Second harmonic scattering reveals different orientational orders inside the hydrophobic cavity of hybrid nanotubes.

Second Harmonic Scattering (SHS) is a suitable technique to investigate the orientational correlations between molecules. This article explores the organization of different dye molecules adsorbed within the hydrophobic porosity of a hybrid organic-inorganic nanotube. Experimental polarization resolved SHS measurements highlight different orientational orders ranking from highly ordered and rigid organizations to disordered assemblies. Microscopic models of assemblies inside the pores are presented and discussed in the context of orientational correlation between the dye molecules. This work shows that the degree of order in the nanotube cavity follows the molecule's affinity within the porosity.

Dried hybrid imogolite nanotubes as solids with a changeable surface area: an insight into textural properties based on the correlation between nitrogen gas adsorption, immersion calorimetry into water, and small angle X-ray scattering.

Powdered samples of three imogolite materials with an inner surface covered with Si-CH3 groups (hybrid IMO-CH3) were prepared by ambient drying at 323 K, freeze drying, and spray drying. Reliable estimates of the intra-tube (SA), inter-tube (SB), and inter-bundle (SC) specific surface areas of these samples were inferred from a model-guided correlation between the results of measurements by small angle X-ray scattering (SAXS), nitrogen gas adsorption, and immersion calorimetry into water. Since the SAXS studies indicated no significant deformations of IMO-CH3 nanotubes upon drying, further studies by gaseous N2 adsorption at 77 K indicated the intra-tube and inter-bundle specific surface areas as being only accessible to this adsorbate. The outer curved surfaces of IMO nanotubes, including the inter-tube surface areas, were evaluated based on the calorimetric measurements of the enthalpy of immersion into water, using the enthalpy of immersion per unit surface area for a modelled curved surface of gibbsite as the conversion factor. Given the uncertainty in the determination of surface areas, the IMO-CH3 samples were found to possess the limiting values of specific surface areas ranging between 1150 and 1480 m2 g-1. In contrast to the two other materials, ambient-dried IMO-CH3 was characterized by the highest value of SC parameter due to the much smaller bundles formed by the constituent imogolite nanotubes. The accessibility of these surface areas, together with the hydrophobic and hydrophilic surface domains, was demonstrated to depend on the nature of the surrounding medium and the size of the adsorbing species.

Renewing Interest in Zeolites as Adsorbents for Capture of Cationic Dyes from Aqueous and Ethanolic Solutions: A Simulation-Based Insight into the Efficiency of Dye Adsorption in View of Wastewater Treatment and Valorization of Post-Sorption Materials.

The impact of solvents on the efficiency of cationic dye adsorption from a solution onto protonated Faujasite-type zeolite (FAU-Y) was investigated in the prospect of supporting potential applications in wastewater treatment or in the preparation of building blocks for optical devices. The adsorption isotherms were experimentally determined for methylene blue (MB) and auramine O (AO) from single-component solutions in water and in ethanol. The limiting dye uptake (saturation capacity) was evaluated for each adsorption system, and it decreased in the order of MB-water > AO-water > AO-ethanol > MB-ethanol. The mutual distances and orientations of the adsorbed dye species, and their interactions with the oxygen sites of the FAU-Y framework, with the solvent molecules, and among themselves were inferred from Monte Carlo simulations and subsequently utilized to rationalize the observed differences in the saturation capacity. The dye-solvent competition and the propensity of the dyes to form compact pi-stacked dimers were shown to play an important role in establishing a non-uniform distribution of the adsorbed species throughout the porous space. The two effects appeared particularly strong in the case of the MB-water system. The necessity of including solvent effects in modeling studies is emphasized.

Hydrophobic dye solubilization via hybrid imogolite nanotubes probed using second harmonic scattering.

This article explores the organization and interactions of Disperse Orange 3 (DO3) hydrophobic dye molecules within hybrid organic-inorganic imogolite nanotubes. In pure water, the DO3 dye molecules self assemble into large insoluble 2D nanosheets whose structure is also explored by molecular dynamics simulations. The dye molecules are however efficiently solubilized in the presence of hybrid imogolite nanotubes. The filling of the internal hydrophobic cavity of the nanotubes is quantified. The organization of the molecules inside the nanotube is probed using the polarization resolved second harmonic scattering (SHS) technique coupled with simulation. At the highest loading, the dyes fill the nanotube with their principal axis parallel to the nanotube walls showing a strong SHS signal due to this encapsulation.

Water Organization around Inorganic Nanotubes in Suspension Probed by Polarization-Resolved Second Harmonic Scattering.

Imogolite nanotube (INT) is a fascinating one-dimensional (1D) material that can be synthesized in the liquid phase. Its behavior in solution is crucial for many applications and depends on the organization of water at the liquid-wall interface. We study here this water organization by using the nonlinear optical technique of polarization-resolved second harmonic scattering (SHS). A microscopic model is proposed to interpret the origin of the coherent SHS signal recovered in this 1D colloidal system. This work demonstrates that the SHS technique is able to probe the shell of water molecules oriented around the nanotubes. Water organization results from the electric field induced by the nanotube walls, and it is strongly dependent on the ionic strength of the suspension.

Driving Forces of Cationic Dye Adsorption, Confinement, and Long-Range Correlation in Zeolitic Materials.

Zeolitic materials are commonly used to capture emergent contaminants in water or complex aqueous effluents. The efficiency of this adsorption depends strongly on the guest-host interactions and on the surrounding environment with possible coadsorption of the solvent. Only a few experimental techniques are available to probe in situ the sequestration processes at the solid/liquid interface. We propose in the present work to combine the second harmonic scattering technique with isothermal titration calorimetry in order to investigate the adsorption and the confinement of a hemicyanine dye adsorbed inside faujasite materials. The methodology described here permits the quantification of the correlations between the confined dyes in the material and thus gives local information about the organization at the nanometer scale. Various impacts, such as the effect of the solvent type and the silicon to aluminum ratio of the zeolitic adsorbent, are quantitatively estimated and discussed. This work highlights that the most correlated system matches the higher adsorption capacity associated with the lower entropic contribution.

PySHS: Python Open Source Software for Second Harmonic Scattering.

The PySHS package is a new python open source software tool which simulates the second harmonic scattering (SHS) of different kinds of colloidal nano-objects in various experimental configurations. This package is able to compute polarizations resolved at a fixed scattered angle or angular distribution for different polarization configurations. This article presents the model implemented in the PySHS software and gives some computational examples. A comparison between computational results and experimental data concerning molecular dye intercalated inside liposomes membrane is presented to illustrate the possibilities with PySHS.

Second-Harmonic Scattering in Layered Double Hydroxide Colloids: A Microscopic View of Adsorption and Intercalation.

The interaction of methyl orange dye with a layered double hydroxide colloidal material is investigated using real-time polarization-resolved second-harmonic scattering (SHS). Interlayer charge compensating anion exchange is studied from initial carbonate or nitrate anions to methyl orange negatively charged dye. A theoretical model, taking into account the field retardation effect, is presented to simulate the polarization-resolved SHS experiments. Various geometrical dye configurations inside or around the host material have been modeled. A comparison with the experimental data permits to give a microscopic description of the dye organization and its time evolution during the intercalation process in the material.

Surface activity and molecular organization of metallacarboranes at the air-water interface revealed by nonlinear optics.

Because of their amphiphilic structure, surfactants adsorb at the water-air interface with their hydrophobic tails pointing out of the water and their polar heads plunging into the liquid phase. Unlike classical surfactants, metallabisdicarbollides (MCs) do not have a well-defined amphiphilic structure. They are nanometer-sized inorganic anions with an ellipsoidal shape composed of two carborane semicages sandwiching a metal ion. However, MCs have been shown to share many properties with surfactants, such as self-assembly in water (formation of micelles and vesicles), formation of lamellar lyotropic phases, and surface activity. By combining second harmonic generation and surface tension measurement, we show here that cobaltabis(dicarbollide) anion {[(C2B9H11)2Co](-) also named [COSAN](-)} with H(+) as a counterion, the most representative metallacarborane, adsorbs vertically at the water surface with its long axis normal to the surface. This vertical molecular orientation facilitates the formation of intermolecular and nonconventional dihydrogen bonds such as the B-H(δ-)···(δ+)H-C bond that has recently been proven to be at the origin of the self-assembly of MCs in water. Therefore, it appears here that lateral dihydrogen bonds are also involved in the surface activity of MCs.