The interaction of the platinum(II) polypyridine complexes [Pt(bipy)(2)](2+), [Pt(quaterpy)](2+), [Pt(terpy)(n-Rpy)](2+) and [Pt(bipy)(py)(2)](2+) (bipy = 2,2'-bipyridine; terpy = 2,2':6',2' '-terpyridine; quaterpy = 2,2':6',2' ':6' ',2' "-quaterpyridine; n-R = H, 2-CH(3), or 4-CH(3) ) with double-helix DNA has been studied with a variety of experimental techniques. Induced circular dichroism, strong hypochromism and red shifts of the absorption maxima of the complexes, increase in melting temperature and viscosity of DNA, and inhibition of the reaction of the complexes with thiourea in the presence of DNA, characterize the processes. Intercalation, implying the whole molecule or part of it, is the suggested binding mode. The binding constants, K(B), determined spectrophotometrically at 25 degrees C, pH 7, and I = 0.15 M, using the McGhee-von Hippel approach, increase in the order [Pt(bipy)(py)(2)](2+)< [Pt(terpy)(py)](2+)< [Pt(quaterpy)](2+), on increasing aromatic planar surface extension. The steric interference with double helix of the methyl group in [Pt(terpy)(2-Mepy)](2+) destabilizes the interaction by reducing the stacking surface.
The interaction with DNA of the platinum(II) square planar complexes [Pt(N-N)(py)(2)](2+) (N-N = 1,10-phenanthroline (phen), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), dipyrido[3,2-a:2',3'-c]phenazine (dppz), benzodipyrido[b:3,2-h:2'3'-f]phenazine (bdppz)) has been investigated by means of absorption, circular and linear dichroism spectroscopy, DNA melting, and viscosity. In the presence of excess [DNA] all the complexes intercalate to the double helix. For those with the most extended phenanthrolines the binding mode depends on the [DNA]/[complex] ratio (q); at low q values the substances bind externally to DNA probably self-aggregating along the double helix. When the DNA concentration is large enough, the aggregate breaks up and the complex intercalates within the nucleobases. The complexes self-aggregate, without added DNA, in the presence of a large salt concentration.
Preconditioning (PC) is an adaptive response to a mild and transient oxidative stress, shown for the first time in myocardial cells and not described in erythrocytes so far. The possible adaptation of human erythrocytes to hydrogen peroxide (HO)-induced oxidative stress has been here verified by monitoring one of band 3 protein functions, i.e., Cl/HCO exchange, through rate constant for SO uptake measurement. With this aim, erythrocytes were exposed to a mild and transient oxidative stress (30 min to either 10 or 100 μM HO), followed by a stronger oxidant condition (300- or, alternatively, 600-μM HO treatment). SO uptake was measured by a turbidimetric method, and the possible role of catalase (CAT, significantly contributing to the anti-oxidant system in erythrocytes) in PC response has been verified by measuring the rate of HO degradation. The preventive exposure of erythrocytes to 10 μM HO, and then to 300 μM HO, significantly ameliorated the rate constant for SO uptake with respect to 300 μM HO alone, showing thus an adaptive response to oxidative stress. Our results show that (i) SO uptake measurement is a suitable model to monitor the effects of a mild and transient oxidative stress in human erythrocytes, (ii) band 3 protein anion exchange capability is retained after 10 μM HO treatment, (iii) PC response induced by the 10 μM HO pretreatment is clearly detected, and (iv) PC response, elicited by low-concentrated HO, is mediated by CAT enzyme and does not involve band 3 protein tyrosine phosphorylation pathways. Erythrocyte adaptation to a short-term oxidative stress may serve as a basis for future studies about the impact of more prolonged oxidative events, often associated to aging, drug consumption, chronic alcoholism, hyperglycemia, or neurodegenerative diseases.
The interaction of the complexes [Pt(bipy)(4-Rpy)(2)](2+) and [Pt(4,4'-Ph(2)bipy)(4-Rpy)(2)](2+) (Ph = phenyl; bipy = 2,2'-bipyridine; R = H, CN, CH(3), NH(2)) with DNA has been studied with a series of techniques. The processes give rise to (i) lengthening of rodlike DNA and unwinding of closed circular DNA and (ii) an increase in the DNA melting temperature comparable with that observed for known intercalators. In addition, the reaction of the complexes [Pt(bipy)(py)(2)](2+) and [Pt(4,4'-Ph(2)bipy)(py)(2)](2+) is inhibited by the presence of DNA. These results have been interpreted by assuming that the substances intercalate in spite of the presence of ligands out of plane. The crystal structure determined for [Pt(4,4'-Ph(2)bipy)(3,5-Me(2)py)(2)](2+) by X-ray analysis shows that also one of the phenyl rings is twisted with respect to the square plane. Binding constants, K(B), determined spectrophotometrically at 25 degrees C and pH 7 using the McGhee-von Hippel approach, increase for both series of complexes on increasing pK(a) of coordinated pyridines and are larger for those with 4,4'-Ph(2)bipy. The increasing affinity for DNA on increasing electron density of the interacting moiety is accounted for by assuming that London dispersion forces play a major role in the processes.
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