Biomimetic photooxidation of noscapine sensitized by a riboflavin derivative in water: The combined role of natural dyes and solar light in environmental remediation.

Noscapine (NSC) is a benzyl-isoquinoline alkaloid discovered in 1930 as an antitussive agent. Recently, NSC has also been reported to exhibit antitumor activity and, according to computational studies, it is able to attack the protease enzyme of Coronavirus (COVID-19) and thus could be used as antiviral for COVID-19 pandemic. Therefore, an increasing use of this drug could be envisaged in the coming years. NSC is readily metabolized with a half-life of 4.5 h giving rise to cotarnine, hydrocotarnine, and meconine, arising from the oxidative breaking of the CC bond between isoquinoline and phthalide moieties. Because of its potentially increasing use, high concentrations of NSC but also its metabolites will be delivered in the environment and potentially affect natural ecosystems. Thus, the aim of this work is to investigate the degradation of NSC in the presence of naturally occurring photocatalysts. As a matter of fact, the present contribution has demonstrated that NSC can be efficiently degraded in the presence of a derivative of the natural organic dye Riboflavin (RFTA) upon exposure to visible light. Indeed, a detailed study of the mechanism involved in the photodegradation revealed the similarities between the biomimetic and the photocatalyzed processes. In fact, the main photoproducts of NSC were identified as cotarnine and opianic acid based on a careful UPLC-MS2 analysis compared to the independently synthesized standards. The former is coincident with one of the main metabolites obtained in humans, whereas the latter is related to meconine, a second major metabolite of NSC. Photophysical experiments demonstrated that the observed oxidative cleavage is mediated mainly by singlet oxygen in a medium in which the lifetime of 1O2 is long enough, or by electron transfer to the triplet excited state of RFTA if the photodegradation occurs in aqueous media, where the 1O2 lifetime is very short.

Photocatalytic degradation of drugs in water mediated by acetylated riboflavin and visible light: A mechanistic study.

There is a current concern, among the scientific community, on the pollutants classified as "persistent organic pollutants (POPs)". Pharmaceuticals and personal care products (PPCPs) belong to this family of contaminants; therefore, it is necessary to find more efficient techniques able to achieve their removal from the environment. This study focuses on two different pharmaceuticals: carbamazepine and atenolol, chosen for their widespread use and their different chemical and medical properties. In this work, an organic dye, acetylated riboflavin, has been used in combination with visible light to achieve the photodegradation of these two POPs in <2 h. Moreover, photophysical experiments demonstrated the involvement of the singlet and triplet excited states of acetylated riboflavin and the generated singlet oxygen in the removal of these drugs. Besides, a detailed UFLC-MS-MS analysis of the photoproducts confirmed the oxidation of the drugs. Finally, a plausible mechanism has been postulated.