The combination of an optical probe and single-drop direct immersion microextraction (DI-SDME-OP) was used for the preconcentration and subsequent spectrophotometric determination of rhodamine 6G (Rh6G). The developed method is based on the formation of an ionic associate between Rh6G and picric acid at pH 3.0 and its extraction with amyl acetate. A microdrop of the organic phase was stably placed in the hole of an optical probe immersed in the sample solution. The absorbance of the extraction phase was monitored at 534 nm. The proposed method combines in a single step several stages of the analytical procedure, such as pre-concentration, phase separation, transfer of the extraction phase to the instrument and online measurement. The sensitivity of the proposed approach is not inferior to existing microextraction methods involving the combination of liquid-phase or solid-phase extraction with spectrophotometry or HPLC with a UV-Vis detector. The evaluation of the greenness of the developed method carried out by the AGREE method (0.58 points) showed that it outperforms other similar existing techniques using this parameter. The calibration plot for the determination of Rh6G by the DI-SDME-OP method was linear over the range of 10-500 nM with a correlation coefficient of 0.9956. The limit of detection was 3.4 nM. The accuracy and applicability of the method were evaluated by the determination of Rh6G in natural waters and lipstick.

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 (lambda ex was 532 nm and 525 nm for laser and LED, respectively; lambda em was 560 nm for both laser and LED) was used a model system to evaluate the new approach. The extractant phase was a 55 mu L 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.

The fluorescence signal increase in deuterated water - D2O is relevant to many methods used in chemical and biological research. We performed fluorescence spectroscopy measurements combined with evaluations of fluorescence-based methods to describe and quantify the practical impacts of D2O on chemical and biological samples. Several novel features are observed in fluorescence spectra and life-time decay curves of molecules including fluorescence probes and labels that are used frequently in biomolecular labelling and bioimaging. The observed characteristics suggest that D2O enhances the fluorescence signal due to the exchange of labile hydrogen on a fluorophore for heavier deuteron and the reduction of energy transfer from excited fluorophores to H2O molecules. Furthermore, performed quantifications approve that D2O increases significantly the detection signal of all examined fluorescence-based approaches where the brightness of fluorophores and sample viability are crucial.

The solvatochromic effect of solvents on the absorption and fluorescence spectra of three carbocyanine dyes, namely 1,1',3,3,3',3'-hexamethylindocarbocyanine chloride (HIC); 1,1',3,3,3',3'-hexamethylindodi carbocyanine iodide (HIDC); and 3,3'-diethyloxadicarbocyanine iodide (DODC), have been investigated. The experimental ground and excited-state dipole moments of the dyes have been estimated via the well-known models by Lippert-Mataga, Bakhshiev, Kawski-Chamma-Viallet, and the Dimroth-Reichardt's empirical model. The influence of the solvation effect on the luminescence quantum yields was also examined and a strong correlation between the luminescence quantum yield values and the solvent viscosity was established. The fluorescence signal enhancement sensitivities between dyes were compared based on the Forster-Hoffmann equation. DFT and TDDFT calculations at the CAM-B3LYP/6-31G(d,p) level of theory were performed for the analysis of the nature of the electron transitions in absorption and excitation processes. Six phases different in polarity were considered during these computations, namely the gas, toluene, chloroform, acetone, methanol, and water. Transition electron density plots, Mulliken atomic partial charges, and Mayer bond orders were used for the analysis of the redistribution of electron density upon excitation. The specific behavior of the dyes in the glycerol medium was interpreted via the analysis of non-covalent interactions between the dye and glycerol molecules in terms of the reduced density gradient method. (C) 2021 Elsevier B.V. All rights reserved.

A new and fully automated system with the interconnection of an Optical Immersion Probe (OIP) – pH meter – peristaltic pump was used to study the spectral and protolytic properties of carbocyanine the dyes 1,1′,3,3,3′,3′-hexamethylindocarbocyanine chloride (HIC); 1,1′,3,3,3′,3′-hexamethylindodicarbocyanine iodide (HIDC); and 3,3′-diethyloxadicarbocyanine iodide (DODC). This system can measure a large number of experimental points in a short time period. The effect of 32 various organic solvents on the UV-ViS spectra of the dyes was studied. The solvatochromic behaviour of studied dyes was characterized by positive solvatochromism for HIDC and negative solvatochromism for HIC and DODC. Through the application of a large number of experimental points, the protonation and hydrolysis constants of dyes were determined with high precision, where the confidence interval of the рK values is ±(0.001–0.005), compared with a confidence interval of ±(0.04–0.10) for standard procedures. The fully automated system presented is accurate, fast, environmentally friendly and promising for multiple analytical applications.

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.