ABSTRACT
The catechol functional group plays a major role in the chemistry of a wide variety of molecules important in biology and technology. In eumelanin, intermolecular hydrogen bonding between these functional groups is thought to contribute to UV photoprotective and radical buffering properties, but the mechanisms are poorly understood. Here, aggregates of 4-t-butylcatechol are used as model systems to study how intermolecular hydrogen bonding influences photochemical pathways that may occur in eumelanin. Ultrafast UV-visible and mid-IR transient absorption measurements are used to identify the photochemical processes of 4-t-butylcatechol monomers and their hydrogen-bonded aggregates in cyclohexane solution. Monomer photoexcitation results in hydrogen atom ejection to the solvent via homolytic O-H bond dissociation with a time constant of 12 ps, producing a neutral semiquinone radical with a lifetime greater than 1 ns. In contrast, intermolecular hydrogen bonding interactions within aggregates retard O-H bond photodissociation by over an order of magnitude in time. Excited state structural relaxation is proposed to slow O-H dissociation, allowing internal conversion to the ground state to occur in hundreds of picoseconds in competition with this channel. The semiquinone radicals formed in the aggregates exhibit spectral broadening of both their electronic and vibrational transitions.
ABSTRACT
Availability of molecular methods, gene sequencing, and phylogenetic species recognition have led to rare fungi being recognized as opportunistic pathogens. Fungal keratitis and onychomycosis are fairly common mycoses in the tropics, especially among outdoor workers and enthusiasts. The frequently isolated etiological agents belong to genera Candida, Aspergillus, and Fusarium. Within the genus Fusarium, known to be recalcitrant to prolonged antifungal treatment and associated with poor outcome, members of the Fusarium solani species complex are reported to be most common, followed by members of the Fusarium oxysporum SC and the Fusarium fujikuroi SC (FFSC). Morphological differentiation among the various members is ineffective most times. In the present study, we describe different species of the FFSC isolated from clinical specimen in south India. All twelve isolates were characterized up to species level by nucleic acid sequencing and phylogenetic analysis. The molecular targets chosen were partial regions of the internal transcribed spacer rDNA region, the panfungal marker and translation elongation factor-1α gene, the marker of choice for Fusarium speciation. Phylogenetic analysis was executed using the Molecular Evolutionary Genetics Analysis software (MEGA7). In vitro susceptibility testing against amphotericin B, voriconazole, posaconazole, natamycin, and caspofungin diacetate was performed following the CLSI M38-A2 guidelines for broth microdilution method. The twelve isolates of the FFSC were F. verticillioides (n = 4), F. sacchari (n = 3), F. proliferatum (n = 2), F. thapsinum (n = 1), F. andiyazi (n = 1), and F. pseudocircinatum (n = 1). To the best of our knowledge, this is the first report of F. andiyazi from India and of F. pseudocircinatum as a human pathogen worldwide. Natamycin and voriconazole were found to be most active agents followed by amphotericin B. Elderly outdoor workers figured more among the patients and must be recommended protective eye wear.
