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The Halloysite (Al2Si2O5(OH)4·2H2O) is an abundant and cheap clay and is considered one of the most promising nano structured and naturally occurring clay mineral. Large deposits of this material are present in France, Belgium, China, New Zealand and USA [1,2]. Among the spheroidal, tubular or platy morphologies, the tubular is the most common and abundant one. Typically, halloysite nanotubes (HNTs) are formed by 15 – 20 aluminosilicate layers, having a length of 1 ± 0.5 μm, and inner and outer diameters of 10 – 15 nm and 50 -70 nm, respectively [1]. In each layer, the SiOH and the AlOH groups are disposed on the external and the internal surfaces, respectively. As consequence, in each nanotube and in a large pH range, there is a charge separation between the inner and the outer surfaces. In particular, the inner surface is positively charged because of protonation of AlOH groups and the outer surface is negatively charged because of the gradual deprotonation of SiOH groups at pH higher than 2. This charge separation is one of the most important features for the HNTs versatility and is strictly dependent on the acid – base properties of their functional groups. In this work, the protonation / deprotonation of SiOH and AlOH groups of HNTs is evaluated by ISE-H+ potentiometric titrations of HNTs aqueous suspensions in different ionic media and ionic strengths (0.025 ≤ I / mol L-1 ≤ 0.750) and in a wide pH range (2 – 11), at T = 25°C.ISE-H+ potentiometric titration data have been processed by using the same models successfully used in a previous work for carboxylic and phenol groups of humic and fulvic substances [3]. Moreover, the change of superficial charge with the changing of pH was also evaluated by ζ potential measurements.Correlations between the ζ potential trend and the distribution of protonated and deprotonated species of HNTs were found.

In this paper, potentiometry and calorimetry were used to determine the thermodynamics of interaction between risedronate and four bivalent metal cations, namely: Mg2+, Zn2+, Pb2+, and Cu2+ in aqueous NaCl solutions at different ionic strengths and at T = 298.15 K. The data analysis allowed us to ascertain that the main species formed were the MLH2, MLH, ML and M2L; however scarcely soluble species precipitated at acidic pH values, between 4 and 7 depending on the metal cation involved, probably due to the formation of the neutral M2L(s) species. Comparison of the stability constants with other similar ligands suggests that metal complexation occurs through the phosphonate with an additional stabilizing contribution due to the pyridine moiety. The dissection of the free energy term revealed that the entropic change is the main contribution to the stability of the complexes for all equilibria, except those regarding the formation of the M2L species, and the main forces involved in these processes are entropic in nature, such as the desolvation of both the ligand and the metal cations. The sequestering ability was evaluated computing the pL0.5 parameter at different pH and ionic strength values; the highest ones were found for Cu2+ in acidic solutions and at low ionic strength, whereas pL0.5 values for both Pb2+ and Zn2+ were slightly lower. Results reported in this work may be helpful in the assessment of the use of risedronate as effective chelating agent and for understanding the mechanism of action of this molecule as a drug.

In this paper, new information on physical and chemical properties of the widely used nanostructured Halloysite mineral are reported. Given that the Halloysite has a tubular structure formed by a variable number of wrapped layers containing Si-OH and Al-OH groups, their proton binding affinity was measured at different ionic strengths and ionic media by means of potentiometric measurements in heterogeneous phase. One protonation constant for the Si-OH groups and two for the Al-OH groups were determined. The protonation constant values increase with increasing of the ionic strength in all the ionic media. This suggests that the presence of a background electrolyte stabilizes the protonated species through the formation of weak complexes between ions of the supporting electrolytes and the protonated species. Ten weak species were determined with different stoichiometry. It was shown that the interactions do not depend on the nature of the supporting electrolytes but on the charge. The surface charge of Halloysite was estimated by ζ potential measurements as a function of pH, and the values obtained are consistent with the nanotubes ionization predicted by using the protonation constants for the Si-OH and Al-OH groups. The total solubility of the Halloysite nanotubes, was also determined in NaCl aqueous solution. These measurements showed that the solubility slightly increases with increasing ionic strength and contact time between Halloysite and NaCl solution. Goodness-of-fit (GOF) criteria were used to test the application of these models with good results. The obtained results confirm that the behavior of Halloysite in water is strictly correlated to the experimental conditions of the aqueous suspension (e.g., pH, ionic strength, and ionic media). The thermodynamic data here reported are of main importance in the several applications where is exploited the charge separation between the inner and outer surfaces of this nanotubular material.