New Insights into the complexation of lead(II) by 1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraazacyclododecane (DOTAM): structural, thermodynamic and kinetic studies
The lead(II) coordination properties of the tetrapodal ligand DOTAM [1,4,7,10-tetrakis(carbamoylmethyl)-1,4,7,10-tetraaza-cyclododecane] have been investigated both in the solid state and in solution in order to ascertain the stereoactivity of the lone pair and to rationalize the structural effects of a cyclen-based scaffold on the metal uptake kinetics. The crystal structure of the free base shows that the pendant acetamide groups are not equivalent: two are folded over the macrocycle and maintained by an intramolecular hydrogen bond involving an amide hydrogen atom and a neighboring tertiary amine of the cyclen ring, while the other two are extended and point away from the macrocyclic cav…
Synthesis, Characterization, and X-ray Crystal Structures of Cyclam Derivatives. 8. Thermodynamic and Kinetic Appraisal of Lead(II) Chelation by Octadentate Carbamoyl-Armed Macrocycles1
En route toward the development of hybrid organic−inorganic extracting materials incorporating lead-selective chelators and their implementation in water purification processes, the lead(II) binding properties of three N-carbamoylmethyl-substituted 1,4,8,11-tetraazacyclotetradecanes (cyclams) have been fully investigated by spectroscopic (IR, UV−vis, MALDI-TOF MS, 1H and 13C NMR), X-ray crystallographic, potentiometric, and kinetic methods. Solution NMR studies revealed that the Pb2+ ion is entrapped in a molecular cage constituted by the four macrocyclic nitrogen and four amidic oxygen atoms. Protonation and lead binding constants determined in aqueous solution were shown to be linearly de…
A molecular approach to remove lead from drinking water
Abstract Corrosion of lead-containing plumbings is responsible for significant contamination of tap water, which can reach several hundreds of micrograms per liter. According to a decision of the European Council applicable in 2013, the maximal lead level in tap water should not exceed 10 μg l −1 . A new concept has been explored that relies on solid-phase extraction by covalent attachment of a lead-selective macrocyclic sequestering agent onto the surface of silica gel. An N -carbamoylmethyl substituted 1,4,8,11-tetraazacyclotetradecane (cyclam) derivative was shown to exhibit favorable protonation properties together with an almost 10 6 -fold selectivity for lead over calcium. Structural …