Direct immersion single-drop microextraction combined with fluorescence detection using an optical probe. Application for highly sensitive determination of rhodamine 6G.

The use of an optical probe for fluorescence detection combined with direct immersion single-drop microextraction has been demonstrated as an innovative approach. The optical probe served both as a drop holder for extractant and as a measuring device which made it possible to eliminate the use of cuvettes. A laser and a light emitting diode (LED) were tested as possible light sources. Both of them showed comparable results. However, given the much smaller half-band width of the laser radiation, its use has proven to be preferable since background correction can be eliminated. Direct immersion single-drop microextraction of an ionic association complex of rhodamine 6G with picric acid with subsequent fluorescent detection (λex was 532 nm and 525 nm for laser and LED, respectively; λem was 560 nm for both laser and LED) was used a model system to evaluate the new approach. The extractant phase was a 55 µL amyl acetate microdrop fixed in the optical part of the probe. LOD, LOQ and linear calibration range were found as 0.14, 0.48 and 0.5-10 nmol L-1, and 0.15, 0.50 and 0.5-5 nmol L-1 for laser and LED light sources, respectively. The accuracy of the method was assessed by analyzing real water samples.

Development of a New Kinetic Spectrophotometric Method for the Determination of Chromium with an Optical Probe.

The aim of this work is the development, optimization, and validation of a new spectrophotometric kinetic method for the determination of dissolved chromium species in water samples with the use of the polymethine dye Astra Phloxine FF. The progress of the chemical reaction was simple, effective, and precisely monitored from the start of the reaction using an optical probe. The method is based on the impact of Cr(VI) concentration on the rate of decrease in the Astra Phloxine FF concentration. The experimental data were evaluated using four experimental data analysis methods, namely with the initial rate method, the average rate method, the fixed time method, and the absorption peak volume change method. Under the optimal reaction conditions, the best results were achieved using the method of the average rate constant for evaluating the experimental data. Using this data evaluation method for the determination of Cr(VI), the LoD was found to be 1.87 µg L-1 and RSD ( n = 6; 0.2 mg L-1 Cr) 3.59%. The presented work was used for the determination of chromium in model samples-CRM material and tap and waste water-and with the calibration line method and the standard additions method.