More room for microphase separation: An extended study on binary liquids confined in SBA-15 cylindrical pores.

The confinement of liquid mixtures in porous channels provides new insight into fluid ordering at the nanoscale. In this study, we address a phenomenon of microphase separation, which appears as a novel fascinating confinement effect for fully miscible binary liquids. We investigate the structure of tert-butanol-toluene mixtures confined in the straight and mono-dispersed cylindrical nanochannels of SBA-15 mesoporous silicates (D = 8.3 nm). Small angle neutron scattering experiments on samples with carefully designed isotopic compositions are performed to systematically vary the scattering length density of the different compounds and assess the radial concentration profile of the confined phases. The resulting modulation of the Bragg reflections of SBA-15 is compared with the predictions from different core-shell models, highlighting a molecular-scale phase-separated tubular structure with the tert-butanol forming a layer at the pore surface, surrounding a toluene-rich core. The present structural study suggests that the microphase separation phenomenon in confinement, which so far had only been reported for a smaller pore size (D = 3.65 nm) and a unique mixture composition, must be considered as a general phenomenon. It also highlights the strength of neutron scattering method with isotopic substitution, which is a unique experimental approach to reveal this phenomenon.

Thermodynamics of binary gas adsorption in nanopores.

MCM-41 nanoporous silicas show a very high selectivity for monoalcohols over aprotic molecules during adsorption of a binary mixture in the gas phase. We present here an original use of gravimetric vapour sorption isotherms to characterize the role played by the alcohol hydrogen-bonding network in the adsorption process. Beyond simple selectivity, vapour sorption isotherms measured for various compositions help to completely unravel at the molecular level the step by step adsorption mechanism of the binary system in the nanoporous solid, from the first monolayers to the complete liquid condensation.

Thermotropic orientational order of discotic liquid crystals in nanochannels: an optical polarimetry study and a Landau-de Gennes analysis.

Optical polarimetry measurements of the orientational order of a discotic liquid crystal based on a pyrene derivative confined in parallelly aligned nanochannels of monolithic, mesoporous alumina, silica, and silicon as a function of temperature, channel radius (3-22 nm) and surface chemistry reveal a competition of radial and axial columnar orders. The evolution of the orientational order parameter of the confined systems is continuous, in contrast to the discontinuous transition in the bulk. For channel radii larger than 10 nm we suggest several, alternative defect structures, which are compatible both with the optical experiments on the collective molecular orientation presented here and with a translational, radial columnar order reported in previous diffraction studies. For smaller channel radii our observations can semi-quantitatively be described by a Landau-de Gennes model with a nematic shell of radially ordered columns (affected by elastic splay deformations) that coexists with an orientationally disordered, isotropic core. For these structures, the cylindrical phase boundaries are predicted to move from the channel walls to the channel centres upon cooling, and vice-versa upon heating, in accord with the pronounced cooling/heating hystereses observed and the scaling behavior of the transition temperatures with the channel diameter. The absence of experimental hints of a paranematic state is consistent with a biquadratic coupling of the splay deformations to the order parameter.

Discotic columnar liquid crystal studied in the bulk and nanoconfined states by molecular dynamics simulation.

A prototypical Gay Berne discotic liquid crystal was studied by means of molecular dynamics simulations both in the bulk state and under confinement in a nanoporous channel. The phase behavior of the confined system strongly differs from its bulk counterpart: the bulk isotropic-to-columnar transition is replaced by a continuous ordering from a paranematic to a columnar phase. Moreover, a new transition is observed at a lower temperature in the confined state, which corresponds to a reorganization of the intercolumnar order. It reflects the competing effects of pore surface interaction and genuine hexagonal packing of the columns. The translational molecular dynamics in the different phases has been thoroughly studied and discussed in terms of collective relaxation modes, non-Gaussian behavior, and hopping processes.

Crossover in structure and dynamics of a primary alcohol induced by hydrogen-bonds dilution.

Primary alcohols show a prominent Debye process in the dielectric relaxation located at a timescale longer than the main structural relaxation. Böhmer and co-workers studied dilution effects of the hydrogen bonding network of n-butanol (BuOH) with n-bromobutane (BuBr) to better understand the origin of this process. Interestingly, this work has evidenced a crossover in Debye relaxation time (τD) for a critical concentration in BuBr xc = 0.5. By using molecular dynamics simulations and NMR experiments we propose here to explore further dilution effects on the dipolar and translational dynamics. Moreover, we discuss the relation between structural and dynamical properties in the context of a detailed study of the microstructure and the H-bond network. The overall results are consistent with the existence of a topological change in the liquid structure occurring at about xc = 0.5 from a hypernetted percolating network to independent nanodomains of n-butanol molecules embedded in the n-bromobutane phase.

Configurational temperature and local properties of the anisotropic Gay-Berne liquid crystal model: applications to the isotropic liquid/vapor interface and isotropic/nematic transition.

Molecular simulations in the isothermal statistical ensembles require that the macroscopic thermal and mechanical equilibriums are respected and that the local values of these properties are constant at every point in the system. The thermal equilibrium in Monte Carlo simulations can be checked through the calculation of the configurational temperature, k(B)T(conf)=<|∇(r)U(r(N))|(2)>/<∇(r) (2)U(r(N))>, where ∇(r) is the nabla operator of position vector r. As far as we know, T(conf) was never calculated with the anisotropic Gay-Berne potential, whereas the calculation of T(conf) is much more widespread with more common potentials (Lennard Jones, electrostatic, ...). We establish here an operational expression of the macroscopic and local configurational temperatures, and we investigate locally the isotropic liquid phase, the liquid / vapor interface, and the isotropic-nematic transition by Monte Carlo simulations.

Molecular simulations of confined liquids: an alternative to the grand canonical Monte Carlo simulations.

Commonly, the confinement effects are studied from the grand canonical Monte Carlo (GCMC) simulations from the computation of the density of liquid in the confined phase. The GCMC modeling and chemical potential (µ) calculations are based on the insertion/deletion of the real and ghost particle, respectively. At high density, i.e., at high pressure or low temperature, the insertions fail from the Widom insertions while the performing methods as expanded method or perturbation approach are not efficient to treat the large and complex molecules. To overcome this problem we use a simple and efficient method to compute the liquid's density in the confined medium. This method does not require the precalculation of µ and is an alternative to the GCMC simulations. From the isothermal-isosurface-isobaric statistical ensemble we consider the explicit framework/liquid external interface to model an explicit liquid's reservoir. In this procedure only the liquid molecules undergo the volume changes while the volume of the framework is kept constant. Therefore, this method is described in the Np(n)AV(f)T statistical ensemble, where N is the number of particles, p(n) is the normal pressure, V(f) is the volume of framework, A is the surface of the solid/fluid interface, and T is the temperature. This approach is applied and validated from the computation of the density of the methanol and water confined in the mesoporous cylindrical silica nanopores and the MIL-53(Cr) metal organic framework type, respectively.

Dynamic Heterogeneities in Liquid Mixtures Confined in Nanopores.

Binary liquid mixtures can exhibit nanosegregation, albeit being fully miscible and homogeneous at the macroscopic scale. This tendency can be amplified by geometrical nanoconfinement, leading to remarkable properties. This work investigates the molecular dynamics of tert-butanol (TBA)-toluene (TOL) mixtures confined in silica nanochannels by quasielastic neutron scattering and molecular dynamics simulation. It reveals a decoupling of the molecular motion of each constituent of the binary liquid, which can be followed independently by selective isotopic H/D labeling. We argue that this behavior is the signature of spatially segregated dynamic heterogeneities, which are due to the recently established core-shell nanophase separation induced by mesoporous confinement.

Structure and dynamics of a Gay-Berne liquid crystal confined in cylindrical nanopores.

Gay-Berne liquid crystals confined in two cylindrical nanopores with different pore sizes were studied by molecular dynamics simulation. Their structure and dynamics properties were obtained and compared with those of the bulk. Our data show that confinement changes the bulk isotropic-to-nematic transition to a continuous ordering from a paranematic to a nematic phase. Moreover, confinement strongly hinders the smectic translational order. The molecular dynamics is characterized by the translational diffusion coefficients and the first-rank reorientational correlation times. Very different characteristic times and temperature variations in the dynamics are observed in confinement. Spatially resolved quantities illustrate that confinement induces predominant structural and dynamical heterogeneities.

Relation between static short-range order and dynamic heterogeneities in a nanoconfined liquid crystal.

We analyze the molecular dynamics heterogeneity of the liquid crystal 4-n-octyl-4'-cyanobiphenyl nanoconfined in porous silicon. We show that the temperature dependence of the dynamic correlation length xi_(wall) , which measures the distance over which a memory of the interfacial slowing down of the molecular dynamics persists, is closely related to the growth of the short-range static order arising from quenched random fields. More generally, this result may also shed some light on the connection between static and dynamic heterogeneities in a wide class of condensed and soft matter systems.

High-resolution dielectric study reveals pore-size-dependent orientational order of a discotic liquid crystal confined in tubular nanopores.

We report a high-resolution dielectric study on a pyrene-based discotic liquid crystal (DLC) in the bulk state and confined in parallel tubular nanopores of monolithic silica and alumina membranes. The positive dielectric anisotropy of the DLC molecule at low frequencies (in the quasistatic case) allows us to explore the thermotropic collective orientational order. A face-on arrangement of the molecular discs on the pore walls and a corresponding radial arrangement of the molecules is found. In contrast to the bulk, the isotropic-to-columnar transition of the confined DLC is continuous, shifts with decreasing pore diameter to lower temperatures, and exhibits a pronounced hysteresis between cooling and heating. These findings corroborate conclusions from previous neutron and x-ray-scattering experiments as well as optical birefringence measurements. Our study also indicates that the relative simple dielectric technique presented here is a quite efficient method in order to study the thermotropic orientational order of DLC-based nanocomposites.

Solid state amorphization kinetic of alpha lactose upon mechanical milling.

It has been previously reported that α-lactose could be totally amorphized by ball milling. In this paper we report a detailed investigation of the structural and microstructural changes by which this solid state amorphization takes place. The investigations have been performed by Powder X-ray Diffraction, Solid State Nuclear Magnetic Resonance ((13)C CP-MAS) and Differential Scanning Calorimetry. The results reveal the structural complexity of the material in the course of its amorphization so that it cannot be considered as a simple mixture made of a decreasing crystalline fraction and an increasing amorphous fraction. Heating this complexity can give rise to a fully nano-crystalline material. The results also show that chemical degradations upon heating are strongly connected to the melting process.

Collective molecular reorientation of a calamitic liquid crystal (12CB) confined in alumina nanochannels.

We study the smectic director structure of the rodlike liquid crystal 4-n-dodecyl-4'-cyanobiphenyl (12CB) confined in cylindrical cavities of 200 nm diameter in porous alumina templates by means of combined broadband dielectric spectroscopy, optical birefringence, and neutron scattering measurements. We show that the collective molecular orientation differs between entering the smectic A phase upon cooling from the isotropic state and entering the same phase upon heating while melting the confined crystal. We discuss this collective molecular realignment in terms of a competition between weak planar anchoring at the p-Al2O3/12CB interface and a preferred texture typical of the crystallization of rodlike molecules in nanochannels (Bridgman growth).

Criticality of an isotropic-to-smectic transition induced by anisotropic quenched disorder.

We report combined optical birefringence and neutron scattering measurements on the liquid crystal 12CB nanoconfined in mesoporous silicon layers. This liquid crystal exhibits strong nematic-smectic coupling responsible for a discontinuous isotropic-to-smectic phase transition in the bulk state. Confined in porous silicon, 12CB is subjected to strong anisotropic quenched disorder: a short-ranged smectic state evolves out of a paranematic phase. This transformation appears continuous, losing its bulk first-order character. This contrasts with previously reported observations on liquid crystals under isotropic quenched disorder. In the low temperature phase, both orientational and translational order parameters obey the same power law.

Continuous paranematic-to-nematic ordering transitions of liquid crystals in tubular silica nanochannels.

The optical birefringence of rodlike nematogens (7CB, 8CB), imbibed in parallel silica channels with 10 nm diameter and 300 microm length, is measured and compared to the thermotropic bulk behavior. The orientational order of the confined liquid crystals, quantified by the uniaxial nematic ordering parameter, evolves continuously between paranematic and nematic states, in contrast to the discontinuous isotropic-to-nematic bulk phase transitions. A Landau-de Gennes model reveals that the strength of the orientational ordering fields, imposed by the silica walls, is beyond a critical threshold, that separates discontinuous from continuous paranematic-to-nematic behavior. Quenched disorder effects, attributable to wall irregularities, leave the transition temperatures affected only marginally, despite the strong ordering fields in the channels.

Incoherent quasielastic neutron scattering study of molecular dynamics of 4-n-octyl-4'-cyanobiphenyl.

We report incoherent quasielastic neutron scattering experiments on the thermotropic liquid crystal 4-n-octyl-4'-cyanobiphenyl. The combination of time-of-flight and backscattering data allows analysis of the intermediate scattering function over about three decades of relaxation times. Translational diffusion and uniaxial molecular rotations are clearly identified as the major relaxation processes in, respectively, the nanosecond and picosecond time scales.

Exploring conformational energy landscape of glassy disaccharides by cross polarization magic angle spinning 13C NMR and numerical simulations. I. Methodological aspects.

This article demonstrates the ability of chemical shift surfaces to provide information on distributions of various conformations of disaccharides in the glassy, solid state. The validity of the general method leading to a simulation of inhomogeneous (13)C chemical shift distributions is discussed in detail. In particular, a proper consideration of extrema and saddle points of the chemical shift map correctly accounts for the observed discontinuities in the experimental cross polarization magic angle spinning spectra. Provided that these basic requirements are met, density functional theory/gauge-independent atomic orbital chemical shift maps calculated on relaxed conformations lead to a very satisfactory description of the experimental line shapes. Using amorphous trehalose as a model disaccharide, the simulation unambiguously defines the range of most populated conformations in the glass.

Exploring the conformational energy landscape of glassy disaccharides by cross polarization magic angle spinning 13C nuclear magnetic resonance and numerical simulations. II. Enhanced molecular flexibility in amorphous trehalose.

This paper uses chemical shift surfaces to simulate experimental (13)C cross polarization magic angle spinning spectra for amorphous solid state disaccharides, paying particular attention to the glycosidic linkage atoms in trehalose, sucrose, and lactose. The combination of molecular mechanics with density functional theory/gauge invariant atomic orbital ab initio methods provides reliable structural information on the conformational distribution in the glass. The results are interpreted in terms of an enhanced flexibility that trehalose possesses in the amorphous solid state, at least on the time scale of (13)C nuclear magnetic resonance measurements. Implications of these findings for the fragility of trehalose glass and bioprotectant action are discussed.

Structure determination of the 1/1 alpha/beta mixed lactose by X-ray powder diffraction.

The mixed form of alpha/beta lactose was obtained by heating amorphous alpha-lactose at 443 K. NMR spectroscopy determined the stoichiometry of this mixed compound to be 1/1. The X-ray powder diffraction pattern was recorded at room temperature with a sensitive curved detector (CPS 120). The structure was solved by real-space methods (simulated annealing) followed by Rietveld refinements with soft constraints on bond lengths and bond angles. The H atoms of the hydroxyl groups were localized by minimization of the crystalline energy. The cell of 1/1 alpha/beta lactose is triclinic with the space group P1 and contains two molecules (one molecule of each anomer). The crystalline cohesion is achieved by networks of O-H...O hydrogen bonds. The width of the Bragg peaks is interpreted through a microstructural approach in terms of isotropic strain effects and anisotropic size effects.