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Cofactor artificial supramolecular basado en caja verde para catálisis fotoenzimática asimétrica impulsada por luz

Chenjing Liu¹, Naiyao Li¹, Zhaoguang Zhang¹

¹Frontier Institute of Science and Technology, Interdisciplinary Research Center of Frontier Science and Technology, State Key Laboratory for Strength and Vibration of Mechanical Structures, Institute of New Concept Sensors and Molecular Materials, Shaanxi Key Laboratory of New Conceptual Sensors and Molecular Materials, Engineering Research Center of Key Materials for Efficient Utilization of Clean Energy of Shaanxi Province, Xi'an Key Laboratory of Electronic Devices and Material Chemistry, Xi'an Jiaotong University, Xi'an, Shaanxi Province 710054, P. R. China.

Journal of the American Chemical Society

|November 17, 2025

Resumen

Los investigadores desarrollaron un nuevo cofactor artificial para la catálisis integrada de fotoenzimas, lo que permite una síntesis asimétrica eficiente de moléculas quirales con alta selectividad y estabilidad.

Área de la Ciencia:

Química supramolecular
Biocatálisis
Fotocatálisis

Sus antecedentes:

Los sistemas de fotoenzimas integran múltiples procesos catalíticos pero sufren pérdidas de eficiencia debido a la separación de los componentes.
Las arquitecturas compactas de tipo Z son deseables para mejorar el rendimiento.

Objetivo del estudio:

Para crear un sistema catalítico integrado de fotoenzimas utilizando un cofactor artificial supramolecular.
Para lograr una síntesis asimétrica eficiente de moléculas bioactivas quirales impulsadas por la luz visible.

Principales métodos:

Complejación huésped-huésped entre un ciclófano basado en selenoviólogo (SeV-Rh-Box) y NAD+ para formar el cofactor artificial.
Integración del cofactor artificial con la alcohol deshidrogenasa para la catálisis de las fotoenzimas.
Análisis espectroscópicos y electroquímicos para estudiar los mecanismos de transferencia de electrones.

Principales resultados:

El cofactor artificial SeV-Rh-BoxNAD+ permitió la síntesis asimétrica impulsada por la luz visible.
Se obtuvieron altos excesos enantioméricos (> 87%) y números de rotación (> 47.700).
Eficiencia catalítica sostenida (> 50% después de 24 horas y 8 ciclos) y regeneración eficiente de los cofactores.

Conclusiones:

La arquitectura supramolecular facilita la transferencia intramolecular de electrones y la regeneración del cofactor.
Presenta una estrategia modular para unir la fotocatálisis y la biocatálisis a través del autoensamblaje.
Ofrece una plataforma generalizable para la síntesis asimétrica impulsada por la luz.

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