The adsorption of berberine by montmorillonite and thermo-XRD analysis of the organo-clay complex

The adsorption of the large cationic alkaloid berberine by montmorillonite in aqueous suspensions was investigated. An adsorption isotherm of berberine and desorption isotherms of exchangeable Na+, K, Mg2+ and Ca2+ were determined by chemical analysis of the non-adsorbed berberine and the released cations in the supernatants. The isotherms suggest that the adsorption of berberine takes place in two different types of reaction mechanism: (1) cation exchange, and (2) a secondary organophyllic adsorption. The cation exchange occurring first is followed by the secondary adsorption which is accompanied by Cl- adsorption. Monovalent cations are exchanged before the divalent cations. Samples loaded with increasing amounts of berberine were examined by X-ray diffraction at room temperature, and after gradual heating up to 420 degrees C. The basal spacing of the loaded samples after the thermal treatment became 1.28 rim, indicating the formation of carbon in the interlayer, thus proving that the adsorbed berberine was located in the interlayer space. At room temperature the basal spacing of samples loaded with 8 and 15 mmol of berberine per 100 g of clay was 1.28-1.30 nm indicating that in the interlayer space berberine cations were lying parallel to the alumino-silicate layers. The basal spacing of a sample with 36 mmol of berberine per 100 g of clay was 1.48 nm. This spacing does not give conclusive information on the arrangement of berberine in the interlayer. The spacing of samples with 57-147 mmol of berberine per 100 g of clay was 1.59 nm, suggesting the presence of bilayers of berberine in the interlayers. During thermal dehydration, the spacing of samples with 36-73 mmol of berberine per 100 g of clay decreased, but that of samples with 105-147 mmol of berberine per 100 g of clay increased to 1.66 nm. These samples contain organophilic adsorbed berberine and it is suggested that due to the thermal treatment berberine was tilted relative to the TOT lamellae, with anhydrous Cl- between the berberine cations.