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New developments in the comprehension of the biotransformation and transport of insulin-enhancing vanadium compounds in the blood serum

Sanna, Daniele and Micera, Giovanni and Garribba, Eugenio (2010) New developments in the comprehension of the biotransformation and transport of insulin-enhancing vanadium compounds in the blood serum. Inorganic Chemistry, Vol. 49 (1), p. 174-187. eISSN 1520-510X. Article.

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DOI: 10.1021/ic9017213

Abstract

The possible biotransformations in the blood serum of four representative insulin-enhancing vanadium compounds, [VO(6-mepic)2], cis-[VO(pic)2(H2O)], [VO(acac)2], and [VO(dhp)2], where 6-mepic, pic, acac, and dhp indicate the deprotonated forms of 6-methylpicolinic and picolinic acids, acetylacetone, and 1,2-dimethyl-3-hydroxy-4(1H)-pyridinone, were examined. In particular, the behavior of the quinary systems formed by the insulin-enhancing species, human serum apo-transferrin (hTf), human serum albumin (HSA), and lactate (lact) or citrate (citr) at physiological pH and conditions was studied. The results indicate that, besides the case in which the ligand is very weak like 6-mepic, the carrier can interact in some form with VO2+ ion until its intake into the cell. In fact with stronger ligands like pic, acac, and dhp, VO2+ is transported not only by transferrin but also as [VO(carrier)2] and as mixed species VO2+−hTF−carrier. There are two ways in which the undissociated form of a bis-chelated complex can interact with transferrin, one “specific” when the carrier possesses a carboxylate group and behaves like a synergistic anion, and another “non-specific” when an imidazole nitrogen of a histidine residue from hTf replaces an equatorially coordinated water molecule giving rise to a ternary species with cis-octahedral geometry and cis-VO(carrier)2(hTf) stoichiometry. It is found that also albumin can participate in the transport of an insulin-enhancing compound forming a mixed species cis-VO(carrier)2(HSA), when the carrier stabilizes in aqueous solution the cis-octahedral form, or the dinuclear compound (VO)2dHSA, when the carrier forms unstable complexes. These insights were confirmed through density functional theory (DFT) calculations.

Item Type:Article
ID Code:3732
Status:Published
Refereed:Yes
Uncontrolled Keywords:Blood serum, biotransformations, insulin-enhancing
Subjects:Area 03 - Scienze chimiche > CHIM/03 Chimica generale e inorganica
Divisions:001 Università di Sassari > 02 Centri > Centro di eccellenza interdisc. sviluppo ricerca biotecnologica e studio biodiversità della Sardegna e dell'area mediterranea
001 Università di Sassari > 01 Dipartimenti > Chimica
002 Altri enti e centri di ricerca del Nord Sardegna > CNR-Consiglio Nazionale delle Ricerche > Istituto di chimica biomolecolare, Sassari
Publisher:American Chemical Society
eISSN:1520-510X
Deposited On:15 Apr 2010 12:11

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