RESUMO
N-acetyl-L-cysteine (NAC), a derivative of the L-cysteine amino acid, presents antioxidant and mucolytic properties of pharmaceutical interest. This work reports the preparation of organic-inorganic nanophases aiming for the development of drug delivery systems based on NAC intercalation into layered double hydroxides (LDH) of zinc-aluminum (Zn2Al-NAC) and magnesium-aluminum (Mg2Al-NAC) compositions. A detailed characterization of the synthesized hybrid materials was performed, including X-ray diffraction (XRD) and pair distribution function (PDF) analysis, infrared and Raman spectroscopies, solid-state 13carbon and 27aluminum nuclear magnetic resonance (NMR), simultaneous thermogravimetric and differential scanning calorimetry coupled to mass spectrometry (TG/DSC-MS), scanning electron microscopy (SEM), and elemental chemical analysis to assess both chemical composition and structure of the samples. The experimental conditions allowed to isolate Zn2Al-NAC nanomaterial with good crystallinity and a loading capacity of 27.3 (m/m)%. On the other hand, NAC intercalation was not successful into Mg2Al-LDH, being oxidized instead. In vitro drug delivery kinetic studies were performed using cylindrical tablets of Zn2Al-NAC in a simulated physiological solution (extracellular matrix) to investigate the release profile. After 96 h, the tablet was analyzed by micro-Raman spectroscopy. NAC was replaced by anions such as hydrogen phosphate by a slow diffusion-controlled ion exchange process. Zn2Al-NAC fulfil basic requirements to be employed as a drug delivery system with a defined microscopic structure, appreciable loading capacity, and allowing a controlled release of NAC.
RESUMO
Three different anionic blue organic dyes have been intercalated into the structure of Zn(2)Al layered double hydroxides, using the co-precipitation method at constant pH. Using the same synthetic procedure, Zn(2)Al-Cl has been prepared and used as an adsorptive phase to retain the blue dyes from an aqueous solution. All the organic/inorganic (O/I) hybrid LDH compounds were analyzed by X-ray powder diffraction (XRPD), thermal analysis (TG/DTA), elemental analysis, solid state (13)C nuclear magnetic resonance (CPMAS (13)C NMR), and Fourier transform infrared spectroscopy (FTIR). In the adsorption experiments, Gibbs free energy DeltaG values for the temperatures in a range between 10 and 40 degrees C were found to be negative, which indicates that the nature of adsorption is spontaneous and shows the affinity of LDH material towards the blue anionic dyes. Additionally a decrease in DeltaG values at higher temperature further indicates that this process is even more favorable at these conditions. The enthalpy DeltaH values were between physisorption and chemisorption, and it may be concluded that the process was a physical adsorption enhanced by a chemical effect, characterized by a combined adsorption/intercalation reaction, making these O/I assemblies reminiscent of the Maya blue.
Assuntos
Compostos de Alumínio/química , Corantes/química , Hidróxidos/química , Compostos de Zinco/química , Adsorção , Ânions/química , Concentração de Íons de Hidrogênio , Estrutura Molecular , Propriedades de Superfície , TemperaturaRESUMO
A series of blue dye molecules, Evans blue (EB), Chicago sky blue (CB), Niagara blue (NB) were incorporated by direct co-precipitation within the galleries of negatively charge layered double hydroxide (LDH). The materials of cation composition Zn/Al = 2 lead to well-defined organic inorganic assemblies. The molecular arrangement of the interleaved dye molecule is proposed by 1D electronic density projection along the stacking direction for the hydrothermally treated samples with alternatively a highly inclined orientation of EB and CB and a parallel-bilayer arrangement for NB. Blue coloured LDH assemblies were subsequently dispersed into polystyrene (PS). It was found that the hybrid fillers do not interfere in the radical polymerization of styrene, giving rise to similar molecular weight and polydispersity than filler free PS, while higher glass transition temperatures were obtained for the nanocomposites. This was consistent with the rheological behaviour with the observation for LDH/NB filler based nanocomposite of shear thinning exponent different from zero, underlining frictional interaction between filler and PS chain. The absorption maximum slightly blue-shifted for the hybrid filler in comparison to the corresponding organic dye was found unmodified for the PS nanocomposite, thus giving rise to blue coloured plastic films, reminiscent somehow of the blue Maya effect.