Sunhee Choi

INTERACTION OF CYTOCHROME C WITH CARDIOLIPIN : AN INFRARED SPECTROSCOPIC STUDY

The interactions of cytochrome c (cyt c) with cardiolipin, a major anionic phospholipid of mitochondrial membranes, and dioleoylphosphatidylglycerol (DOPG), have been compared by infrared (IR) spectroscopy. The Fourier self-deconvoluted IR spectra of the lipid carbonyl groups indicate that both cyt c3+ and cyt c2+ perturb and/or dehydrate the interfacial region of cardiolipin bilayers. Only a slight perturbation, if any, is observed in the interfacial region of DOPG bilayers. However, the phosphate head region of DOPG is perturbed by cyt c3+, which was not detected in cardiolipin. The results suggest that cytochrome c in both redox states can partially penetrate into cardiolipin but not into DOPG bilayers. The interaction of cyt c with cardiolipin and DOPG is mainly hydrophobic and electrostatic, respectively. The Fourier self-deconvoluted IR spectra in the amide I region reveal that ca. 10% of the cyt c3+ alpha-helix unfolds to random coil upon binding to cardiolipin bilayers. However, only very slight secondary structural changes, if any, were detected when cyt c3+ binds to DOPG bilayers.

Oxidation of a guanine derivative coordinated to a Pt(IV) complex initiated by intermolecular nucleophilic attacks

In this study we report that fac-[Pt(IV)(dach)(9-EtG)Cl(3)](+) (dach = d,l-1,2-diaminocyclohexane, 9-EtG = 9-ethylguanine) in high pH (pH 12) or phosphate solution (pH 7.4) produces 8-oxo-9-EtG and Pt(II) species. The reaction in H(2)(18)O revealed that the oxygen atom in hydroxide or phosphate ends up at the C8 position of 8-oxo-G. The kinetics of the redox reaction was first order with respect to both Pt(IV)-G and free nucleophiles (OH(-) and phosphate). The oxidation of G initiated by hydroxide was approximately 30∼50 times faster than by phosphate in 100 mM NaCl solutions. The large entropy of activation of OH(-1) (ΔS(‡) = 26.6 ± 4.3 J mol(-1) K(-1)) due to the smaller size of OH(-) is interpreted to be responsible for the faster kinetics compared to phosphate (ΔS(‡) = -195.5 ± 11.1 J mol(-1) K(-1)). The enthalpy of activation for phosphate reaction is more favorable relative to the OH(-) reaction (ΔH(‡) = 35.4 ± 3.5 kJ mol(-1) for phosphate vs. 96.6 ± 11.4 kJ mol(-1) for OH(-1)). The kinetic isotope effect of H8 was determined to be 7.2 ± 0.2. The rate law, kinetic isotope effect, and isotopic labeling are consistent with a mechanism involving proton ionization at the C8 position as the rate determining step followed by two-electron transfer from G to Pt(IV).

Fourier transform infrared spectroscopy.

Publisher Summary The very term “Fourier transform infrared spectroscopy” (FTIR) has become obsolete because there are now no research-quality non-Fourier transform (dispersive) mid-infrared spectrometers being manufactured commercially. Fundamental differences between an FTIR spectrometer and a dispersive-IR spectrometer go well beyond the mere convenience of having data in digital format. The way in which an FTIR spectrometer records a spectrum must be understood to set the optimum data collection parameters for a particular sample. There is no one combination of instrument, data collection parameters, and sampling device that will provide the best possible signal-to-noise ratio (S/N) throughout the infrared spectrum. A typical sample of a submillimolar protein solution in water pushes the limits of the instrument because of the dilute analyte and the high absorbance due to water. The optimum sample path length, detector, detector amplifier gain, and data sampling rate will depend on a region of the spectrum. This chapter discusses the basics of Fourier transform spectroscopy and spectrometers that are important in obtaining the highest S/N in a spectrum of an aqueous biological sample. This chapter discusses and illustrates some of the sampling devices and techniques that have been successfully used for aqueous protein FTIR studies.

Glycation of Lys-16 and Arg-5 in amyloid-β and the presence of Cu2+ play a major role in the oxidative stress mechanism of Alzheimer’s disease

Extensive research has linked the amyloid-beta (Aβ) peptide to neurological dysfunction in Alzheimer’s disease (AD). Insoluble Aβ plaques in the AD patient brain contain high concentrations of advanced glycation end-products (AGEs) as well as transition metal ions. This research elucidated the roles of Aβ, sugars, and Cu2+ in the oxidative stress mechanism of AD at the molecular level. Mass spectral (MS) analysis of the reactions of Aβ with two representative sugars, ribose-5-phosphate (R5P) and methylglyoxal (MG), revealed Lys-16 and Arg-5 as the primary glycation sites. Quantitative analysis of superoxide

Reduction and Anticancer Activity of Platinum(IV) Complexes

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Vinyl influences on protoheme resonance Raman spectra: nickel(II) protoporphyrin IX with deuterated vinyl groups

O2∙- production by a cyt c assay showed that Lys-16 generated four times as much

STRUCTURAL CORRELATIONS AND VINYL INFLUENCES IN RESONANCE RAMAN SPECTRA OF PROTOHEME COMPLEXES AND PROTEINS

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