X-ray Photoelectron Spectroscopic Study of Some Organic and Inorganic Modified Clay Minerals

Layered clay systems intercalated with inorganic and organic compounds were analyzed to highlight how XPS can provide information on the different environments surrounding a particular atom as well as provide discernments on the size, coordination, and structural and oxidative transformations of the intercalating/pillaring compounds. XPS data on the intercalation of urea and K-acetate in low- and high-defect kaolinite revealed the interaction of the intercalating group NH2 with the siloxane functional groups in the interlayer surface. The intercalation of HDTMA in Mt demonstrated the use of XPS in monitoring the change in conformation assumed by alkylammonium intercalating compounds in Mt with increasing CEC. Studies on the pillaring of Mt by Al13 and Ga13 by XPS allowed determination of the coordination of the pillaring compound within the Mt layer. Lastly, the intercalation of hexacyanoferrate in hydrotalcite demonstrated the capability of XPS in following changes in the oxidation state of the iron compound. These were gleaned from interpretation of the shifts in binding energies and presence of multiplet splitting in the XPS of the component elements of the minerals or the intercalating compounds.

Oxidative Transformations of 3,4-Dihydroxyphenylacetaldehyde Generate Potential Reactive Intermediates as Causative Agents for Its Neurotoxicity

Neurogenerative diseases, such as Parkinson’s disease, are associated, not only with the selective loss of dopamine (DA), but also with the accumulation of reactive catechol-aldehyde, 3,4-dihydroxyphenylacetaldehyde (DOPAL), which is formed as the immediate oxidation product of cytoplasmic DA by monoamine oxidase. DOPAL is well known to exhibit toxic effects on neuronal cells. Both catecholic and aldehyde groups seem to be associated with the neurotoxicity of DOPAL. However, the exact cause of toxicity caused by this compound remains unknown. Since the reactivity of DOPAL could be attributed to its immediate oxidation product, DOPAL-quinone, we examined the potential reactions of this toxic metabolite. The oxidation of DOPAL by mushroom tyrosinase at pH 5.3 produced conventional DOPAL-quinone, but oxidation at pH 7.4 produced the tautomeric quinone-methide, which gave rise to 3,4-dihydroxyphenylglycolaldehyde and 3,4-dihydroxybenzaldehyde as products through a series of reactions. When the oxidation reaction was performed in the presence of ascorbic acid, two additional products were detected, which were tentatively identified as the cyclized products, 5,6-dihydroxybenzofuran and 3,5,6-trihydroxybenzofuran. Physiological concentrations of Cu(II) ions could also cause the oxidation of DOPAL to DOPAL-quinone. DOPAL-quinone exhibited reactivity towards the cysteine residues of serum albumin. DOPAL-oligomer, the oxidation product of DOPAL, exhibited pro-oxidant activity oxidizing GSH to GSSG and producing hydrogen peroxide. These results indicate that DOPAL-quinone generates several toxic compounds that could augment the neurotoxicity of DOPAL.

Synthesis and Oxidative Transformations of New Chiral Pinane-Type γ-Ketothiols: Stereochemical Features of Reactions

Chiral γ-ketothiols, thioacetates, thiobenzoate, disulfides, sulfones, thiosulfonates, and sulfonic acids were obtained from β-pinene for the first time. New compounds open up prospects for the synthesis of other polyfunctional compounds combining a biologically active pinane fragment with various pharmacophore groups. It was shown that the syntheses of sulfanyl and sulfonyl derivatives based on 2-norpinanone are characterized by high stereoselectivity in comparison with similar reactions of pinocarvone. The conditions for the preparation of diastereomerically pure thioacetyl and thiobenzoyl derivatives based on pinocarvone, as well as for the chemoselective oxidation of γ-ketothiols with chlorine dioxide to the corresponding thiolsulfonates and sulfonic acids, were selected. The effect of the VO(acac)2 catalyst on the increase in the yields of thiosulfonates was shown. A new direction of the transformation of thiosulfonates with the formation of sulfones was revealed. In the case of pinocarvone-based sulfones, the configuration is inversed at the C2 atom. An epimerization scheme is proposed.