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Dos flavoenzimas convierten el péptido fúngico policetídeo no ribosómico en cis-2-buteno-1,4-tipo carcinógeno a
Jin-Mei Zhang1, Guan-Yin Yuan1, Min-Xiu Shi1
1College of Pharmaceutical Sciences, Southwest University, Chongqing 400715, P. R. China.
Journal of the American Chemical Society
|October 17, 2025
Resumen
Los investigadores descubrieron dos flavoenzimas en Fusarium reticulatum que modifican las columnas vertebrales del péptido poliquetídeo no ribosómico (PK-NRP). Una enzima produce diolos vicinales, mientras que otra produce un carcinógeno recientemente identificado, el cis-2-metil-2-buteno-1,4-dial, que plantea riesgos para la salud.
Área de la Ciencia:
- Biosíntesis de productos naturales
- Enzimología
- Micología
Sus antecedentes:
- La posmodificación de las columnas vertebrales de péptidos policetídicos no ribosómicos (PK-NRP) por enzimas de oxidación genera diversos productos naturales.
- La modificación de los polienos conjugados dentro de las columnas vertebrales de PK-NRP es un área menos explorada en la biosíntesis de productos naturales.
Objetivo del estudio:
- Identificar y caracterizar las flavoenzimas involucradas en la decoración de la columna vertebral del núcleo de PK-NRP.
- Elucidar los mecanismos enzimáticos para modificar los polienos conjugados en los PK-NRPs.
- Identificar nuevos metabolitos y evaluar sus actividades biológicas.
Principales métodos:
- Identificación de las flavoenzimas (FrtD y FrtB) del grupo frt en Fusarium reticulatum.
- Ensayos enzimáticos para determinar las actividades catalíticas de la FrtD (monooxigenasa dependiente de la FAD) y de la FrtB (oxidasa similar a la enzima puente de la berberina).
- Caracterización estructural de los productos de reacción, incluidos los diolos vicinales y el cis-2-metil-2-buteno-1,4-dial.
Principales resultados:
- El FrtD cataliza la dihidroxilación de un precursor de PK-NRP de cinco polienos conjugados, produciendo diolos vicinales (1a/1b).
- FrtB convierte 1a en cis-2-metil-2-buteno-1,4-dial (17) y cetonas conjugadas de polieno α,β-insaturadas (12) a través de la deshidrogenación, la escisión del enlace C-C y la isomerización.
- El cis-2-metil-2-buteno-1,4-dial (17) se ha identificado como un nuevo carcinógeno capaz de unirse a los aminoácidos e inducir daños en el ADN.
Conclusiones:
- El estudio revela funciones inusuales de las flavoenzimas en la modificación de los PK-NRPs, particularmente en los polienos conjugados.
- Un nuevo metabolito de la micotoxina, el cis-2-metil-2-buteno-1,4-dial, producido por Fusarium sp. ha sido descubierto.
- El carcinógeno identificado plantea riesgos potenciales para la salud, lo que requiere una mayor investigación y atención.
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