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Reversible Oxygenation of ?-Amino Acid-Cobalt(II) Complexes.

ABSTRACT: We systematically investigated the reversibility, time lapse, and oxygenation-deoxygenation properties of 15 natural ?-amino acid-Co(II) complexes through UV-vis spectrophotometer, polarographic oxygen electrode, and DFT calculations, respectively, to explore the relationship between the coordinating structure and reversible oxygenation of ?-amino acid-Co(II) complexes. Results revealed that the ?-amino acid structure plays a key role in the reversible oxygenation properties of these complexes. The specific configuration of the ?-amino acid group affects the eg (1) electron of Co(II) transfer to the ? (?) orbit of O2; this phenomenon also favors the reversible formation and dissociation of Co-O2 bond when O2 coordinates with Co(II) complexes. Therefore, the co-coordination of amino and carboxyl groups is a determinant of Co complexes to absorb O2 reversibly. The group adjacent to the ?-amino acid unit evidently influences the dioxygen affinity and antioxidation ability of the complexes. The presence of amino (or imino) and hydroxy groups adjacent to the ?-amino acid group increases the oxygenation-deoxygenation rate and the number of reversible cycles. Our findings demonstrate a new mechanism to develop reversible oxygenation complexes and to reveal the oxygenation of oxygen carriers.

SUBMITTER: Zhang X

PROVIDER: S-EPMC4789021 | biostudies-literature | 2016

REPOSITORIES: biostudies-literature

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Reversible Oxygenation of α-Amino Acid-Cobalt(II) Complexes.

Zhang Xincun X Yue Fan F Li Hui H Huang Yan Y Zhang Yi Y Wen Hongmei H Wang Jide J

Bioinorganic chemistry and applications 20160228

We systematically investigated the reversibility, time lapse, and oxygenation-deoxygenation properties of 15 natural α-amino acid-Co(II) complexes through UV-vis spectrophotometer, polarographic oxygen electrode, and DFT calculations, respectively, to explore the relationship between the coordinating structure and reversible oxygenation of α-amino acid-Co(II) complexes. Results revealed that the α-amino acid structure plays a key role in the reversible oxygenation properties of these complexes. ...[more]

PMID: 27022316

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Project description:BACKGROUND:The paper examines Co(II)-amino acid-imidazole systems (where amino acid = L-α-amino acid: alanine, asparagine, histidine) which, when in aqueous solutions, activate and reversibly take up dioxygen, while maintaining the structural scheme of the heme group (imidazole as axial ligand and O2 uptake at the sixth, trans position) thus imitating natural respiratory pigments such as myoglobin and hemoglobin. The oxygenated reaction shows higher reversibility than for Co(II)-amac systems with analogous amino acids without imidazole. Unlike previous investigations of the heteroligand Co(II)-amino acid-imidazole systems, the present study accurately calculates all equilibrium forms present in solution and determines the [Formula: see text]equilibrium constants without using any simplified approximations. The equilibrium concentrations of Co(II), amino acid, imidazole and the formed complex species were calculated using constant data obtained for analogous systems under oxygen-free conditions. Pehametric and volumetric (oxygenation) studies allowed the stoichiometry of O2 uptake reaction and coordination mode of the central ion in the forming oxygen adduct to be determined. The values of dioxygen uptake equilibrium constants [Formula: see text] were evaluated by applying the full mass balance equations. RESULTS:Investigations of oxygenation of the Co(II)-amino acid-imidazole systems indicated that dioxygen uptake proceeds along with a rise in pH to 9-10. The percentage of reversibility noted after acidification of the solution to the initial pH ranged within ca 30-60% for alanine, 40-70% for asparagine and 50-90% for histidine, with a rising tendency along with the increasing share of amino acid in the Co(II): amino acid: imidazole ratio. Calculations of the share of the free Co(II) ion as well as of the particular complex species existing in solution beside the oxygen adduct (regarding dioxygen bound both reversibly and irreversibly) indicated quite significant values for the systems with alanine and asparagine-in those cases the of oxygenation reaction is right shifted to a relatively lower extent. The experimental results indicate that the "active" complex, able to take up dioxygen, is a heteroligand CoL2L'complex, where L = amac (an amino acid with a non-protonated amine group) while L' = Himid, with the N1 nitrogen protonated within the entire pH range under study. Moreover, the corresponding log [Formula: see text] value at various initial total Co(II), amino acid and imidazole concentrations was found to be constant within the limits of error, which confirms those results. The highest log [Formula: see text] value, 14.9, occurs for the histidine system; in comparison, asparagine is 7.8 and alanine is 9.7. This high value is most likely due to the participation of the additional effective N3 donor of the imidazole side group of histidine. CONCLUSIONS:The Co(II)-amac-Himid systems formed by using a [Co(imid)2]n polymer as starting material demonstrate that the reversible uptake of molecular oxygen occurs by forming dimeric μ-peroxy adducts. The essential impact on the electron structure of the dioxygen bridge, and therefore, on the reversibility of O2 uptake, is due to the imidazole group at axial position (trans towards O2). However, the results of reversibility measurements of O2 uptake, unequivocally indicate a much higher effectiveness of dioxygenation than in systems in which the oxygen adducts are formed in equilibrium mixtures during titration of solutions containing Co(II) ions, the amino acid and imidazole, separately.

Dataset Information

Reversible Oxygenation of ?-Amino Acid-Cobalt(II) Complexes.

Publications

Reversible Oxygenation of α-Amino Acid-Cobalt(II) Complexes.

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