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Modified montmorillonite was prepared at different surfactant (HDTMA) loadings through ion exchange. The conformational arrangement of the loaded surfactants within the interlayer space of MMT was obtained by computational modelling. The conformational change of surfactant molecules enhance the visual understanding of the results obtained from characterization methods such as XRD and surface analysis of the organoclays. Batch experiments were carried out for the adsorption of p-chlorophenol (PCP) and different conditions (pH and temperature) were used in order to determine the optimum sorption. For comparison purpose, the experiments were repeated under the same conditions for p-nitrophenol (PNP). Langmuir and Freundlich equations were applied to the adsorption isotherm of PCP and PNP. The Freundlich isotherm model was found to be the best fit for both of the phenolic compounds. This involved multilayer adsorptions in the adsorption process. In particular, the binding affinity value of PNP was higher than that of PCP and this is attributable to their hydrophobicities. The adsorption of the phenolic compounds by organoclays intercalated with highly loaded surfactants was markedly improved possibly due to the fact that the intercalated surfactant molecules within the interlayer space contribute to the partition phases, which result in greater adsorption of the organic pollutants.

Kaolinite as a remarkable industrial raw material has notable structural features despite its simple chemical composition (Al2O3·2SiO2·2H2O). We report here a systematic development of a coordination chemical model for the [6Al-6(OH)] honeycomb-like unit of kaolinite's octahedral sheet, which was proposed to be the adsorption site for small molecules from earlier studies. The coordination environment of the Al(3+) ions was completed with outer sphere groups from both octahedral and tetrahedral sheets. Dangling bonds were terminated by additional Al(3+) and Si(4+) ions with hydroxide and oxide groups from the second coordination sphere versus simple protonation. A cage of Na(+) and Mg(2+) ions rendered the computational model to be charge neutral. In this exfoliated kaolinite model, the inner hydroxide groups and the adjacent Al(3+) ions have compositionally the most complete environments with respect to the crystal structure. Thus, their atomic positions were used as a benchmark for the level of theory dependence of the optimized structures. We evaluated the performance of a representative set of density functionals, basis sets, point-charges, identified pitfalls and caveats. Importantly, the structural changes during optimization of periodic and cluster models suggest pliability for the exfoliated kaolinite layers, which is influenced by the external chemical environment.

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Clay-based nanostructures were prepared from kaolinites of varying structural order by two different methods. In the first method the kaolinite-urea precursor, obtained by dry grinding, was intercalated further with triethanolamine and the tetraalkylammonium salt was synthesized in the interlamellar space. Exfoliation was achieved by the use of sodium polyacrylate (PAS). In the second method, the kaolinite-potassium acetate (kaolinite-KAc) precursor, obtained via two different methods, was intercalated further with ethylene glycol (EG) and then n-hexylamine (HA). Intercalation with EG was also achieved by heating either directly or with microwaves. The morphology that results depends on the method of precursor preparation, the method of heat treatment and the degree of structural order of the original clay. Higher structural order facilitates the formation of a tubular morphology, while mechanical treatment and microwave agitation may result in broken tubes. Molecular mechanical (MM) calculations showed that organo-complexes may be exfoliated to a d value of 10–11 Å.

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Here, we report a study on the complexation behavior of carotenoids with cyclodextrins (CDs) using solubility experiments and molecular-modelling methods. Carotenoids are an important group of naturally occurring dyes found in vegetables and fruits. Their antioxidant property has initiated investigations on their possible use as drugs. However, carotenoids are lipophilic molecules with very little inherent aqueous solubility. Cyclodextrin complexation has been widely used in order to increase the potential applications of hydrophobic compounds. Thus, the aim of our investigation was to design carotenoids with enhanced water solubility by cyclodextrin complexation. Molecular modelling of carotenoid-cyclodextrin complexes with a 1 : 1 stoichiometry successfully explained the experimentally observed capability of beta-cyclodextrins (beta-CDs) to form complexes with carotenoids as opposed to alpha-cyclodextrins (alpha-CDs) and gamma-cyclodextrins (gamma-CDs). Furthermore, molecular-dynamics calculations revealed that the aggregation properties of CD derivatives significantly influence their complexation behavior. Our docking calculations showed that RAMEB (random methylated beta-CD) is the beta-CD derivative that possesses the lowest tendency to aggregate. Solubility experiments yielded the same results, namely, RAMEB complexes possess the best water solubility. Our results showed that complexation of a ligand not buried inside of the CD cavity is dependent on two factors: i) the geometry of the inclusion part of the complex; ii) the self-aggregation property of the CD itself. The lower affinity the CDs possess for self-aggregation, the more likely are they involved in interactions with carotenoids. These results suggest that self-aggregation of CDs should be considered as an important parameter determining complexation in general.

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