Interaction of Zinc Oxide and Copper Oxide Nanoparticles with Chlorophyll: A Fluorescence Quenching Study

The present study aims to investigate the interactions of zinc oxide nanoparticles and copper oxide nanoparticles with the major photosynthetic pigment chlorophyll using ultraviolet-visible, steady state, and time resolved laser induced fluorescence spectroscopy. The steady state fluorescence measurements show that zinc oxide and copper oxide nanoparticles quench the fluorescence of chlorophyll in concentration-dependent manner. The Stern-Volmer plot for the chlorophyll-zinc oxide nanoparticles is linear, and the value of quenching constant has been observed to increase with temperature indicating the possibility of dynamic quenching. A decrease in the lifetime of chlorophyll with increase in the concentration of zinc oxide nanoparticles confirms the involvement of dynamic quenching in the chlorophyll–zinc oxide nanoparticle interaction. In the case of copper oxide nanoparticles, the Stern-Volmer plot deviates from linearity observed in the form of upward curvature depicting the presence of both static and dynamic quenching. In addition, the lifetime of chlorophyll decreases with increase in the concentration of copper oxide nanoparticles displaying the dominance of dynamic quenching in the chlorophyll-copper oxide nanoparticle interaction. The decrease observed in the value of binding constant with increasing temperature and negative values of change in enthalpy, entropy, and Gibb’s free energy indicates that van der Waal and hydrogen bonding are the prominent forces during the interaction of chlorophyll with both zinc oxide and copper oxide nanoparticles and that the process is spontaneous and exothermic. The interaction of zinc oxide and copper oxide nanoparticles with chlorophyll occurs through electron transfer mechanism. The obtained results are useful in understanding the sensitization processes involving chlorophyll and zinc oxide and copper oxide nanoparticles.