Optimum conditions for the direct reversed-phase LC determination of fluoride based on the ternary M-(F-)-(5-Br-PADAP) complexes [M = ZrIV or HfIV and 5-Br-PADAP = 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol] were evaluated. Chromatographic separation was performed with C18 end-capped column with an eluent consisting of acetonitrile-water (85 + 15 v/v) mixture of pH 4.0 +/- 0.3 (flow rate 1 ml min-1), and the eluate was monitored spectrophotometrically at lambda max = 585 nm. The calibration curves were linear over a wide range of fluoride concentrations: from 1 to 110 and 150 ng ml-1 for the ZrIV-(F-)-(5-Br-PADAP) and HfIV-(F-)-(5-Br-PADAP) systems, respectively (using a 20 microliters loop). Under such conditions the detection limits were 0.8 and 0.7 ng ml-1, respectively, and the quantification limit is 1.0 ng ml-1 for both methods. When a 100 microliters loop was used, the limits of both detection and quantification in the method based on the zirconium system were 0.2 ng ml-1. Using the proposed method, fluoride was determined directly in tap water, saliva and an anti-cancer agent for prostatic cancer (Leuprolid).
The solvatochromic shift of the most intensive band of fluorenone radical anion (FN*‐) in the visible region has been examined in 10 polar formally aprotic media. It has been found that this shift depends on the solvent acceptor number (AN) and static dielectric constant (D) according to planar regression:
It is suggested that the ground state of FN*‐ is relatively stabilized in a solvent with a high acceptor number and the dipole moment of the solute increases during an excitation.
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