Spectrophotometric Fluoride Determination Using St. John's Wort Extract as a Green Chromogenic Complexant for Al(III).

In this study, we applied an innovative approach of green analytical chemistry to develop a novel and eco-friendly chromogenic agent for fluoride determination by making use of the nontoxic Al(III)-flavonoid complex in a natural extract from St. John's wort plant. The initial intensely yellow-colored Al(III)-flavonoid complex formed in the plant extract was converted to a colorless AlF6 3- complex with increasing amounts of fluoride, and color bleaching of the Al-flavonoid chromophore (measured as absorbance decrement) was proportional to fluoride concentration. The developed method gave a linear response within the F- concentration range of 0.11-1.32 mM with the LOD and LOQ values of 0.026 mM (0.5 mg L-1) and 0.079 mM (1.5 mg L-1), respectively. The LOD value for fluoride was below the WHO-permissible limit (1.5 mg L-1) and the US-EPA-enforceable limit (4 mg L-1) in water. The possible interference effects of common anions (Cl-, Br-, I-, NO3 -, HCO3 -, SO4 2-, and PO4 3-) and cations (K+, NH4 +, Ag+, Ca2+, Mg2+, Mn2+, Fe2+, and Fe3+) were investigated; the observed interferences from Fe2+, Fe3+, and PO4 3- were easily eliminated by masking iron with the necessary amount of Na2EDTA without affecting the blank absorbance of the Al(III)-flavonoid complex, precipitating phosphate with Ag(I) salt, and partly neutralizing alkaline water samples to pH 4 with acetic acid. The developed method was applied to real water samples and also validated against a reference spectroscopic method at the 95% confidence level.

Ethylenediamine-bound magnetite nanoparticles as dual function colorimetric sensor having charge transfer and nanozyme activity for TNT and tetryl detection.

A reusable, low-cost, and convenient ethylenediamine (EDA)-bound magnetite nanoparticles (MNPs)-based colorimetric sensor has been developed for dual function colorimetric determination of nitroaromatic explosives such as TNT and tetryl. Colorimetric detection of analytes may occur through two independent routes: (1) nano-Fe3O4- EDA- NH2 as σ-donor may interact with the σ- and π-acceptor aromatic-poly(NO2) groups to produce a colored charge-transfer (CT) complex; (2) nano-Fe3O4-EDA-NH2 as a Fenton-type nanozyme may generate reactive species that comprise hydroxyl radicals (•OH) with H2O2 to oxidize 3,3',5,5'-tetramethylbenzidine (TMB) to a blue-colored diimine (oxTMB-TMB) CT complex, where this color is bleached with TNT/tetryl because of donor-acceptor interactions between the explosive -NO2 groups and the -NH2 group of Fe3O4-EDA nanoparticles of restricted nanozyme activity. Both methods can quantify TNT well below the EPA recommended TNT residential screening level in soil, LOD being in the micromolar range. As EDA was covalently bound to MNPs, the same sensor can be separately reused six times for TNT and eight times for tetryl determination, using method (1). Common metal ions, anions, energetic materials, several camouflage materials, and soil components such as humates did not interfere with the nanosensor performance for TNT and tetryl. The combination of charge-transfer and nanozyme ability of Fe3O4- EDA-NH2 nanoparticles may bring a new approach to dual function colorimetric sensor design. To the best of our knowledge, this is the first dual function colorimetric sensor for TNT and tetryl using the same nanoparticles as sensing elements in two different detection systems involving either formation or bleaching of colored species. The proposed colorimetric sensor can determine nitroaromatic explosives in two different ways: method-1 for TNT and tetryl sensing with EDA-MNPs relies on the donor-acceptor interaction between the electron-deficient nitroaromatics and electron-rich amine groups covalently functionalized on MNPs to produce an absorbance at 512 nm. In method-2, EDA-MNPs having nanozyme activity react with H2O2 to form reactive species that can oxidize TMB to its blue-colored charge-transfer (CT) complex, where TNT and tetryl addition may partially inhibit the nanozyme activity of EDA-MNPs and cause color bleaching (decrement of 650 nm absorbance) by disrupting the CT complex formed from TMB. This is the first dual function colorimetric sensor for nitro explosives uniquely combining charge-transfer and nanozyme ability of EDA-Fe3O4 nanoparticles in the same nano-sensor.