Layered double hydroxide and zirconium phosphate as ion exchangers for the removal of 'black crusts' from the surface of ancient monuments.

The chloride form of MgAl layered double hydroxide (hereafter MgAlCl) as an anion exchanger and the semisodic form of α-zirconium phosphate (hereafter ZrPNaH) as a cation exchanger are proposed as new cleaning agents for the removal of gypsum from ancient monuments. The ability of these exchangers to capture the calcium and sulphate ions of the gypsum powder was first investigated separately and then as a coupled system. MgAlCl/gypsum, ZrPNaH/gypsum and MgAlCl/ZrPNaH/gypsum mixtures were characterized by X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and dispersive X-ray spectroscopy (EDX). ZrPNaH in the form of a wet paste exhibited a rapid uptake of calcium from gypsum powder via Na+ and H+/Ca2+ cation exchange. Gypsum powder was also successfully dissolved by a wet paste of MgAlCl by exploiting the Cl-/SO42- anion exchange reaction. However, the dehydration of the paste favoured the reprecipitation of a secondary gypsum that was characterized by lower crystallinity and smaller particle size than the pristine gypsum. The combination of wet MgAlCl and ZrPNaH showed a synergic effect on the dissolution of gypsum and partially prevented the reprecipitation of gypsum in the dry paste. Finally, a preliminary test of the removal of gypsum crust grown on a sandstone sample was performed.

Ag/AgCl nanoparticle decorated layered double hydroxides: synthesis, characterization and antimicrobial properties.

A layered double hydroxide (LDH) surface was employed as a substrate for growing silver nanoparticles (NPs). An efficient method to produce stable silver/silver chloride nanoparticles supported on the ZnAl-LDH surface was developed. NPs of AgCl were grown on the ZnAl-LDH surface by using AgNO3 as the silver source. The ZnAl-LDH in chloride form acts as a nucleating agent, and depending on the pH of the LDH dispersion, AgClNPs with different dimensions were obtained. In particular AgClNPs with a diameter of 60 nm were formed at pH 5. The AgClNPs supported on LDH sheets were partially reduced by different reducing agents (NaBH4 and formaldehyde) resulting in a Ag/AgCl-LDH nanocomposite. The silver chloride and silver NP dimensions were evaluated by X-ray powder diffraction, field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM). UV-Vis spectra of the samples upon reduction showed a band centred at 415 nm due to the surface plasmon resonance of silver nanoparticles with a diameter of about 10 nm, in agreement with the TEM analysis. The AgCl-LDH and Ag/AgCl-LDH nanocomposites, subjected to antimicrobial tests, exhibited good antimicrobial activity against both Gram-negative (Pseudomonas aeruginosa) and Gram-positive (Staphylococcus epidermidis and S. aureus) bacteria and yeast (Candida albicans). The nanocomposites were also studied for their ability to release silver by obtaining release curves, under conditions of antibacterial assays. Finally, the nanocomposites antibacterial behavior, as a function of time, was investigated by performing time-kill experiments using S. aureus and Candida albicans.

Effect of gliclazide immobilization into layered double hydroxide on drug release.

This paper deals with a new hydrotalcite-like compound used as a matrix to improve dissolution rate of the poorly water-soluble drug gliclazide and to administer at the same time micro- and oligo-elements useful to improve insulin performance. Gliclazide is a second-generation sulfonylurea compound used in the treatment of type II diabetes mellitus. As a consequence of the poor water solubility, its absorption is limited. Thus, a new hydrotalcite-like compound containing Zinc and Chromium, micronutrients directly involved in the physiology of insulin and in the carbohydrate, lipid and protein metabolism, was synthesized. The gliclazide-hydrotalcite-like clay nanohybrid was prepared via ion-exchange in its nitrate form and was characterized by inductively coupled plasma-optical emission spectrometry and thermogravimetric analysis. The drug loading resulted in 42.9% (w/w). As a consequence of the intercalation, the interlayer distance of the host increased from 0.89 nm (interlayer distance of nitrate form) to 1.5 nm. The intercalation product was submitted to solubility measurements and in vitro dissolution test. A remarkable improvement of the apparent solubility and dissolution rate in comparison to the crystalline drug was observed in acid fluids (pH 1.2 and 3). The presence of chromium and zinc cations was also found in the medium. These results showed that the hybrid nanostructure could represent a promising system to improve drug dissolution rate and to release cations involved in the performance of insulin.

Molecular modeling of layered double hydroxide intercalated with benzoate, modeling and experiment.

The structure of Zn4Al2 Layered Double Hydroxide intercalated with benzencarboxylate (C6H5COO-) was solved using molecular modeling combined with experiment (X-ray powder diffraction, IR spectroscopy, TG measurements). Molecular modeling revealed the arrangement of guest molecules, layer stacking, water content and water location in the interlayer space of the host structure. Molecular modeling using empirical force field was carried out in Cerius(2) modeling environment. Results of modeling were confronted with experiment that means comparing the calculated and measured diffraction pattern and comparing the calculated water content with the thermogravimetric value. Good agreement has been achieved between calculated and measured basal spacing: d(calc) = 15.3 A and d(exp) = 15.5 A. The number of water molecules per formula unit (6H2O per Zn4Al2(OH)12) obtained by modeling (i.e., corresponding to the energy minimum) agrees with the water content estimated by thermogravimetry. The long axis of guest molecules are almost perpendicular to the LDH layers, anchored to the host layers via COO- groups. Mutual orientation of benzoate ring planes in the interlayer space keeps the parquet arrangement. Water molecules are roughly arranged in planes adjacent to host layers together with COO- groups.