Synthetic, structural and solution speciation studies on binary Al(III)-(carboxy)phosphonate systems. Relevance to the neurotoxic potential of Al(III).
Efforts to delineate the interactions of neurotoxic Al(III) with low molecular mass substrates relevant to neurodegenerative processes, led to the investigation of the pH-specific synthetic chemistry of the binary Al(III)-[N-(phosphonomethyl) iminodiacetic acid] (Al-NTAP), Al(III)-[nitrilo-tris(methylene-phosphonic acid)] (Al-NTA3P), and Al(III)-[1-hydroxy ethylidene-1,1-diphosphonic acid] (Al-HEDP) systems, in correlation with solution speciation studies. Reaction of Al(NO(3))(3).9H(2)O with NTAP at pH 7.0 and 4.0 afforded the new species (CH(6)N(3))(4)[Al(2)(C(5)H(6)NPO(7))(2)(OH)(2)].8H(2)O (1) and (NH(4))(2)[Al(2)(C(5)H(6)NPO(7))(2)(H(2)O)(2)].4H(2)O (2), while reaction of Al(NO(3))(3).9H(2)O with NTA3P led to K(8)[Al(2)(C(3)H(6)NP(3)O(9))(2)(OH)(2)].20H(2)O (3). Complexes 1-3 were characterized by elemental analysis, FT-IR, (13)C, (31)P, (1)H NMR (for 1-2 solid state and solution NMR where feasible), and X-ray crystallography. The structures of 1-3 reveal the presence of uniquely defined dinuclear complexes of octahedral Al(III) bound to fully deprotonated phosphonate ligands, water and hydroxo moieties. The aqueous solution speciation studies on the aforementioned binary systems project a clear picture of the binary Al(III)-(carboxy)phosphonate interactions and species under variable pH-conditions and specific Al(III):ligand stoichiometry. The concurrent solid state and solution work (a) exemplifies essential structural and chemical attributes of soluble aqueous species, reflecting well-defined interactions of Al(III) with phosphosubstrates and (b) strengthens the potential linkage of neurotoxic Al(III) chemical reactivity toward O,N-containing (carboxy)phosphate-rich cellular targets.
Georgantas
V
V
Laboratory of Inorganic Chemistry, Department of Chemical Engineering, Aristotle University of Thessaloniki, Thessaloniki 54124, Greece.
Kotsakis
N
N
Raptopoulou
C P
CP
Terzis
A
A
Iordanidis
L
L
Zervou
M
M
Jakusch
T
T
Kiss
T
T
Salifoglou
A
A
D000535:Aluminum / Q000737:chemistry / Q000633:toxicity*; D018360:Crystallography, X-Ray; D012968:Etidronic Acid / Q000138:chemical synthesis / Q000737:chemistry; D006801:Humans; D007098:Imino Acids / Q000737:chemistry; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D019636:Neurodegenerative Diseases / Q000139:chemically induced; D009474:Neurons / Q000187:drug effects*; D063065:Organophosphonates / Q000737:chemistry / Q000633:toxicity*
D007098:Imino Acids; D008024:Ligands; D063065:Organophosphonates; D000535:Aluminum; D012968:Etidronic Acid; C008109:iminodiacetic acid