Fluorescence and Photophysical Properties of Anthracene and Phenanthrene in Water.

Polyaromatic hydrocarbons (PAHs) are widely spread pollutants in the environment, including soil and water. Anthracene (anth) and phenanthrene (phen) pose severe health impacts on human lives due to their carcinogenic nature by increasing cancer risk to the skin, lungs, and bladder. Fluorescence spectroscopy is a promising , efficient and straightforward tool for characterizing these trace PAHs in water. Therefore, the current work provides a detailed insight into the fluorescence properties of anth and phen in water. The fluorescence EEMs (excitation-emission matrices) of anth showed emissions at 380 nm, 400 nm, and 425 nm with single excitation at 250 nm, whereas phen showed two emissions < 380 nm, at 350 nm and 365 with single excitation at 250 nm. Then the theoretical EX/EM wavelengths were calculated by DFT and CIS-B3LYP for these compounds in water. The environmental effect of pH variation on fluorescence EEM shows a significant difference in fluorescence intensity without changing in peak locations, with highest fluorescence intensity at neutral pH than acidic and alkaline. Furthermore, the theoretical pH effect was described for the first time by simulating the protonated (+ 1), deprotonated (-1) and neutral molecules in water at the DFT level of theory. The variation in simulated oscillator strengths was similar in trend with the experimental fluorescence intensity of these compounds. The HOMO-LUMO were calculated to obtain the energy gap, molecular softness, molecular hardness, electronic potential and electrophilicity of anth and phen. To find the fluorophore contribution, the fluorescence of homogeneous mixture of both isomers was analyzed, which showed an enhanced fluorescence intensity of anth by 12-20%, whereas a decrease of 9-14% was observed in phen. This study describes that the fluorescence technique could be a fast and easy method to distinguish and identify PAHs isomers (anth and phen) in water.