Water quality control employs techniques mostly targeting individual analytes; group detection is also practiced, but the choice of group methods is limited, which supports interest in developing such methods. We have examined the interaction of hypochlorite with a chlorine-containing heptamethine carbocyanine dye in the presence of 30 organic and inorganic model analytes that were found to induce diverse color changes in the system. The main supposed mechanisms are retardation of the dye oxidation with hypochlorite (presumably by scavenging chlorine radicals) and substitution of chlorine atom in the dye by the most nucleophilic analytes (amines, amino acids, proteins, DNA, phenol). The grass-green substitution product is more contrastingly visible against the dark-purple hypochlorite oxidation product of the dye than against the original emerald-green dye. The indicator reaction is monitored photographically for 10–40 min and the images are processed using principal component analysis (PCA) or linear discriminant analysis (LDA), allowing for data convolution for the complex color transitions. Nitrogen compounds are discriminated from the others, and more reactive analytes (tryptophan, cysteine, bovine serum albumin, and DNA) are detected in the presence of less reactive ones in natural water. The system is promising for the development of group assays for dissolved organic matter and the discrimination of water samples.
Substitution reactions in carbocyanine dyes are used to determine nucleophilic compounds. The interaction of a chlorine-containing carbocyanine dye with a number of medicinal substances is studied. It is shown that, in the reaction with isoniazid in the presence of a surfactant, this dye selectively changes color from yellow-green to violet. The formation of a product of the substitution of chlorine for isoniazid is proven by chromatography–mass spectrometry. The reaction proceeds in 20 min in the presence of 1 mM cetyltrimethylammonium bromide. The limit of detection for isoniazid in water by the photometric method is 10 μg/mL and in diluted artificial urine using fluorimetry, 0.3 μg/mL. The procedure does not use full-spectrum equipment, which simplifies the determination.
1 November 2024 in Journal of Analytical Chemistry
The work focuses on the development of a fluorimetric version of the fingerprint method based on conducting indicator reactions in the presence of a test sample. Observation of these reactions over time provides a more detailed information compared to batch methods, thereby improving sample recognition and enabling quantitative analysis. The proposed indicator reaction utilizes a commercial carbocyanine dye and 4-dimethylaminobenzaldehyde, whose interaction results in a decrease in fluorescence intensity and changes in absorbance over time. Three fluoroquinolones—moxifloxacin, levofloxacin, and ofloxacin—selectively change the signal in concentrations of 1 μM or higher, while other drugs, including different fluoroquinolones, do not interfere with the determination. Ofloxacin was detected in human urine samples at various times post-drug intake. A potential of using the same indicator reaction for sample recognition was demonstrated on examples of apple juices, soil extracts, and meat of varying freshness. Chemometric methods, including linear discriminant analysis, were used for data processing. The method achieved 97% accuracy in discriminating fifteen apple juice samples, 94% accuracy for ten apple juices from 2022 and 2023, 99% accuracy for ten soil samples, and successfully determined the freshness of five meat samples.
24 September 2026 in Journal of Analytical Chemistry
A fluorimetric fingerprinting method was developed for distinguishing dairy product samples according to their manufacturer and for detecting adulteration. The approach is based on the use of magnetite–particle–fluorophore sandwich systems formed through the interaction of polyhexamethylene guanidine-modified magnetite particles with milk components, followed by the addition of a fluorophore (carbocyanine dyes or carbon dots). The resulting sandwich systems were separated from excess fluorophore using a magnet, and the fluorescence of the aggregates was recorded photographically. The photographs were then digitized, and the resulting data were processed using chemometric methods. For comparison, the proposed method was evaluated against two alternative approaches: one based on the intrinsic fluorescence of the samples and the other based on the fluorescence of fluorophore-supplemented samples without magnetic separation. The proposed approach enables highly accurate detection of dairy product adulteration using common adulterants (100% accuracy) and discrimination of samples according to their manufacturer (93%).
Water quality control employs techniques mostly targeting individual analytes; group detection is also practiced, but the choice of group methods is limited, which supports interest in developing such methods. We have examined an interaction of hypochlorite with a chlorine-containing heptamethine carbocyanine dye in the presence of 30 organic and inorganic model analytes that were found to induce diverse color changes in the system. The main supposed mechanisms are retardation of the dye oxidation with hypochlorite (presumably by scavenging chlorine radicals) and substitution of chlorine atom in the dye by the most nucleophilic analytes (amines, amino acids, proteins, DNA, phenol). The grass-green substitution product is more contrastingly visible against the dark-purple hypochlorite oxidation product of the dye than against the original emerald-green dye. The indicator reaction is monitored photographically for 10–40 min and the images are processed using principal component analysis (PCA) or linear discriminant analysis (LDA), allowing for data convolution for the complex color transitions. Nitrogen compounds are discriminated from the others, and more reactive analytes (tryptophan, cysteine, bovine serum albumin, and DNA) are detected in the presence of less reactive ones in natural water. The system is promising for the development of group assays for dissolved organic matter and discrimination of water samples.