Using a cotton thread-based colorimetric sensor modified by carboxymethylcellulose and cuprizone with smartphone detection for quantification of copper.

In the present work, we report the development of a novel cotton thread-based colorimetric sensor modified by carboxymethylcellulose (CMC) and cuprizone (CPZ) with smartphone detection and its application for the quantitative determination of cupric ions in water and cachaça. The cotton thread/smartphone detection-based colorimetric method is an easily affordable, low-cost technique which allows one to perform real-time and on-field determination analyses, especially with limited financial resources. The method involves the complexation of Cu(II) with CPZ, which causes a change in the coloration of the cotton thread from a shade of white to blue in the detection zone of the colorimetric sensor. The immobilization of CPZ on CMC in the cotton thread leads to the pre-concentration of Cu(II) via a complexation mechanism with colorimetric reaction. The application of the colorimetric sensor allows the quantification of copper in the range from 1 to 12 mg L-1, with a low limit of detection of 0.21 mg L-1. In addition, the recovery assays conducted in samples of water and cachaça resulted in recovery percentages ranging from 84.9% to 107%, which is indicative of a precise method. To validate the precision of the proposed colorimetric method, the values obtained from the quantification analysis were compared with those of the flame atomic absorption spectrometry and a good agreement at the 95% confidence level was obtained.

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.

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%.

An environment-friendly spot test method with digital imaging for the micro-titration of citric fruits.

A new method to determine the total titratable acidity of orange, lemon and passion fruit, based on a spot test obtained from digital images and using anthocyanins as the biodegradable indicator, is presented for the first time. The colorimetric reactions were carried out by acid-base titration on a microscale, employing anthocyanin with a microplate for spot test purposes, with detection by digital imaging. To obtain highly precise data, a chamber based on a diffuser was developed to control the illumination supplied by the light emitting diodes, and coupled to a smartphone to acquire adequate digital images. High precision was obtained with a relative standard deviation of 0.758% for n = 95. The RGB values were extracted from the digital images and used as analytical signals, the values being correlated with the micro-volume of the titrant and used to construct the titration curves and obtain the first and second derivatives, respectively. For comparative purposes, the official AOAC (Association of Official Analytical Chemists) and MAPA (Ministry of Agriculture, Livestock and Food Supply of Brazil) methods were used and the results compared by applying the paired t-test at the 95% confidence level (n = 3). No difference was found between the values and the relative errors were less than 2.8%. The micro-titrimetric method was fast, uses anthocyanins as the natural indicator, is practical, and permits a reduction of 922 times or 99.9% of the volume required in a conventional titration. It is therefore ideal for routine analyses leading to a reduction in the waste generated, according to the principles of green chemistry.

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.

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.

Amphetamine and derivatives in natural weight loss pills and dietary supplements by capillary electrophoresis-tandem mass spectrometry.

A capillary electrophoresis-tandem mass spectrometry (CE-MS/MS) method for amphetamine (AM), phentermine (PTM), methamphetamine (MAM), methylenedioxyamphetamine (MDA), methylenedioxymethamphetamine (MDMA), and methylenedioxyethylamphetamine (MDEA) in commercial samples of homeopathic and phytotherapic medicines and dietary supplements is presented. The samples were submitted to a modified QuEChERS extraction procedure (at apparent pH 13) followed by electrophoretic separation in 0.1molL-1 formic acid electrolyte (pH 2.4) and detection by ESI-MS/MS. A polyvinyl alcohol coated capillary was employed to prevent the adsorption of the analytes to the capillary wall. The limits of detection and quantitation were from 0.02 to 0.06µgL-1 and from 0.06 to 0.21µgL-1, respectively, with recovery ranging from 85 to 123% and the standard deviations were not greater than 6.1%. In addition, the separation occurs in less than six minutes.

Determination of biogenic amines in beer and wine by capillary electrophoresis-tandem mass spectrometry.

A capillary electrophoresis-tandem mass spectrometry (CE-MS/MS) method for the simultaneous assessment of nine biogenic amines (spermine, spermidine, putrescine, cadaverine, histamine, phenylethylamine, tryptamine, tyramine, and urocanic acid) in commercial samples of beer and wine is introduced. The samples were submitted to a simple clean-up step with poly(vinylpolypyrrolidone) followed by filtration. Electrophoretic separation in a polyvinyl alcohol (PVA)-coated capillary using 0.5 mol L(-1) acetic acid (pH 2.5) as background electrolyte and detection by electrospray-tandem mass spectrometry was employed. The range of the correlation coefficients of the calibration curves of the analyzed compounds was 0.996-0.999, and the limits of detection and limits of quantification were in the range of 1-2 µg L(-1) and 3-8 µg L(-1), respectively. The recovery values for samples spiked at three concentration levels (0.2, 0.5, and 1.0 mg L(-1)) ranged from 87 to 113% with standard deviation not greater than 5.8%. The use of a PVA-coated silica capillary allows suppressing the electroosmotic flow and, consequently, increasing of the separation efficiency. The method was successfully used to determine biogenic amines in commercial samples of beer and wine.

Determination of halosulfuron-methyl herbicide in sugarcane juice and tomato by capillary electrophoresis-tandem mass spectrometry.

A capillary electrophoresis-tandem mass spectrometry (CE-MS/MS) method for the determination of halosulfuron-methyl (HSU) residue in samples of sugarcane juice and tomato is introduced and validated. The samples were submitted to a QuEChERS extraction procedure followed by electrophoretic separation in NH4HCO3 electrolyte (adjusted to pH 8.5) and detection by electrospray-tandem mass spectrometry. The total HSU migration took place in less than 3.5 min, and the detection was accomplished by monitoring three fragmentation processes of this anion: m/z 435-182, 139, and 83. The R(2) values for concentrations up to 100 ppb (µg kg(-1)) were, respectively, 0.992, 0.992, and 0.978. Recovery values for samples spiked at three concentration levels (10, 20 and 50 ppb) were in the range of 96-104% with standard deviation not greater than 5.0%. The limit of detection for HSU in sugarcane juice and tomato was 2 ppb for both samples.

A simple approach to compensate the suction caused by the electrospray ionization source in capillary electrophoresis-mass spectrometry systems.

ESI sources continuously consume the liquid at the tip of the capillary, which causes the dragging of the BGE. The laminar nature of this flow causes the broadening of the peaks and loss of separation efficiency. The usual solution for this problem is to compensate this phenomenon by reducing the pressure at the inlet vial by either leveling of this vial or pumping off the air that is over it. However, one must know the pressure to be applied in order to prevent under- or over-compensation. The procedure herein introduced allows the easy calculation of this pressure by obtaining two electropherograms at two different values of separation voltage. The migration times of the peaks allow the calculation of the apparent mobilities even in the presence of the laminar flow. Therefore, one can calculate the contributions from both electrophoresis and hydrodynamic flow, and finally the pressure associated with the undesirable flow. This pressure is then applied as a negative pressure at the inlet vial in the following experiments. Increase of up to 192% in the number of plates was obtained in a simple experiment. In addition, the bubble forming caused by the ESI suction during injection was prevented by turning off the nebulizer gas during the changes of inlet vials.

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.

Digital image-based flame emission spectrometry.

A digital image-based flame emission spectrometric (DIB-FES) method for the quantitative chemical analysis is proposed here for the first time. The DIB-FES method employs a webcam to capture the digital images which are associated to a radiation emitted by the analyte into an air-butane flame. Since the detection by webcam is based on the RGB (red-green-blue) colour system, a novel mathematical model was developed in order to build DIB-FES analytical curves and estimate figures of merit for the proposed method. In this approach, each image is retrieved in the three R, G and B individual components and their values were used to define a position vector in RGB three-dimensional space. The norm of this vector is then adopted as the RGB-based value (analytical response) and it has revealed to be linearly related to the analyte concentration. The feasibility of the DIB-FES method is illustrated in three applications involving the determination of lithium, sodium and calcium in anti-depressive drug, physiological serum and water, respectively. In comparison with the traditional flame emission spectrometry (trad-FES), no statistic difference has been observed between the results by applying the paired t-test at the 95% confidence level. However, the DIB-FES method has offered the largest sensitivities and precision, as well as the smallest limits of detection and quantification for the three analytes. These advantageous characteristics are attributed to the trivariate nature of the detection by webcam.

An inexpensive, portable and microcontrolled near infrared LED-photometer for screening analysis of gasoline.

A microcontrolled, portable and inexpensive photometer is proposed. It uses a near infrared light emitting diode (NIR LED) as radiation source, a PbSe photoresistor as infrared detector and a programmable interrupt controller (PIC) microcontroller as control unit. The detector system presents a thermoresistor and a thermoelectric cooling to control the detector temperature and keep the noise at low levels. The microcontroller incorporated total autonomy on the proposed photometer. As its components are inexpensive and of easy acquisition, the proposed NIR LED-photometer is an economical alternative for chemical analyses in small routine, research and/or teaching laboratories. By being portable and microcontrolled, it also allows carrying out field chemical analyses. The instrument was successfully applied on the screening analysis to verify adulteration in gasoline samples.