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Exploring Biliverdin's Molecular Interactions with Cu- and Fe-Based MOFs: A Unified In Vitro Study with Photoacoustic
Hamideh R Alanagh1, Parinaz Fathi1, Hailey J Knox2
1Department of Bioengineering, Beckman Institute of Advanced Science and Technology, Department of Materials Science and Engineering University of Illinois at Urbana-Champaign, Carle Foundation Hospital, 611 West Park Street, Urbana, Illinois 61801, United States.
Abstract:
Metal-organic frameworks (MOFs) have shown promise in enhancing the stability of biomolecules. Herein, biliverdin (BVD), a photoacoustic (PA) and fluorescent agent, was immobilized within the pores of NH2-MIL-101 (Fe) (FeMOFs) and on the surface of CuBTC crystallites (CuMOFs). MOFs were found to enhance the fluorescence emission and quench the PA intensity of biliverdin. Fluorescence and PA studies, in tandem with DFT simulations, demonstrated that the spectral interactions between MOFs and BVD resulted from interactions between biliverdin and the MOF pores and surfaces in addition to alterations in the HOMO-LUMO energy gap. The MOF internal structure of the MOF played a role in BVD loading, with the FeMOFs enabling greater BVD encapsulation, while CuMOF interactions with BVD primarily took place on the MOF surface. The role of these surface vs pore interactions in the release of biliverdin was explored. This study demonstrates that the effects of the MOF internal structure, surface interactions, and energy interactions should be taken into consideration for biomolecule loading in MOFs.
