Biliverdin (BV), a product of heme catabolism, is known to interact with transition metals, but the details of such interactions under physiological conditions are scarce. Herein, we examined coordinate/redox interactions of BV with Cu2+ in phosphate buffer at pH 7.4, using spectrophotometry, HESI-MS, Raman spectroscopy, H-1 NMR, EPR, fluorimetry, and electrochemical methods. BV formed a stable coordination complex with copper in 1:1 stoichiometry. The structure of BV was more planar and energetically stable in the complex. The complex showed strong paramagnetic effects that were attributed to an unpaired delocalized e(-). The delocalized electron may come from BV or Cu2+, so the complex is formally composed either of BV radical cation and Cu1+ or of BV radical anion and Cu3+. The complex underwent oxidation only in the presence of both O-2 and an excess of Cu2+, or a strong oxidizing agent, and it was resistant to reducing agents. The biological effects of the stable BV metallocomplex... containing a delocalized unpaired electron should be further examined, and may provide an answer to the long-standing question of high energy investment in the catabolism of BV, which represents a relatively harmless molecule per se.
TY - JOUR
AU - Dimitrijević, Milena
AU - Bogdanović Pristov, Jelena
AU - Žižić, Milan
AU - Stanković, Dalibor M.
AU - Bajuk-Bogdanović, Danica
AU - Stanić, Marina
AU - Spasic, Snežana
AU - Hagen, Wilfred
AU - Spasojević, Ivan
PY - 2019
UR - http://rimsi.imsi.bg.ac.rs/handle/123456789/1246
AB - Biliverdin (BV), a product of heme catabolism, is known to interact with transition metals, but the details of such interactions under physiological conditions are scarce. Herein, we examined coordinate/redox interactions of BV with Cu2+ in phosphate buffer at pH 7.4, using spectrophotometry, HESI-MS, Raman spectroscopy, H-1 NMR, EPR, fluorimetry, and electrochemical methods. BV formed a stable coordination complex with copper in 1:1 stoichiometry. The structure of BV was more planar and energetically stable in the complex. The complex showed strong paramagnetic effects that were attributed to an unpaired delocalized e(-). The delocalized electron may come from BV or Cu2+, so the complex is formally composed either of BV radical cation and Cu1+ or of BV radical anion and Cu3+. The complex underwent oxidation only in the presence of both O-2 and an excess of Cu2+, or a strong oxidizing agent, and it was resistant to reducing agents. The biological effects of the stable BV metallocomplex containing a delocalized unpaired electron should be further examined, and may provide an answer to the long-standing question of high energy investment in the catabolism of BV, which represents a relatively harmless molecule per se.
PB - Royal Soc Chemistry, Cambridge
T2 - Dalton Transactions
T1 - Biliverdin-copper complex at physiological pH
EP - 6070
IS - 18
SP - 6061
VL - 48
DO - 10.1039/c8dt04724c
ER -
@article{
author = "Dimitrijević, Milena and Bogdanović Pristov, Jelena and Žižić, Milan and Stanković, Dalibor M. and Bajuk-Bogdanović, Danica and Stanić, Marina and Spasic, Snežana and Hagen, Wilfred and Spasojević, Ivan",
year = "2019",
abstract = "Biliverdin (BV), a product of heme catabolism, is known to interact with transition metals, but the details of such interactions under physiological conditions are scarce. Herein, we examined coordinate/redox interactions of BV with Cu2+ in phosphate buffer at pH 7.4, using spectrophotometry, HESI-MS, Raman spectroscopy, H-1 NMR, EPR, fluorimetry, and electrochemical methods. BV formed a stable coordination complex with copper in 1:1 stoichiometry. The structure of BV was more planar and energetically stable in the complex. The complex showed strong paramagnetic effects that were attributed to an unpaired delocalized e(-). The delocalized electron may come from BV or Cu2+, so the complex is formally composed either of BV radical cation and Cu1+ or of BV radical anion and Cu3+. The complex underwent oxidation only in the presence of both O-2 and an excess of Cu2+, or a strong oxidizing agent, and it was resistant to reducing agents. The biological effects of the stable BV metallocomplex containing a delocalized unpaired electron should be further examined, and may provide an answer to the long-standing question of high energy investment in the catabolism of BV, which represents a relatively harmless molecule per se.",
publisher = "Royal Soc Chemistry, Cambridge",
journal = "Dalton Transactions",
title = "Biliverdin-copper complex at physiological pH",
pages = "6070-6061",
number = "18",
volume = "48",
doi = "10.1039/c8dt04724c"
}
Dimitrijević, M., Bogdanović Pristov, J., Žižić, M., Stanković, D. M., Bajuk-Bogdanović, D., Stanić, M., Spasic, S., Hagen, W.,& Spasojević, I.. (2019). Biliverdin-copper complex at physiological pH. in Dalton Transactions
Royal Soc Chemistry, Cambridge., 48(18), 6061-6070.
https://doi.org/10.1039/c8dt04724c
Dimitrijević M, Bogdanović Pristov J, Žižić M, Stanković DM, Bajuk-Bogdanović D, Stanić M, Spasic S, Hagen W, Spasojević I. Biliverdin-copper complex at physiological pH. in Dalton Transactions. 2019;48(18):6061-6070.
doi:10.1039/c8dt04724c .
