Formation of hydrotalcite in aqueous solutions and intercalation of ATP by anion exchange

The formation reaction and the intercalation of adenosine triphosphate (ATP) were studied for hydrotalcite (HT), a layered double hydroxide (LDH) of magnesium and aluminum. Hydrotalcite with nitrate ions in the interlayer (HT-NO3) was formed (A) by dropwise addition of a solution of magnesium and aluminum nitrates (pH ca. 3) to a sodium hydroxide solution (pH ca. 14) until the pH decreased from 14 to 10 and (B) by dropwise addition of the NaOH solution to the solution of magnesium and aluminum nitrates with pH increasing from 3 to 10. The precipitate obtained with method B was contaminated with aluminum hydroxide and the crystallinity of the product was low, possibly because aluminum hydroxide precipitates at pH 4 or 5 and remains even after HT-NO3 forms at pH above 8. With method A, however, the precipitate was pure HT-NO3 with increased crystallinity, since the solubility of aluminum hydroxide at pH above and around 10 is high as dissolved aluminate anions are stable in this high pH region, and there was no aluminum hydroxide contamination. The formed HT-NO3 had a composition of [Mg0.71Al0.29(OH)2](NO3)0.29⋅0.58H2O. To intercalate ATP anions into the HT-NO3, HT-NO3 was dispersed in an ATP solution at pH 7. It was found that the interlayer nitrate ions were completely exchanged with ATP anions by ion exchange, and the interlayer distance expanded almost twice with a free space distance of 1.2 nm. The composition of HT-ATP was established as [Mg0.68Al0.32(OH)2](ATP)0.080⋅0.88H2O. The increased distance could be explained with a calculated molecular configuration of the ATP as follows: An ATP molecule is bound to an interlayer surface with the triphosphate group, the adenosine group bends owing to its bond angles and projects into the interlayer to a height of 1 nm, and the adenosine groups aligned in the interlayer support the interlayer distance.

An ATP molecule intercalated into hydrotalcite stretches up into the interlayer space supporting the interlayer free space. The adenosine groups of the ATP bind the two hydrotalcite layers by attractive interactions.Figure optionsDownload as PowerPoint slide