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J Photochem Photobiol B. 2019 Aug 21;199:111600. doi: 10.1016/j.jphotobiol.2019.111600. [Epub ahead of print]

Light-induced full aromatization and hydroxylation of 7-methoxy-1-methyl-3,4-dihydro-2H-pyrido[3,4-b]indole alkaloid: Oxygen partial pressure as a key modulator of the photoproducts distribution.

Author information

1
Instituto Tecnológico de Chascomús (INTECH), Universidad Nacional de San Martín (UNSAM), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Av. Intendente Marino Km 8.2, CC 164, B7130IWA Chascomús, Argentina; Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), CCT-La Plata, Universidad Nacional de La Plata, Diag. 113 y 64, 1900 La Plata, Argentina.
2
Instituto Tecnológico de Chascomús (INTECH), Universidad Nacional de San Martín (UNSAM), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Av. Intendente Marino Km 8.2, CC 164, B7130IWA Chascomús, Argentina.
3
Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), CCT-La Plata, Universidad Nacional de La Plata, Diag. 113 y 64, 1900 La Plata, Argentina.
4
Universidad de Buenos Aires, Facultad de Ciencias Exactas y Naturales, Departamento de Química Orgánica, Pabellón II, 3er P., Ciudad Universitaria, 1428 Buenos Aires, Argentina; CONICET, Universidad de Buenos Aires, Centro de Investigación en Hidratos de Carbono (CIHIDECAR), Facultad de Ciencias Exactas y Naturales, Pabellón II, 3er P., Ciudad Universitaria, 1428 Buenos Aires, Argentina.
5
Instituto Tecnológico de Chascomús (INTECH), Universidad Nacional de San Martín (UNSAM), Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Av. Intendente Marino Km 8.2, CC 164, B7130IWA Chascomús, Argentina. Electronic address: fcabrerizo@intech.gov.ar.

Abstract

Full-aromatic and partially hydrogenated β-carboline (βC) derivatives constitute a group of alkaloids widely distributed in a great variety of living systems. In plants and bacteria, tetrahydro-βCs are the primary product of the Pictet-Spengler enzymatically catalyzed condensation. Tetrahydro-βC skeleton is further modified giving rise to the formation of a vast set of derivatives including dihydro- and full-aromatic βCs. However, in most of the cases, the later processes still remain unclear and other sources, such as photo-triggered reactions, deserve to be explored. In this context, the photophysic and photochemistry of 7-methoxy-1-methyl-3,4-dihydro-2H-pyrido[3,4-b]indole or harmaline (Hlina) in aqueous solution is reported herein. UV-visible absorption and fluorescence emission spectroscopy coupled with multivariate data analysis (PARAFAC), HPLC and HRESI-MS techniques were used for both quantitative and qualitative analysis. The formation singlet oxygen and hydrogen peroxide reactive oxygen species (ROS) was quantified and their role together with the influence of pH and oxygen partial pressure on the photochemical degradation of HlinaH+ was assessed. We report herein the first study on photochemical full-aromatization of a dihydro-βC derivative. These results can shed some light on the βCs biosynthesis and role in living systems.

KEYWORDS:

Harmaline; Harmine; PARAFAC; Photochemistry; β-Carbolines

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