15 K. This low-temperature superfluid response is highly anisotropic and drops sharply as the temperature increases to T approximately 0.3 K. These calculations provide definitive theoretical evidence that an anisotropic superfluid state exists for molecular hydrogen in this microscopic solvation layer.     

Surface reorientation induced by short light pulses in doped liquid crystals

Fast surface reorientation induced by a single 4-ns low-energy laser pulse in dye-doped liquid crystals is reported. The reorientation is due to light-induced modification of the surface anisotropy, which affects the liquid crystal's director through the appearance of a preferred direction on the irradiated surface. The detected signals can be interpreted as being the result of light-induced desorption and adsorption of dye molecules.     

First-principles molecular-dynamics simulations of a hydrated electron in normal and supercritical water

A first principles study of a hydrated electron in water at ordinary and supercritical conditions is presented. In the first case, the electron cleaves a cavity in the hydrogen bond network in which six H2O molecules form the solvation shell. The electron distribution assumes an ellipsoidal shape, and the agreement of the computed and the experimental optical absorption seems to support this picture. At supercritical conditions, instead, the H-bond network is not continuous and allows us to predict that the electron localizes in preexisting cavities in a more isotropic way. Four water molecules form the solvation shell but the localization time shortens significantly.     

Nematic order in nanoscopic liquid crystal droplets

We have used atomistic molecular-dynamics simulations to model the detailed molecular configuration of 5CB (4-n-pentyl-4'-cyanobiphenyl) molecules in the form of a nanoscopic liquid crystal droplet in a vacuum microgravity environment. We find the equilibrium state of droplets consisting of as few as 26 or 50 molecules to exhibit significant nematic ordering. The shape of the droplets is also anisotropic, but there is little angular correlation between the nematic director and the long axis of the droplet. Some tendency to micelle formation is observed in droplets of 50 molecules.     

Generalising the mean spherical approximation as a multiscale,nonlinear boundary condition at the solute–solvent interface

ABSTRACT

In this paper, we extend the familiar continuum electrostatic model to incorporate finite-size effects in the solvation layer, by perturbing the usual macroscopic interface condition. The perturbation is based on the mean spherical approximation (MSA), to derive a multiscale solvation-layer interface condition (SLIC/MSA). We show that SLIC/MSA reproduces MSA predictions for Born ions in a variety of polar solvents, including water as well as other protic and aprotic solvents. Importantly, the SLIC/MSA model predicts not only solvation free energies accurately but also solvation entropies, which standard continuum electrostatic models fail to predict. The SLIC/MSA model depends only on the normal electric field at the dielectric boundary, similar to our recent development of a SLIC model for charge-sign hydration asymmetry, and the reformulation of the MSA as an effective boundary condition enables its straightforward application to complex molecules such as proteins, whereas traditionally it is primarily a bulk theory. This work also opens the possibility for other electrolyte models to be incorporated into fast implicit-solvent models of biomolecular electrostatics.     

Mechanistic models of the ion-solvation shell system

The eigenfrequencies of solvation shell oscillations with respect to the ion are estimated in various approximations describing the ion–solvation shell system. The results of comparisonwith experiments suggest that the most appropriate is the model in which the solvated ion is considered to be a spherical rotator formed either by the entire solvation shell or by a layer of solvent molecules adjacent to the outer boundary of the solvation shell.     

Cracks and topological defects in lyotropic nematic gels

We report on the effects of the coupling of nematic order and elasticity in anisotropic lyotropic gels consisting of large nematic domains of surfactant coated single wall carbon nanotubes embedded in a cross-linked N-isopropyl acrylamide polymer matrix. We observe the following striking features: (i) undulations and then cusping of the gel sidewalls, (ii) a nematic director field that evolves as the gel sidewalls deform, (iii) networks of surface cracks that are orthogonal to the nematic director field, and (iv) fissures at the sidewall cusps and associated topological defects that would not form in liquid nematics.     

Does salting-out effect nucleate nanobubbles in water: Spontaneous nucleation?

The solubility of gases in aqueous salt solution decreases with the salt concentration, often termed the “salting-out effect.” The dissolution of salt in water is followed by dissociation of salt and further solvation of ions with water molecules. The solvation weakens the affinity of gaseous molecules, and thus it releases the excess dissolved gas. Now it is interesting to know that what happens to the excess gas released during salting-out? Since it is imperative to note that the transfer of the dissolved gas in the bulk liquid may often occur in the form of nanobubbles. In this work, we have answered this question by investigating the nano-entities nucleation during the salting-out effect. The solubility of gases in aqueous salt solution decreases with the salt concentration, and it is often termed as the “salting-out effects.” The dissolution of salt in water undergoes dissociation of salt and further solvation of ions with water molecules. The solvation weakens the affinity of gaseous molecules, and thus it releases the excess dissolved gas. Now it is interesting to know that what happens to the excess gas released during salting-out? While it is also imperative to note that the gas transfer in the bulk liquid often occurs in the form of bubbles. With this hypothesis, we have experimentally investigated that whether the salting-out effect nucleates nanobubble or not. What is the strong scientific evidence to prove that they are nanobubbles? Does the salting-out parameter affect the number density? The answers to such questions are essential for the fundamental understanding of the origin and driving force for nanobubble generation. We have provided three distinct proofs for the nano-entities to be the nanobubbles, namely, (1) by freezing and thawing experiments, (2) by destroying the nanobubbles under ultrasound field, and (3) we also proposed a novel method for refractive index estimation of nanobubbles to differentiate them from nano drops and nanoparticles. The refractive index (RI) of nanobubbles was estimated to be 1.012 for mono- and di-valent salts and 1.305 for trivalent salt. The value of RI closer to 1 provides strong evidence of gas-filled nanobubbles. Both positive and negative charged nanobubbles nucleate during the salting-out effect depending upon the valency of salt. The nanobubbles during the salting-out effect are stable only for up to three days. This shorter stability could plausibly be due to reduced colloidal stability at a low surface charge.     

Size and shape effects on the orientation of solutes in nematic liquid crystals

A new model is introduced to describe the ordering of solute molecules in nematic liquid crystals where the average electric field gradient experienced by the solute is zero. For such cases the average orientation of the solute correlates with its size and shape. We assume a mean-field potential that depends on the length of the projection of the solute onto the axis parallel to the director and the circumference of the projection onto the plane perpendicular to the director. The model is used to fit the experimental values of the order parameters of a variety of rigid molecules having different symmetries. Very good fits for the order parameters of 1CB and the quadrupolar coupling of 5CB were obtained using the same set of parameters used to fit the rigid solutes. This shows that the contribution to orientational order from size and shape effects can be calculated from a potential with solute-independent parameters.     

Correlations among hydrogen bonds in liquid water

By performing computer simulations of water with the TIP5P potential we show that structures formed by two or more hydrogen bonds affect the dynamical and static properties of water, especially in the vicinity of freezing temperature. In particular, the short time correlation between two coupled hydrogen bonds cannot be predicted assuming the statistical independence of the single hydrogen bonds. This introduces an additional relaxation time of approximately 9 ps close to the freezing point. We also find that the time persistence of structures formed by several hydrogen bonds (the first solvation shell) correlates with the local density, which is smaller around water molecules with a long-living environment.     

Critical voltages and blocking stresses in nematic gels

We present a model of the dynamics of director rotation in nematic gels under combined electro-mechanical loading. Focusing on a model specimen, we describe the critical voltages that must be exceeded to achieve director reorientation, and the blocking stresses that prevent alignment of the nematic director with the applied electric field. The corresponding phase diagram shows that the dynamic thresholds defined above are different from those predicted on the sole basis of energetics. Multistep loading programs are used to explore the energy landscape of our model specimen, showing the existence of multiple local minima under the same voltage and applied stress. This leads us to conclude that hysteresis should be expected in the electro-mechanical response of nematic gels.