Two imines of different molecular sizes namely 3-(phenylimino) indolin-2-one (PII) and 3,3- (1,4-phenylenebis (azan-1-yl-1-ylidene) diindolin-2-one (PDI) were investigated for their corrosion inhibition on mild steel in 1 M HCl solution using electrochemical impedance spectroscopy (EIS). The bigger molecule PDI containing double the amount of isatin moiety exhibited higher inhibition efficiency of 87.3% while PII that contained monoisatin moiety showed a lower inhibition efficiency of 74.8%. Both compounds had an increase in inhibition efficiencies percentage as concentrations increased. Density functional theory (DFT) was used to determine the correlation between the corrosion inhibition efficiency and electronic parameters. The DFT calculations indicated that the corrosion inhibition efficiency was mainly dependant on the frontier orbital energy gap and the chemical softness/hardness of the imines.
Hispidin oligomers are styrylpyrone pigments isolated from the medicinal fungi Inonotus xeranticus and Phellinus linteus. They exhibit diverse biological activities and strong free radical scavenging activity. To rationalize the antioxidant activity of a series of four hispidin oligomers and determine the favored mechanism involved in free radical scavenging, DFT calculations were carried out at the B3P86/6-31+G (d, p) level of theory in gas and solvent. The results showed that bond dissociation enthalpies of OH groups of hispidin oligomers (ArOH) and spin density delocalization of related radicals (ArO•) are the appropriate parameters to clarify the differences between the observed antioxidant activities for the four oligomers. The effect of the number of hydroxyl groups and presence of a catechol moiety conjugated to a double bond on the antioxidant activity were determined. Thermodynamic and kinetic studies showed that the PC-ET mechanism is the main mechanism involved in free radical scavenging. The spin density distribution over phenoxyl radicals allows a better understanding of the hispidin oligomers formation.