TY - JOUR
T1 - Evidence for polynuclear aggregates of ferric daunomycin: A Mössbauer, EPR, X‐ray absorption spectroscopy and magnetic susceptibility study
AU - MATZANKE, Berthold F.
AU - BILL, Eckhard
AU - BUTZLAFF, Christian
AU - TRAUTWEIN, Alfred X.
AU - WINKLER, Heiner
AU - HERMES, Christoph
AU - NOLTING, Hans‐Friedrich ‐F
AU - BARBIERI, Renato
AU - RUSSO, Umberto
PY - 1992/1/1
Y1 - 1992/1/1
N2 - The interaction of the antitumor agent daunomycin (DN) with ferric iron has been analysed by Mössbauer spectroscopy, EPR, extended X‐ray absorption fine structure (EXAFS), and magnetic susceptibility measurements. In contrast to literature data, at millimolar iron and anthracycline concentrations no solitary Fe(DN)3 complexes are formed in appreciable amounts. The Mössbauer spectroscopic analysis revealed severe dependencies on temperature, on the preparation procedure, the time allowed for equilibration, and on the metal/ligand ratio. The Mössbauer spectra exhibit two components: a broad magnetic sextet and a quadrupole doublet at an Fe/DN molar ratio of 1:3 and exclusively a doublet at a molar ratio of 1:20, indicating an equilibrium of these two spectral components. The EPR spectra are dominated by a signal at geff=2. Double integration of the EPR signals enabled the determination of thier spin density and a correlation between EPR and Mössbauer spectra. The Mössbauer sextet species is EPR invisible and corresponds to magnetically ordered polynuclear aggregates with high magnetic anisotropy. EXAFS and susceptibility measurements provide additional evidence for the formation of polynuclear aggregates of ferric daunomycin. The quadrupole doublet species in the Mössbauer spectra correlates with the g=2 signal in EPR. This species is also related to a magnetically ordered system, exhibiting, however, superparamagnetic behavior due to loss magnetic anisotropy. Since daunomycin forms dimers in aqueous solution at millimolar concentrations, we conclude that the cooperative phenomena observed in EPR and Mössbauer spectra are a consequence of its stacking effects.
AB - The interaction of the antitumor agent daunomycin (DN) with ferric iron has been analysed by Mössbauer spectroscopy, EPR, extended X‐ray absorption fine structure (EXAFS), and magnetic susceptibility measurements. In contrast to literature data, at millimolar iron and anthracycline concentrations no solitary Fe(DN)3 complexes are formed in appreciable amounts. The Mössbauer spectroscopic analysis revealed severe dependencies on temperature, on the preparation procedure, the time allowed for equilibration, and on the metal/ligand ratio. The Mössbauer spectra exhibit two components: a broad magnetic sextet and a quadrupole doublet at an Fe/DN molar ratio of 1:3 and exclusively a doublet at a molar ratio of 1:20, indicating an equilibrium of these two spectral components. The EPR spectra are dominated by a signal at geff=2. Double integration of the EPR signals enabled the determination of thier spin density and a correlation between EPR and Mössbauer spectra. The Mössbauer sextet species is EPR invisible and corresponds to magnetically ordered polynuclear aggregates with high magnetic anisotropy. EXAFS and susceptibility measurements provide additional evidence for the formation of polynuclear aggregates of ferric daunomycin. The quadrupole doublet species in the Mössbauer spectra correlates with the g=2 signal in EPR. This species is also related to a magnetically ordered system, exhibiting, however, superparamagnetic behavior due to loss magnetic anisotropy. Since daunomycin forms dimers in aqueous solution at millimolar concentrations, we conclude that the cooperative phenomena observed in EPR and Mössbauer spectra are a consequence of its stacking effects.
UR - http://www.scopus.com/inward/record.url?scp=0026635263&partnerID=8YFLogxK
U2 - 10.1111/j.1432-1033.1992.tb17105.x
DO - 10.1111/j.1432-1033.1992.tb17105.x
M3 - Journal articles
C2 - 1321721
AN - SCOPUS:0026635263
SN - 0014-2956
VL - 207
SP - 747
EP - 755
JO - European Journal of Biochemistry
JF - European Journal of Biochemistry
IS - 2
ER -
