A fluorescence digital image-based method using carbon quantum dots to evaluate the compliance of a biocidal agent.

In this work, a simple, low-cost and easy-to-handle analytical procedure based on carbon quantum dots (CQDs) is proposed to check commercially available formulated microbicides that are used to mitigate the transmission of viruses, such as SARS-COV-2, or bacterial diseases. For this purpose, CQDs were synthesized via pyrolysis using citric acid and ethylenediamine as precursors to produce an intense fluorescence that is used to measure the concentration of hypochlorite, an important biocidal agent present in sanitizing mats, by quenching mechanisms. The characterization of the CQDs was performed using IR spectrophotometry, UV-Vis spectrophotometry, spectrofluorometry, thermogravimetric analysis, scanning electron microscopy, dynamic light scattering, X-ray diffraction, energy-dispersive spectroscopy, and zeta potential measurements. For analytical purposes, fluorescence was measured in a UV chamber irradiated using an LED with the maximum emission at 350 nm. A smartphone was coupled to the UV chamber to measure the fluorescence quenching due to the presence of hypochlorite, and further the digital images were decomposed by RGB data using free software. Tests of pH, CQD concentration and stability of the fluorescence emitted were performed. The stability study of the fluorescence emitted by the CQD solution showed a relative standard deviation lower than 5.0%. The fluorescence digital image-based (FDIB) method resulted in a linear range from 17.44 µmol L-1 to 90.0 µmol L-1 with an LOD of 3.30 µmol L-1 for the determination of hypochlorite using a microplate made of PLA (polylactic acid) customized using a 3D printer. Furthermore, the hypochlorite concentration was tested in situ for its compliance in a sanitizing mat, in a real use situation (daily, a group of four people, each one kept their feet on the mat for 30 s). After 2.5 h, the monitored concentration of hypochlorite was 0.04953% (w/v) or 7.63 mmol L-1, and therefore, it was inefficient to act as a sanitizing agent. Thus, for the first time in the literature, an FDIB method with CQDs is used to verify in situ microbicide practices with a fast and low-cost analytical procedure.

In situ voltammetric analysis of 2,4-dichlorophenoxyacetic acid in environmental water using a boron doped diamond electrode and an adapted unmanned air vehicle sampling platform.

In the present work a voltammetric method was developed for in situ detection of 2,4-dichlorophenoxyacetic acid (2,4-D) in environmental water samples, using a compact and lightweight electrochemical cell using a fused deposition modeling (FDM) 3D printer with biodegradable polylactic acid filament, and a boron-doped diamond electrode (BDDE). The samples were collected by an adapted unmanned aerial vehicle (UAV) with a micropump and a miniature solenoid valve powered by an open source microcontroller. After optimizing the supporting electrolyte, pH and parameters of the square wave voltammetry (SWV) a linear analytical curve for 2,4-D in 0.5 mol L-1 Na2SO4 (pH = 2.0 regulated using 0.5 mol L-1 H2SO4 solution) in a concentration range from 100 nmol L-1 to 911 nmol L-1 with 34 nmol L-1 as the limit of detection was obtained. The same samples in situ analyzed by SWV were sent to the laboratory for gas chromatography-mass spectrometry (GC-MS) analysis; and there was no statistical difference from the concentration of 2,4-D in any of the samples at a 95% confidence level. Therefore, the method developed for quantification of 2,4-D in water provides an important environmental monitoring tool since it enables access to difficult areas in a fast, practical and safe way. This is the first time that an adapted UAV with these features has been used to collect environmental water for in situ electrochemical analysis as a screening tool to alert the presence of environmental hazard compounds, such as 2,4-D. Thus, this method can be used by environmental and sanitary control agencies to monitor or to supervise environmental water quality with response in real time.

A color reaction for the determination of Cu2+ in distilled beverages employing digital imaging.

In this work, we describe for the first time the synthesis of a thiocarbazone for the selective determination of Cu2+ in distilled beverages. The method was based on the complexation reaction of Cu2+ with the thiocarbazone, and the colored product was analyzed using a smartphone application. The thiocarbazone reacts with Cu2+ to form a 1:1 (metal:ligand) complex. The Cu2+ complex was characterized by UV, IR and NMR spectral analyses. The proposed reaction yields a yellow color, and therefore, channel B of the RGB system was used in the analysis. After optimizing the reaction conditions, an analytical curve was obtained to determine Cu2+ concentrations ranging between 0.25 and 6.75 mg L-1; the use of 400 µL sample volumes led to a relative standard deviation (n = 5) of 3.2% and a detection limit of 0.18 mg L-1. Recovery experiments were performed with sugar cane spirits, whiskies and tequilas to evaluate the accuracy of the method, and the recovery obtained ranged from 80.5 to 112.2%.

Novel Hg (II) selective fluorescent green sensor based on carbon dots synthesized from starch and functionalized with methimazole.

We describe a green new method for the synthesis of water-soluble photoluminescent carbon dots (CDs) that were functionalized with methimazole (MTZ) and applied to determine Hg2+ based on the fluorescence extinction. Starch obtained from rice was used as a natural source for the production of CDs by hydrothermal treatment. Also, it was proposed a factorial design to optimize the parameters for CD synthesis and the results showed that the luminescence intensity is a function of temperature and not of the heating time in the hydrothermal process. The synthesized CDs were characterized using fluorescence techniques, Fourier transform infrared spectroscopy (FTIR), and UV-Vis spectroscopy. Through transmission electron microscopy (TEM) and dynamic light scattering (DLS), it was found the formation of CDs on a nanometer scale with an average size of 11 nm. The functionalization with MTZ, eliminated all interferences from other metals, indicating a selective response to Hg2+ ions. The method was applied to Hg2+ determination in waters. Under optimal conditions, was obtained a limit of detection of 1.8 × 10-7 mol L-1 with a linear range from 3.3 × 10-7 to 50.0 × 10-6 mol L-1. Therefore, the proposed method can be considered a simple, selective, and precise alternative that minimizes the number of reagents used for Hg2+ determination in natural waters, and can be applied on a large scale in environmental analyzes.

Microanalysis based on paper device functionalized with cuprizone to determine Cu2+ in sugar cane spirits using a smartphone.

In this work we propose for the first time, a paper-based test strip to analyse Cu2+ content in sugar cane spirits, which, due to its simplicity, high portability and fast analytical response (3 min), can be easily applied to in situ analyses by producers. The test strip was developed aiming: i) identify qualitatively the Cu2+ content in sugar cane spirits, and, ii) determine quantitatively the Cu2+ content using a digital image method employing a smartphone. The paper-based test strip was functionalized with cuprizone and optimized through a Box-Behnken, an experimental design for obtaining the best reaction conditions. Based on qualitative method with naked eyes approach performed by six volunteers analyst untrained, the method present a percentage of accuracy of 93%. For the quantitative analysis, it was determined the metal content at a level of statistical agreement with the reference method, as well as it was obtained the dynamic linear range from 2 to 13 mg L-1 with limits of detection and quantification of 0.034 and 0.103 mg L-1, respectively. Furthermore, the quantitative method showed a reliable precision with an RSD of 4.3% (n = 10) and the recovery of Cu2+ ranged from 80 to 103.8%.

Low cost in situ digital image method, based on spot testing and smartphone images, for determination of ascorbic acid in Brazilian Amazon native and exotic fruits.

In this work, we propose a method that employed a smartphone to capture images obtained from a colorimetric spot test to determine ascorbic acid (AA) in Brazilian Amazon native and exotic fruits. The spot test reaction was based on reduction of Fe(III) by AA and further complexation with 1,10-phenanthroline. After optimization, the limit of detection was 8.5 × 10-7 mol L-1. Brazilian Amazon native fruits such as bacuri, cupuaçu, muruci, yellow mombin, as well as others as cashew, mango, orange and passion fruit, were analyzed. In order to determine the accuracy of this method, iodometric titration was used; results were in close agreement with a confidence level of 95% (paired t-test). Moreover, recoveries ranged from 87.1 to 116%. The method is economic, environmentally friendly, and portable, and might useful for small producers and family agriculture businesses unable to afford specialized laboratory analysis in the north region of Brazilian Amazon.

Smartphone application for captopril determination in dosage forms and synthetic urine employing digital imaging.

A simple, accurate, and low-cost analytical procedure for captopril determination through digital imaging is presented. The method relies on the spot test reaction between captopril and palladium (II) chloride, which produces a yellow and water-soluble complex with maximum absorption at 380 nm. A smartphone camera and a portable apparatus built for internal lighting control were put together to acquire digital images of reaction mixtures. Digital image processing through the RGB approach was used to establish a quantitative relationship between color intensity and captopril concentration. Under the most suitable operational and experimental conditions, an analytical curve was built monitoring the Blue channel within the concentration range of 3.12 × 10-5 to 1.21 × 10-3 mol L-1. Limits of detection and quantification were equal to 8.06 × 10-6 and 2.69 × 10-5 mol L-1, respectively. Recovery percentage in synthetic urine samples ranged from 97.1% to 102.9%. Results were compared with a reference method and no significant differences were detected at the 95% confidence level. The developed method presents budgetary and environmental advantages concerning the use of cheap and easy-handled devices and the consumption of very low volumes of reagent (800 µL per determination). It can be a useful analytical tool for laboratories with limited financial resources while abiding by green chemistry principles.

A digital image method of spot tests for determination of copper in sugar cane spirits.

In this work the development and validation of analytical methodology for determination of copper in sugarcane spirit samples is carried out. The digital image based (DIB) method was applied along with spot test from the colorimetric reaction employing the RGB color model. For the determination of copper concentration, it was used the cuprizone - a bidentate organic reagent - which forms with copper a blue chelate in an alkaline medium. A linear calibration curve over the concentration range from 0.75 to 5.00mgL-1 (r2=0.9988) was obtained and limits of detection and quantification of 0.078mgL-1 and 0.26mgL-1 were acquired, respectively. For the accuracy studies, recovery percentages ranged from 98 to 104% were obtained. The comparison of cooper concentration results in sugar cane spirits using the DIB method and Flame Atomic Absorption Spectrometry as reference method showed no significant differences between both methods, which were performed using the paired t-test in 95% of confidence level. Thus, the spot test method associated with DIB allows the use of devices as digital cameras and smartphones to evaluate colorimetric reaction with low waste generation, practicality, quickness, accuracy, precision, high portability and low-cost.

Flow-injection spectrophotometric determination of captopril in pharmaceutical formulations using a new solid-phase reactor containing AgSCN immobilized in a polyurethane resin

A simple flow-injection analysis procedure was developed for determining captopril in pharmaceutical formulations employing a novel solid-phase reactor containing silver thiocyanate immobilized in a castor oil derivative polyurethane resin. The method was based on silver mercaptide formation between the captopril and Ag(I) in the solid-phase reactor. During such a reaction, the SCN- anion was released and reacted with Fe3+, which generated the FeSCN2+ complex that was continuously monitored at 480 nm. The analytical curve was linear in the captopril concentration range from 3.0 × 10-4 mol L-1 to 1.1 × 10-3 mol L-1 with a detection limit of 8.0 × 10-5 mol L-1. Recoveries between 97.5% and 103% and a relative standard deviation of 2% for a solution containing 6.0 × 10-4 mol L-1 captopril (n = 12) were obtained. The sample throughput was 40 h-1 and the results obtained for captopril in pharmaceutical formulations using this procedure and those obtained using a pharmacopoeia procedure were in agreement at a 95% confidence level.

Um procedimento simples de análise por injeção em fluxo foi desenvolvido para a determinação de captopril em formulações farmacêuticas empregando um novo reator em fase sólida contendo tiocianato de prata imobilizado em resina poliuretana obtida a partir de óleo de mamona. O método foi baseado na formação de um mercapto composto de prata, no reator em fase sólida, obtido entre o captopril e Ag (I) imobilizada. Durante a reação, íons SCN- eram liberados e reagiam com Fe3+, gerando o complexo FeSCN2+, que foi continuamente monitorado em 480 nm. A curva analítica foi linear no intervalo de concentração de captopril entre 3,0 × 10-4 a 1,1 × 10-3 mol L-1 com um limite de detecção de 8,0 × 10-5 mol L-1. Recuperações entre 97,5-103% e desvio padrão relativo de 2% para uma solução contendo 6,0 × 10-4 mol L-1 de captopril (n = 12) foram obtidos. A frequência de amostragem foi de 40 h-1 e os resultados obtidos para captopril em formulações farmacêuticas utilizando este procedimento e o da Farmacopeia, estão de acordo em um nível de confiança de 95%.

A compact miniaturized continuous flow system for the determination of urea content in milk.

A multicommutation-based flow system with photometric detection was developed, employing an analytical microsystem constructed with low temperature co-fired ceramics (LTCC) technology, a solid-phase reactor containing particles of Canavalia ensiformis DC (urease source) immobilized with glutaraldehyde, and a mini-photometer coupled directly to the microsystem which monolithically integrates a continuous flow cell. The determination of urea in milk was based on the hydrolysis of urea in the solid-phase reactor and the ammonium ions produced were monitored using the Berthelot reaction. The analytical curve was linear in the urea concentration range from 1.0 x 10(-4) to 5.0 x 10(-3) mol L(-1) with a limit of detection of 8.0 x 10(-6) mol L(-1). The relative standard deviation (RSD) for a 2.0 x 10(-3) mol L(-1) urea solution was lower than 0.4% (n = 10) and the sample throughput was 13 h(-1). To check the reproducibility of the flow system, calibration curves were obtained with freshly prepared solutions on different days and the RSD obtained was 4.7% (n = 6). Accuracy was assessed by comparing the results of the proposed method with those from the official procedure and the data are in close agreement, at a 95% confidence level.

Generation and destruction of unstable reagent in flow injection system: determination of acetylcysteine in pharmaceutical formulations using bromine as reagent.

A flow injection spectrophotometric procedure was developed for determination of acetylcysteine in sachets and liquid formulations. The determination of this drug was carried out by reacting it with bromine chemically generated in flow injection system monitored continuously at 400 nm. Acetylcysteine reacts with bromine causing a decrease in the absorbance that is proportional to the analyte concentration. The bromine in excess was destroyed on-line by an ascorbic acid solution before the discard. The calibration curve for acetylcysteine determination was linear in the concentration range from 1.6 x 10(-4) to 1.6 x 10(-3) mol/l with a detection limit of 8.0 x 10(-5) mol/l. The relative standard deviation (R.S.D.) was lesser than 1.2% for a solution containing 5.3 x 10(-4) mol/l acetylcysteine (n=10), and 60 determinations per hour were obtained.