Photoinduced visible regeneration of NADH cofactor mediated by NH2-MIL-125

AGUIRRE, MATÍAS E.; ISLA NAVEIRA, ROCIO; GRELA, MARÍA A.

Villa Carlos Paz

Congreso; XIII Encuentro Latinoamericano de fotoquímica y fotobiología; 2017

XIII Encuentro Latinoamericano de fotoquímica y fotobiología

Photoinduced visible regeneration of NADH cofactor mediated by NH2-MIL-125Matías E. Aguirre,a,b Rocío Isla Naveira a and María A Grela a,ba Departamento de Química, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Mar del Plata, Funes 3350, (7600) Mar del Plata, Prov. de Buenos Aires, Argentina.b Instituto de Investigaciones Físicas de Mar del Plata, IFIMAR (CONICET), Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Mar del Plata.meaguirre@mdp.edu.ar Enzymatic catalysis is an interesting approach to carry out chemical reactions with low energy cost and high specificity. However, its practical application requires the development of efective methods of immobilization to facilitate enzyme recovery and reuse. As part of our ongoing efforts in this line of research, we have recently used metal-organic frameworks (MOFs) to develop hybrid systems coupled with magnetic particles for the immobilization and recycling of formate dehydrogenase enzyme to mediate the reduction of carbon dioxide. Metal-organic frameworks are a class of hybrid materials made up from inorganic centres (metal ions or metal oxide clusters) coordinated by organic molecules. [1] These materials are very interesting because of their high surface areas and particularly because of their semiconductor properties, which can be exploited for the development of photobiocatalysts either to activate the enzyme directly or to regenerate the cofactor (i.e., Nicotinamide Adenine Dinucleotide, NADH). It is noteworthy to recall that bibliographic reports of the regeneration of NADH often involve the photoexcitation of rare and expensive metal complexes such as ruthenium, plasmonics nanoparticles of Pt or semiconductors of toxic nature as CdS.[2]In this presentation, we report the use of NH2-MIL-125 as a photoactive species to mediate NADH regeneration induced by visible irradiation from its oxidized form (NAD+). NH2-MIL-125 is a metal-organic framework based on titanium oxo clusters and aminoterephthalic acid as ligands, which good biocompatibility, strong absorption response in the visible region (onset ≈ 550 nm) and efficient photoinduced charge separation. [3] The regeneration of NADH was performed by visible irradiation (irrad≥400 nm under anaerobic conditions of aqueous suspensions of NH2-MIL-125 in the presence of NAD+ and isopropyl alcohol as a sacrificial electron donor. The evolution of NADH in the solution was evaluated by UV-Visible spectroscopy monitoring the absorbance at 340 nm (see Figure) and by emission spectroscopy. The synthesis and characterization of the photocatalytic material as well as the mechanism of NADH photo-regeneration is discussed in detail.[1] K. K. Gangu, S. Maddila, B. S. Mukkamala, S. B. Jonnalagadda, Inorg. Chim. Acta 2016, 446, 61.[2] a) K. T. Oppelt, J. Gasiorowski, D. Ayuk Mbi Egbe, J. P. Kollender, M. Himmelsbach, A. W. Hassel, N. S. Sariciftci, G. Knör, J. Am. Chem. Soc. 2014, 136, 12721. b) K. A. Brown, M. B. Wilker, M. Boehm, H. Hamby, G. Dukovic, P. W. King, ACS Catal. 2016, 6, 2201.[3] a) W. de Miguel, F. Ragon, T. Devic, C. Serre, P. Horcajada, H. García, ChemPhysChem 2012, 13, 3651. b) S.-N. Kim, J. Kim, H.-Y. Kim, H.-Y. Cho, W.-S. Ahn, Catalysis Today 2013, 204, 85.