Reusable graphite-based electrochemical sensors for L-dopa and dopamine detection.

A fully reusable electrochemical device is proposed for the first time made from laser cutting and a homemade conductive ink composed of carbon and nail polish. As a sensor substrate, we applied polymethyl methacrylate, which allows the surface to be renewed by simply removing and reapplying a new layer of ink. In addition to the ease of renewing the sensor's conductive surface, the design of the device has allowed for the integration of different forms of analysis. The determination of L-Dopa was performed using DPV, which presented a linear response range between 5.0 and 1000.0 µmol L-1, and a LOD of 0.11 µmol L-1. For dopamine, a flow injection analysis system was employed, and using the amperometric technique measurements were performed with a linear ranging from 2.0 to 100.0 µmol L-1 and a LOD of 0.26 µmol L-1. To demonstrate its applicability, the device was used in the quantification of analytes in pharmaceutical drug and synthetic urine samples.

Environmentally friendly and novel solid-liquid phase microextraction of maneb fungicide in fruits and vegetables.

The dithiocarbamates class has been widely used in agriculture practices because of lower toxicity and instability than organophosphates and carbamates. Among them, the maneb has been used to produce several fruits and vegetables, but its high ingestion can adversely affect human health. This work developed the Solid-Liquid Phase Microextraction (SLPME) for extraction of the maneb in foods sample with posterior determination by Flow injection analysis-Flame Absorption Atomic Spectroscopy (FIA-FAAS). Curve analytical had a linear range from 0.9 to 20.0 µmol L-1 maneb (A = 5.94 × 10-4 C (µmol L-1) + 6.93 × 10-4), good repeatability (4.07%) and reproducibility (3.39%), limits of quantification (5.98 µmol L-1) and detection (0.197 µmol L-1), which was above of the established by regulatory agencies. The extraction of the maneb was performed using 685 µL of the solution of the 1.00 × 10-3 mol L-1 of EDTA, and it has excellent recovery values from 80.85 to 106.51%. Therefore, the developed SLPME demonstrated an alternative environmentally friendly for quickly extracting maneb from food samples (apple, papaya, and tomato).

Development of a 3D disposable device for the electrochemical determination of diclofenac in different matrices.

In this work, the development of a disposable electrochemical device (US$ 0.02 per electrode) using a 3D printed support (3Ds) of acrylonitrile butadiene styrene (ABS) insulating filament with a composite material (CM) based on graphite and nail polish, immobilized on the support surface, was described for the electrochemical determination of diclofenac (DCF). The device was compared to the commercial glassy carbon electrode (GCE) and showed superior electroanalytical performance with approximately 1.8-fold higher current density. Additionally, an amperometric method for DCF determination in tap water, synthetic urine, and pharmaceutical formulation samples with the proposed electrode, using a flow injection analysis (FIA-AD) system, was developed. The optimized method presented excellent detectability (LOD = 0.47 µmol L-1), with excellent precision and accuracy (relative standard deviation < 5.6%) and percent recovery from spiked samples ranging from 89 to 106%. In addition, the sensor showed optimal analytical frequency with approximately 108 injections per hour, which demonstrates the potential of this system using the proposed disposable electrode for implementation in routine analysis and quality control with good selectivity and sensitivity.

A simple method to quantify azo dyes in spices based on flow injection chromatography combined with chemometric tools.

Para Red (PR) and Sudan dyes have been illegally used as colorants to adulterate certain foods by enhancing their red/orange colour. In addition, they are toxic and carcinogenic. This work presents the development of a simple flow injection chromatographic method combined with chemometric tools to perform the determination of PR, Sudan I (SI) and Sudan II (SII) in food samples. The flow chromatographic system consisted of a low-pressure manifold coupled to a reverse phase monolithic column. A Partial Least Square (PLS) model was applied to resolve overlapped absorption spectra registered for each dye at the corresponding retention time. The relative errors of calibration (RMSECV, %) were 0.49, 0.85 and 0.23, and the relative errors of prediction (RMSEP, %) were 1.12, 0.75 and 0.33 for PR, SI and SII, respectively. The residual predictive deviation (RPD) values obtained were higher than 3.00 for all analytes. The method was successfully applied to quantify the dyes in six different commercial spices samples. The results were compared with the HPLC reference method concluding that there were no significant differences at the studied confidence level (α = 0.05). The proposed method can be used to rapidly determine the analytes in a simple, reliable, low-cost and environmentally-friendly manner. Supplementary Information: The online version contains supplementary material available at 10.1007/s13197-021-05299-8.

Determination of chromium(III) picolinate in dietary supplements by flow injection - electrospray ionization - tandem mass spectrometry, using cobalt(II) picolinate as internal standard.

In this work, a principle of flow injection analysis (FIA) was applied for sample introduction to an electrospray ionization - ion trap mass spectrometer (ESI-ITMS) with the aim to quantify chromium(III) picolinate (CrPic3) in commercial supplements by multiple reaction monitoring, and using cobalt(II) picolinate as internal standard (IS). FIA system was operated with ammonium formate 10 mmol L-1 in methanol-water (1:1, v/v) as a carrier solution at a flow rate 200 µL min-1; 100 µL injections were performed in 2-min intervals. Setting ion transitions m/z 419 â†’ 270 and 304 â†’ 260 for the analyte and IS, respectively, and 100 ms integration time, the method detection and quantification limits 12 ng g-1 and 40 ng g-1 of Cr (as CrPic3) in the air-dried powder. Acetonitrile extracts of the real-world samples presented varying from sample-to-sample chemical composition and IS efficiently compensated for ionization interferences. Mean results from triplicate analysis of four different supplements were obtained with relative standard deviation 0.1-4.0%, indicating acceptable precision. Trueness of the proposed FIA-ESI-ITMS/MS procedure was demonstrated by 95.8-108% percentage recoveries attained in the analysis of the CrPic3-spiked samples. For comparative purposes, total Cr was determined by ICP-MS. The quantitative results obtained indicate the necessity of analytical control of Cr(III) supplements commercially available and demonstrate that the proposed FIA-ESI-ITMS/MS procedure is well-suited for the determination of CrPic3 in such products.

Renewable column on-line magnetic preconcentration of Cd(II) using Fe3O4 nanoparticles functionalized with l-glutamine for determination by flame atomic absorption spectrometry.

This work reports the development of a flow injection analysis (FIA) system for online magnetic preconcentration and determination of Cd(II) in water by flame atomic absorption spectrometry (F AAS). Magnetic nanoparticles of Fe3O4, functionalized with l-glutamine (GlnMNP), were synthesized and used as a support for Cd(II) retention and preconcentration. Each measurement cycle was performed through online complexation of Cd(II) by l-glutamine attached to Fe3O4 magnetic nanoparticles at pH 10.5, followed by their retention in a coil due to the action of a cylindrical permanent magnet. Subsequently, the retained magnetic nanoparticles containing Cd(II) were dissolved with an acid solution (4 mol L-1 HCl solution), releasing Cd(II) for transportation to the detector. The main chemical and flow parameters that affected the performance of the system were optimized. Under optimum experimental conditions, the limits of detection and quantification were 2 and 5 µg L-1, respectively, and a relative standard deviation of 6.5% (at 50 µg L-1, n = 10) was observed. The FIA system allowed the injection of 24 samples per hour and presented an enrichment factor of four. The method was applied in the analysis of river and pond water samples. The pond water sample was irradiated with ultraviolet light prior to the analysis, in order to eliminate the organic matter. Accuracy of the method was assessed by recovery tests, which provided recovery percentages between 82 and 111%. The developed method was also compared to the direct determination by graphite furnace atomic absorption spectrometry (GF AAS). In this case, the results were not statistical different at 95% confidence level when the Student's t-test was applied.

Magnetic restricted-access carbon nanotubes for the extraction/pre-concentration of organophosphates from food samples followed by spectrophotometric determination.

In this work, magnetic restricted-access carbon nanotubes (M-RACNTs) were synthesized, characterized and used in the dispersive solid-phase extraction (d-SPE) of organophosphate pesticides (OPPs) from food samples (broccoli, eggplant, cauliflower, and soy milk), followed by spectrophotometric determination in a flow injection analysis system. Fe3O4 nanoparticles were incorporated in the multi-walled carbon nanotubes employing dimethylformamide. The dimethylformamide was used as a solvent in the incorporation process, forming the suspension of both particles. The resulting M-CNTs were covered with an external bovine serum albumin (BSA) layer, chemically crosslinked. M-RACNTs were able to efficiently capture OPPs, excluding about 95% of the proteins from food matrices. The analyses were carried out in a flow injection analysis system (FIA), with the spectrophotometric detection (at 560 nm) of the complex formed by the reaction between OPPs, N-bromosuccinimide and rhodamine B. A fractional factorial design method was used to optimize the experimental parameters. The addition/recovery test showed results from 95.5% to 108.9%. Accuracies were checked by comparing the results obtained with the proposed and standard HPLC methods, which were in agreement. The proposed method was linear from 5 to 90 µg L-1 of OPPs, with limits of detection and quantification of 0.74 and 5 µg L-1 and precision of 3.67%, expressed as relative standard deviation. The pre-concentration factor was about 164 times.

Direct analysis of ascorbic acid in food beverage samples by flow injection analysis using reduced graphene oxide sensor.

In this paper, a simple, sensitive and precise electroanalytical method was developed using flow injection analysis (FIA) with amperometric detection and reduced graphene oxide sensor for ascorbic acid determination in samples of multivitamin beverages, milk, fermented milk, and milk chocolate. The advantages of this sensor include a potential displacement of 450 mV and a 2-fold peak current increase for electrochemical oxidation of ascorbic acid, which resulted in a highly sensitive method. No interference of sample matrix was observed, avoiding solvent extraction procedures (samples were only diluted). The FIA allowed a high analytical frequency, approximately 96 injections per hour, together with adequate detection limit of 4.7 µmol L-1. Good precision (RSD < 7%) and accuracy (recoveries between 91 and 108%) evidenced the robustness of the method. The method was compared with ultra-fast liquid chromatography (UFLC) obtaining statistically similar results (95% confidence level). The ascorbic acid content in samples varied from 0.065 to 2.53 mmol L-1.

Oxidized carbon nanotubes as sorbent for miniaturized solid-phase extraction of progestins from environmental water samples prior to their determination by HPLC-UV.

A solid-phase extraction method is presented for micro-extraction of three progestins (levonorgestrel, 19-norethisterone acetate and medroxyprogesterone acetate) from water samples. A mini-column was packed with 60 mg of oxidized multiwalled carbon nanotubes and coupled to a flow injection assembly. The extraction parameters, such as washing solution, eluent type, eluent volume, flow rate and sample volume, were optimized. Separation and determination were performed by HPLC with UV detection. The method has a good linear range (0.90-9.0 µg L-1), acceptable limits of detection (0.05-0.14 µg L-1) and low RSDs (0.8-4.6%). Attractive features of the method include low consumption of organic solvents and preconcentration factors of up to 100. The method was applied to analyze stream, underground and effluent water samples, and recoveries between 74 and 121% were obtained. Graphical abstractSchematic representation of the flow injection assembly couples to an ox-MWCNTs extraction column used to perform the solid phase extraction procedure of progestins in environmental water samples.

Rapid Analysis in Continuous-Flow Electrochemical Paper-Based Analytical Devices.

A simple and low-cost continuous-flow (CF) electrochemical paper-based analytical device (ePAD) coupled with thermoplastic electrodes (TPEs) was developed. The fast, continuous flow combined with flow injection analysis was made possible by adding two inlet reservoirs to the same paper-based hollow channel flowing over detection electrodes, terminating in a fan-shaped pumping reservoir. The upstream inlet reservoir was filled with buffer and provided constant flow through the device. Sample injections were performed by adding 2 µL of the sample to the downstream sample inlet. Differences in flow resistance resulted in sample plugs displacing buffer as the solution flowed over the working electrodes. The electrodes were fabricated by mixing carbon black and polycaprolactone (50% w/w). CF-TPE-ePADs were characterized with chronoamperometry using ferrocenylmethyl trimethylammonium as the electrochemical probe. Optimized flow rates and injection volumes gave analysis times roughly an order of magnitude faster than those of previously reported flow injection analysis ePADs. To demonstrate applicability, the CF-TPE-ePADs were used to quantify caffeic acid in three different tea samples. The proposed method had a linear range from 10 to 500 µmol L-1 and limits of detection and quantification of 2.5 and 8.3 µmol L-1, respectively. Our approach is promising for fabricating simple, inexpensive, yet high-performance, flow injection analysis devices using paper substrates and easy-to-make electrodes that do not require external mechanical pumping systems or complicated valves.

Flow analysis during the 60 years of Talanta.

A parallel within the development of flow analysis and the consolidation of Talanta as one of the main journals in analytical chemistry is drawn. Influence of scientific divulgation, meeting organizations, thematic issues devoted to scientific events and Talanta awards in the recent development of flow analysis is emphasized. For didactic purposes, the discussion is focused on three 20-year periods. A scientometric overview demonstrated the consolidation of Talanta as the main journal for divulgation of recent innovations in flow analysis.

Tolfenamic acid on-line preconcentration strategy on carbon nanotubes minicolumn with fluorimetric detection.

Nonsteroidal anti-inflammatory agents (NSAIDs) are a group of pharmaceuticals considered one of the most popular drugs used in clinical practice applied to the treatment of acute and chronic conditions. Some pharmaceuticals products are excreted reaching the environment and altering the balance of ecosystems. This work proposes a new fluorimetric flow injection (FI) methodology for the NSAID tolfenamic acid quantification based on the quenching effect of the analyte on fluorescent signal of bovine serum albumin fluorophore. Results put in evidence a mechanism of static quenching, with a Stern Volmer constant value of 1.8 × 107 L mol-1. To achieve the selective on-line preconcentration of analyte, a carbon nanotubes mini column was introduced in the FI configuration producing a beneficial effect on high sampling frequency, minimum sample and reagents consumption. The experimental factors that influence batch fluorescent signal and FI analysis have been studied and optimized. At optimal experimental conditions, an adequate tolerance to foreign species was shown. With the flow configuration, a LOD of 0.019 µg L-1, a LOQ of 0.058 µg L-1 were obtained with a sampling rate of 30 samples h-1. The new methodology was successfully applied to analyte determination in tap water and pharmaceutical and factory waste samples with recuperation near to 100%.

Development of new analytical method for preconcentration/speciation of inorganic antimony in bottled mineral water using FIA-HG AAS system and SiO2/Al2O3/SnO2 ternary oxide.

In the present paper, a new analytical preconcentration/speciation method for antimony species determination in bottled mineral water samples using the SiO2/Al2O3/SnO2 adsorbent was developed. The method is based on selective adsorption of Sb(III) ions by SiO2/Al2O3/SnO2 under a wide pH range (2.5-7.5). Total antimony was determined with previous sample treatment using 0.1% (w/v) l-cysteine and the concentration of Sb(V) species was determined by the difference between total and Sb(III). The proposed method provided an analytical curve ranging from 0.50 to 5.00 µg L-1 (r = 0.999), limit of detection (LD) of 0.17 µg L-1 and preconcentration factor (PF) of 136-fold. The method exhibited tolerance to different metal ions and the accuracy was attested from addition and recovery tests (95.2-106.0%) in bottled mineral water samples using 2.0% (w/v) l-cysteine, as well as by analysis of certified material. Only Sb(III) species were determined in mineral water (0.54-1.04 µg L-1).

Boron Doped Diamond Electrodes in Flow-Based Systems.

Boron-doped diamond (BDD) electrodes present several notable properties, such as the largest potential window of all electrode materials (especially in anodic potentials), low background and capacitive currents, reduced fouling compared to other electrodes, mechanical robustness, and good stability over time. On the other hand, flow-based systems are known as well-established approaches to minimize reagent consumption and waste generation and with good compromise between sample throughput and analytical performance (mechanization of chemical assays). This review focuses on the use of BDD electrodes for electrochemical detection in flow systems, such as flow injection analysis (FIA), batch injection analysis (BIA), high performance liquid chromatography (HPLC), and capillary electrophoresis (CE). The discussion deals with the historical evolution of BDD, types of electrochemical pre-treatments (cathodically/H-terminated or anodically/O-terminated), cell configurations, and analytical performance. Articles are discussed in chronological order and subdivided according to the type of flow system: FIA, BIA, HPLC, and CE.

FIA-coupled spectrophotometric method for determination of Cr (VI) traces in natural waters: application of in-line dissolution of 1,5-diphenylcarbazide after heat treatment and activated alumina as adsorbent for preconcentration.

This work proposes the quantification of Cr (VI) ions in natural waters in trace level, using activated alumina (Al2O3) as preconcentration support, controlled in-line dissolution of the solidified chromophore diphenylcarbazide after heat treatment and spectrophotometric detection. The manifold ensures high sensitivity of analytical response, good repeatability, and stability. In this work, optimization of experimental conditions of a flow injection system was chosen as the parameters for greater sensitivity and better selectivity. The selected optimized conditions were 0.30 mol L-1 for H2SO4 concentration, system flow rate as 0.40 mL min-1, sample injection volume of 192.50 µL, 2 min for preconcentration time, and 0.10 mol L-1 for eluent concentration. The analytical curves obtained for real sample analysis show linear range from 0.192 to 0.961 µM, linear correlation coefficient R = 0.9997 and LOD = 0.024 µM. The preconcentration factor of about four times was obtained through the passage of 800 µL of a standard solution containing 0.961 µM of Cr (VI) through mini-column of preconcentration followed by elution at 192.5 µL of NH4OH 0.1 mol L-1 solution. The solid chromogenic reagent presented high durability (weeks in daily use with mass of 0.0993 g) and good reproducibility in analytical signal. The reactivation of the mini-column of alumina should be executed after ten injections of eluent, using 800 µL of HCl 0.02 mol L-1 solution in flow through the same. Each cycle of injection and elution of the sample takes about 5 min on the proposed terms. Despite the length of each cycle still be high, low concentrations can be detected using a technique of relatively low cost. This is due in part, the association dissolution of the chromogenic reagent directly in the line and the preconcentration step. Another important factor is the economy of reagent chromogenic, low generation of reject contributing to better quality of the environment, and the high potential for applications to work in field.

3D printed device for the automated preconcentration and determination of chromium (VI).

A 3D printed device for the fully automated disk-based solid-phase extraction (SPE) of Cr (VI) from water samples has been fabricated. The compatibility of the use of organic solvents for analyte elution with 3D printed flow devices based on polymers fabricated using stereolithograph​y has been evaluated. The developed methodology comprises the complexation of Cr (VI) with 1, 5-diphenylcarbazide (DPC) in acidic medium and the subsequent retention of the complex in a SBD-RPS disk contained within the 3D printed device. A multisyringe flow injection analysis system with online spectrophotometric detection has been used for the automation of the method. The fabricated 3D printed device integrates the different components of the flow analysis manifold, including connectors and mixers, being a powerful approach towards the reproducible construction of highly integrated flow-based manifolds. The extracted Cr (VI)-DPC complex is eluted with a mixture of methanol- sulfuric acid and quantified at 540 nm. The effect on the analytical signal and the optimization of variables were evaluated using multivariate and univariate techniques. A detection limit of 1 ng Cr (VI) and a linear working range of 3.2-600 ng Cr (VI) were obtained using a sample volume of 2 ml. The intra-day and inter-day RSDs were 4.8% (10 µg L-1, n = 12) and 3.4% (n = 5, different day with a different disk), respectively. The applicability of the fabricated 3D printed device has been proved by the determination of Cr (VI) in groundwater, surface water and leachates.

Evaluation of total phenol pollution in water of San Martin Canal from Santiago del Estero, Argentina.

Santiago del Estero is a province located in northwestern Argentina. The Dulce River is used for irrigation through a vast network of channels and ditches, including the San Martin Canal (SMC), which crosses the capital city of Santiago del Estero. This canal's water is used for drinking, as well as recreational use for the general population. However, this river has been seriously polluted for several decades. The present study focuses on the identification and the quantification of the water pollution levels of total phenols in the SMC according to the seasonal periods. Water samples from various areas of the canal in different months of the year, extending from December to September, were collected for analysis. Additionally, the concentration of total dissolved solids (TDS), chlorides, sulphates, nitrites and organic matter, as well as water hardness and alkalinity, were analysed in order to conduct a more complete study of the contamination of this area. The results showed a worrying total phenol concentration that exceeded the limit set by Argentine legislation for drinking water, as well as water for recreational use (5 µg/L). The total phenol (TP) concentration was directly determined by a molecular absorption spectroscopy method based on a new flow injection analysis system (FIA). Under the selected experimental conditions, the detection and quantification limits were 0.0490 and 0.1633 µg/mL, respectively. The developed method provides a number of improvements related to the speed of analysis, the restricted consumption of the reagents and sample volumes and the unnecessary sample treatment that contribute to environmentally friendly analytical chemistry. The results showed that TP make a significant contribution in the SMC pollution, especially during the months of April (400 ±â€¯110 µg/L) and September (240 ±â€¯20 µg/L). A high sulphate concentration that was higher than the limit allowed by the legislation was also found.

3D printed device including disk-based solid-phase extraction for the automated speciation of iron using the multisyringe flow injection analysis technique.

The development of advanced manufacturing techniques is crucial for the design of novel analytical tools with unprecedented features. Advanced manufacturing, also known as 3D printing, has been explored for the first time to fabricate modular devices with integrated features for disk-based automated solid-phase extraction (SPE). A modular device integrating analyte oxidation, disk-based SPE and analyte complexation has been fabricated using stereolithographic 3D printing. The 3D printed device is directly connected to flow-based analytical instrumentation, replacing typical flow networks based on discrete elements. As proof of concept, the 3D printed device was implemented in a multisyringe flow injection analysis (MSFIA) system, and applied to the fully automated speciation, SPE and spectrophotometric quantification of Fe in water samples. The obtained limit of detection for total Fe determination was 7ng, with a dynamic linear range from 22ng to 2400ng Fe (3mL sample). An intra-day RSD of 4% (n = 12) and an inter-day RSD of 4.3% (n = 5, 3mL sample, different day with a different disk), were obtained. Incorporation of integrated 3D printed devices with automated flow-based techniques showed improved sensitivity (85% increase on the measured peak height for the determination of total Fe) in comparison with analogous flow manifolds built from conventional tubing and connectors. Our work represents a step forward towards the improved reproducibility in the fabrication of manifolds for flow-based automated methods of analysis, which is especially relevant in the implementation of interlaboratory analysis.

A simple and new reverse liquid-liquid microextraction for the automated spectrometric determination of doxycycline in chicken fat.

This work presents a new, simple and inexpensive reverse liquid-liquid microextraction of doxycycline (DOC) from chicken fat. In this just 13min extraction methodology, acidulated water, as extraction solvent (400µL), was used. A monochannel flow injection system was designed for the spectrometric determination of the analyte (ʎ=344nm). The extracted solution containing DOC was loaded into the injection valve of the continuous flow manifold. A lineal range between 100 and 700µgDOCkg-1 sample was obtained. The LOD and LOQ were 33µgkg-1 and 100µgkg-1 respectively. The relative standard deviation was 4.87% and the sample throughput for the entire process was 4.5h-1. As recovery values when the method was applied to real samples showed variability, the expanded uncertainties were calculated. Their values indicated that the new method is independent of the concentration of the analyte and the origin of the sample.

Novel spectrofluorimetric method for boldine alkaloid determination in herbal drugs and phytopharmaceuticals.

A new green on-line method for Boldine determination (BOL) in herbal drugs and phytopharmaceuticals, using its native fluorescence in acid media (λex=282nm; λem=373nm) has been developed. The presented methodology involves for the first time, a flow injection (FI) strategy using a mini-column of multiwalled carbon nanotubes as retention agent coupled with molecular fluorescence. Different parameters influence as sample pH and flow rate, eluent flow rate and composition; on BOL sensitivity and elution time was investigated by multifactorial techniques. Adequate dynamic calibration range (r2=0.9993) was obtained over a concentration interval of 0.029-27.0µgmL-1 BOL. The limits of detection (LOD) and quantification (LOQ) were 0.008 and 0.029µgmL-1, respectively. The average recoveries in explored samples ranged from 95% to 103%. Under optimized conditions, the throughput sample as high as 30h-1 was achieved with high repeatability performance (99%). The proposed development represents a useful and valuable tool emulating the analytical efficiency of the official methodologies for quality control of herbal and phytopharmaceutical drugs containing BOL. Moreover, this approach shows advantages respect to low cost, simplicity and environmental and analyst friendly.