PubMed · 5607596
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1967-06-30. [Daunomycin].. https://pubmed.ncbi.nlm.nih.gov/5607596/
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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 g(eff) = 2. Double integration of the EPR signals enabled the determination of their 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 less 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.
A rapid method for the determination of daunorubicin, doxorubicin and epirubicin in human plasma is described. Samples are pretreated and concentrated by liquid-liquid extraction with chloroform and back-extraction into phosphoric acid, respectively. This pretreatment results in a sample matrix of low ionic strength in comparison with the electrophoresis buffer, permitting a 20-30-fold increase in the injected amount by zone sharpening when electrokinetic injection is applied. Analyte interaction with the capillary wall is prevented by using high acetonitrile contents in the electrophoresis buffer, which results in reproducible migration times and highly efficient separations. Laser-induced fluorescence detection provides an extremely sensitive and selective method without detectable biological interferences. The limit of determination of daunorubicin, epirubicin and doxorubicin in plasma ranges from 125 to 250 pg/ml.
We describe the long-term results after treatment of 68 eyes showing advanced stages of proliferative vitreoretinopathy with vitrectomy, daunomycin perfusion, and silicone-oil injection. Six reoperations were performed. After 18 months, 73% of the eyes showed no signs of retinal detachment and 89% had a visual acuity of greater than 20/800. These results are better than those reported in previously published studies. Whether this improvement was due to the daunomycin treatment or to more aggressive surgical techniques such as retinotomies remains to be answered by a randomized trial.