Mechanistic Insights into the Light-Driven Catalysis of an Immobilized Lipase on Plasmonic Nanomaterials

Author(s)

Ribeiro de Barros, Heloise ^{[1, 2]} ; Garcia, Isabel ^{[2, 3]} ; Kuttner, Christian ^[2] ; Zeballos, Nicoll ^[2] ; Camargo, Pedro H. C. ^{[1, 4]} ; Cordoba de Torresi, Susana Ines ^[1] ; Lopez-Gallego, Fernando ^{[5, 2]} ; Liz-Marzan, Luis M. ^{[5, 2, 3]}

Affiliation

^[1] Univ Sao Paulo, Dept Fundamental Chem, Inst Chem, BR-05508000 Sao Paulo - Brazil

^[2] Basque Res & Technol Alliance BRTA, CIC BiomaGUNE, Donostia San Sebastian 20014 - Spain

^[3] Ctr Invest Biomed Red Bioingn Biomat & Nanomed CI, Donostia San Sebastian 20014 - Spain

^[4] Univ Helsinki, Dept Chem, Helsinki 00100 - Finland

^[5] Basque Fdn Sci, Ikerbasque, Bilbao 48013 - Spain

• Document type: Journal article
• Source: ACS CATALYSIS; v. 11, n. 1, p. 414-423, JAN 1 2021.
• Web of Science Citations: 0

Abstract

The use of light as an external stimulus to control the enzyme activity is an emerging strategy that enables accurate, remote, and noninvasive biotransformations. In this context, immobilization of enzymes on plasmonic nanoparticles offers an opportunity to create light-responsive biocatalytic materials. Nevertheless, a fundamental and mechanistic understanding of the effects of localized surface plasmon resonance (LSPR) excitation on enzyme regulation remains elusive. We herein investigate the plasmonic effects on biocatalysis using Au nanospheres (AuNSp) and nanostars (AuNSt) as model plasmonic nanoparticles, lipase from Candida antarctica fraction B (CALB) as a proof-of-concept enzyme, and 808 nm as near-infrared light excitation. Our data show that LSPR excitation enables an enhancement of 58% in the enzyme activity for CALB adsorbed on AuNSt, compared with the dark conditions. This work shows how photothermal heating over the LSPR excitation enhances the CALB activity through favoring product release in the last step of the enzyme mechanism. We propose that the results reported herein shed important mechanistic and kinetic insights into the field of plasmonic biocatalysis and may inspire the rational development of plasmonic nanomaterial-enzyme hybrids with tailored activities under external light irradiation. (AU)

• FAPESP's process: 18/13492-2 - Synthetic and natural scaffolds applied to regenerative medicine
• Grantee: Luiz Henrique Catalani
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 19/09668-0 - Understanding the biophysiochemical interactions between plasmonic nanoparticles and enzymes to obtain bio-nanomaterials with controlled properties
• Grantee: Heloise Ribeiro de Barros
• Support Opportunities: Scholarships abroad - Research Internship - Post-doctor
• FAPESP's process: 15/26308-7 - Optimization of the physicochemical properties of nano -structured materials for applications in molecular recognition, catalysis and energy conversion/storage
• Grantee: Roberto Manuel Torresi
• Support Opportunities: Research Projects - Thematic Grants
• FAPESP's process: 17/20892-4 - Nanobioplasmonic catalysts: a novel approach to controlling the selectivity in light-driven one-pot reactions
• Grantee: Heloise Ribeiro de Barros
• Support Opportunities: Scholarships in Brazil - Post-Doctoral