Biliverdin (BV) structure was analyzed by using NMR techniques and unrestricted density function theory simulations to explain the incapacity of BV to build coordination complex(es) with Cu2+ in dimethyl sulfoxide, which was confirmed by UV-Vis, EPR and NMR spectroscopy. NMR showed that N atoms are protonated in all four pyrrole rings. The structure is stabilized by two hydrogen bonds between NH moieties and carbonyl oxygens from opposite terminal pyrrole rings, and by the bending of propionyl chain with carboxyl group out of the plain toward central position of BV. The simulations of deprotonated BV, which builds copper complexes in water and chloroform as described previously, showed a different conformation and organization of hydrogen bonds. Taking into account that deprotonation represents a critical step in coordinate bonds formation, the protonation of an additional N atom may represent a key difference between the interactions of BV with copper in different solvents.
TY - JOUR
AU - Dimitrijević, Milena
AU - Žižić, Milan
AU - Piccioli, Mario
AU - Bogdanović Pristov, Jelena
AU - Spasojević, Ivan
PY - 2019
UR - http://rimsi.imsi.bg.ac.rs/handle/123456789/1210
AB - Biliverdin (BV) structure was analyzed by using NMR techniques and unrestricted density function theory simulations to explain the incapacity of BV to build coordination complex(es) with Cu2+ in dimethyl sulfoxide, which was confirmed by UV-Vis, EPR and NMR spectroscopy. NMR showed that N atoms are protonated in all four pyrrole rings. The structure is stabilized by two hydrogen bonds between NH moieties and carbonyl oxygens from opposite terminal pyrrole rings, and by the bending of propionyl chain with carboxyl group out of the plain toward central position of BV. The simulations of deprotonated BV, which builds copper complexes in water and chloroform as described previously, showed a different conformation and organization of hydrogen bonds. Taking into account that deprotonation represents a critical step in coordinate bonds formation, the protonation of an additional N atom may represent a key difference between the interactions of BV with copper in different solvents.
PB - Springer/Plenum Publishers, New York
T2 - Structural Chemistry
T1 - The conformation of biliverdin in dimethyl sulfoxide: implications for the coordination with copper
EP - 2166
IS - 6
SP - 2159
VL - 30
DO - 10.1007/s11224-019-01354-5
ER -
@article{
author = "Dimitrijević, Milena and Žižić, Milan and Piccioli, Mario and Bogdanović Pristov, Jelena and Spasojević, Ivan",
year = "2019",
abstract = "Biliverdin (BV) structure was analyzed by using NMR techniques and unrestricted density function theory simulations to explain the incapacity of BV to build coordination complex(es) with Cu2+ in dimethyl sulfoxide, which was confirmed by UV-Vis, EPR and NMR spectroscopy. NMR showed that N atoms are protonated in all four pyrrole rings. The structure is stabilized by two hydrogen bonds between NH moieties and carbonyl oxygens from opposite terminal pyrrole rings, and by the bending of propionyl chain with carboxyl group out of the plain toward central position of BV. The simulations of deprotonated BV, which builds copper complexes in water and chloroform as described previously, showed a different conformation and organization of hydrogen bonds. Taking into account that deprotonation represents a critical step in coordinate bonds formation, the protonation of an additional N atom may represent a key difference between the interactions of BV with copper in different solvents.",
publisher = "Springer/Plenum Publishers, New York",
journal = "Structural Chemistry",
title = "The conformation of biliverdin in dimethyl sulfoxide: implications for the coordination with copper",
pages = "2166-2159",
number = "6",
volume = "30",
doi = "10.1007/s11224-019-01354-5"
}
Dimitrijević, M., Žižić, M., Piccioli, M., Bogdanović Pristov, J.,& Spasojević, I.. (2019). The conformation of biliverdin in dimethyl sulfoxide: implications for the coordination with copper. in Structural Chemistry
Springer/Plenum Publishers, New York., 30(6), 2159-2166.
https://doi.org/10.1007/s11224-019-01354-5
Dimitrijević M, Žižić M, Piccioli M, Bogdanović Pristov J, Spasojević I. The conformation of biliverdin in dimethyl sulfoxide: implications for the coordination with copper. in Structural Chemistry. 2019;30(6):2159-2166.
doi:10.1007/s11224-019-01354-5 .
Dimitrijević, Milena, Žižić, Milan, Piccioli, Mario, Bogdanović Pristov, Jelena, Spasojević, Ivan, "The conformation of biliverdin in dimethyl sulfoxide: implications for the coordination with copper" in Structural Chemistry, 30, no. 6 (2019):2159-2166,
https://doi.org/10.1007/s11224-019-01354-5 . .
