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abstracts
Layered double hydroxides are versatile materials used for intercalating bioactive molecules, both in pharmaceutical and cosmetic fields, with the purpose of protecting them from degradation, enhancing their water solubility to increase bioavailability, and/or obtaining modified release properties. Hydrotalcite is commercially available in its carbonate form, which is usually transformed into the nitrate form and finally exchanged by organic anions to obtain or regulate bioactivity or photo-activity effects (1). In this study all the steps of these transformations were characterized from the structural viewpoints by X-ray powder diffraction (XRPD) and automated electron diffraction tomography (ADT). ADT allowed shedding light on the nitrate position and conformation inside LDH. XRPD demonstrated at first that the presence of carbonate impurities is able to drive the intercalation of organic molecules into LDH, since CO32- contaminated samples tend to assume d-spacings roughly multiple of LDH-CO3 d-spacing. Finally XRPD was employed at in situ conditions to unravel the structural transformation occurring during the substitution of carbonate by nitrate ion and of the nitrate ion by organic anions. The carbonate-nitrate substitutions resulted to be very rapid (only few seconds) and only the use of a fast area detector, coupled to synchrotron radiation, allowed obtaining reliable patterns to perform XRPD refinement of the disordered structure at the sub-second time resolution. The nitrate-organic substitution resulted slower and depending on the chemical properties of the organic molecules.
abstracts
Layered double hydroxides are versatile materials used for intercalating bioactive molecules, both in pharmaceutical and cosmetic fields, with the purpose of protecting them from degradation, enhancing their water solubility to increase bioavailability, and/or obtaining modified release properties. The crystal chemistry of hydrotalcite-like compounds is investigated by X-ray powder diffraction (XRPD) and hyphenated TGA-GC-MS to shed light on the mechanisms involved in ion exchange and absorption of contaminants, mainly carbonate anions. XRPD demonstrated that the presence of carbonate is able to drive the intercalation of organic molecules into LDH, since CO3 contaminated samples tend to assume d-spacing roughly multiple of LDH-CO3 d-spacing. TGA-GC-MS allowed distinguishing and quantifying intercalated and surface adsorbed organic molecules, confirming the presence and amount of carbonate, especially at low (ppm) concentrations and separating the different types and strength of adsorption, in relation with the temperature of elimination. Also the importance of the intercalation method on the carbonate absorption was examined. This is probably due to the fact that the larger molecules leave some voids in the packing and the carbonate can occupy these voids during the intercalation. Finally the presence of adsorbed and not intercalated organic guest was quantified by TGA-GC-MS.
