Spectroscopic and photochemical properties of some annulated boldine derivatives

Abstract

O objetivo deste estudo foi determinar a influência dos grupos substituintes na fotoestabilidade de oito derivados de boldina, incluindo alguns derivados de oxazol e oxazinona, com o propósito de aumentar as propriedades de proteção solar previamente demonstradas para boldina. Tais derivados apresentaram bandas similares à boldina nos espectros de absorção e emissão. As propriedades espectroscópicas são dependentes do pH. A fotoestabilidade dos derivados foi maior que a da boldina, em conformidade com o baixo valor obtido para o rendimento de fotoconsumo quântico. Os baixos valores de rendimento quântico de fluorescência observados para a boldina 1 e 4, tanto na sua forma de base como hidrocloreto, possibilitam postular que esses compostos são desativados por um mecanismo diferente ao da fluorescência, provavelmente devido ao efeito retirador de elétron do grupo NO para a boldina 1 e ao aumento da aromaticidade para a boldina 4.The aim of this study was to determine the influence of the substituent groups on the photostability of eight boldine derivatives, including some oxazole and oxazinone derivatives, in order to increase the sunscreen protection properties previously demonstrated for boldine. Such derivatives showed bands similar to those of boldine in the absorption and emission spectrum. The spectroscopic properties are pH dependent. The photostability of the derivative compounds was higher than that of boldine, in accordance with the low value of the photoconsumption quantum yield determined. The low fluorescence quantum yield values observed for boldine 1 and 4 as both base and hydrochloride derivative compounds led us to postulate that these compounds are deactivated by a mechanism different to the fluorescence pathway, probably due to the electron-withdrawing inductive effect of NO for boldine 1, and to the increase of the aromatic framework for boldine 4.

Applied Biological and Physicochemical Activity of Isoquinoline Alkaloids: Oxoisoaporphine and Boldine

“…However, the aporphine alkaloid structure remained unchanged and the photoproducts of glaucine exhibited a higher photoprotection factor (SPF) than the non-irradiated compounds. We also found [ 17 ] that boldine derivatives bearing substituent groups and annelated heterocycles with the aporphine framework have a greater photostability against UVB radiation. Thus, the compounds derived from boldine bearing oxazole and oxazinone annelated rings have promising photophysical and photochemical properties that could allow their possible use as sunscreens.…”