Spectral features of interaction of hemin and zinc porphyrin with sodium hexamolybdenicelate

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Abstract

The interaction of hemin and the Zn(II)-complex of tetra(4-pyridyl)porphyrin (ZnTPP) with hexamolybdenonickelate anions in an aqueous medium has been studied by electron absorption spectroscopy and spectrofluorimetry. Differences in spectral behavior of two metal porphyrins when interacting with heteropoly compounds are associated with differences in the structure of these porphyrins. Both the transformation of the porphyrins characteristic bands is manifested, and new bands are found in the electron absorption spectra that indicates the formation of hybrid organo-inorganic complexes. In addition, fluorescence quenching of ZnTPP, predominantly of the static type, is observed, which also testifies the formation of hybrid complexes. The binding ability of the ZnTPP system - crystalline hydrate of sodium hexamolibdenonicelate (HMN) was evaluated, as well as the stability of the obtained hybrid complex. The results of the study will be useful when creating hybrid complexes by molecular design in order to further incorporate them into various biomedical applications.

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About the authors

I. V. Klimenko

Emanuel Institute of Biochemical Physics, Russian Academy of Sciences

Author for correspondence.
Email: inna@deom.chph.ras.ru
Russian Federation, Moscow

E. V. Kitushina

Emanuel Institute of Biochemical Physics, Russian Academy of Sciences; Moscow State Pedagogical University, Institute of Biology and Chemistry

Email: inna@deom.chph.ras.ru
Russian Federation, Moscow; Moscow

A. V. Oreshkina

Moscow State Pedagogical University, Institute of Biology and Chemistry

Email: inna@deom.chph.ras.ru
Russian Federation, Moscow

A. V. Lobanov

Emanuel Institute of Biochemical Physics, Russian Academy of Sciences; Moscow State Pedagogical University, Institute of Biology and Chemistry

Email: inna@deom.chph.ras.ru
Russian Federation, Moscow; Moscow

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2. Fig. 1. Structure of GPS (a), ZnTPP (b) and FePP (c).

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3. Fig. 2. Electronic absorption spectra of GMN and porphyrins: a – spectra of GMN (10-5 mol/l) in water (1), FePP (10-5 mol/l) in DMF (2), GMN (10-5 mol/l) and FePP (10-5 mol/l) in the water–DMF system in a ratio of 1:1 (3), FePP (10-5 mol/l) in the water–DMF system in a ratio of 1:1 (4); b – spectra of GMN (10-5 mol/l) in water (1), ZnTPP (10-5 mol/l) in DMF (2), ZnTPP (10-5 mol/l) in the water – DMF system in a ratio of 1:1 (3), GMN (10-5 mol/l) and ZnTPP (10-6 mol/l) in the water – DMF system in a ratio of 1:1 (4), GMN (10-5 mol/l) and ZnTPP (10-5 mol/l) in the water – DMF system in a ratio of 1:1 (5).

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4. Fig. 3. Fluorescence spectra of ZnTPP in DMF during titration with a solution of HMN in water (10-5 mol/L); СZnTPP in the system: 1 – 1 ∙ 10-5 mol/L (without adding HMN); 2 – 8 ∙ 10-6 mol/L; 3 – 6.7 ∙ 10-6 mol/L; 4 – 5.7 ∙ 10-6 mol/L; 5 – 5 ∙ 10-6 mol/L; 6 – 4.4 ∙ 10-6 mol/L; 7 – 4 ∙ 10-6 mol/L; 8 – 3.6 ∙ 10-6 mol/L; 9 – 3.3 ∙ 10-6 mol/L; λex = 430 nm. The inset shows a graph for calculating the Stern–Volmer constant, where Ifl0 and Ifl are the fluorescence intensities in the absence and presence of the quencher, respectively.

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5. Fig. 4. Absorption spectra of ZnTPP in DMF during titration with a solution of HMN in water (10-5 mol/L); CZnTPP in the system: 1 – 1 ∙ 10-5 mol/L (without adding HMN); 2 – 8 ∙ 10-6 mol/L; 3 – 6.7 ∙ 10-6 mol/L; 4 – 5.7 ∙ 10-6 mol/L; 5 – 5 ∙ 10-6 mol/L; 6 – 4.4 ∙ 10-6 mol/L; 7 – 4 ∙ 10-6 mol/L; 8 – 3.6 ∙ 10-6 mol/L; 9 – 3.3 ∙ 10-6 mol/L. The inset shows a graph for calculating the binding constant in Benesi–Hildebrand coordinates.

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