RESUMEN

The 3D printing (or additive manufacturing, AM) technology is capable to provide a quick and easy production of objects with freedom of design, reducing waste generation. Among the AM techniques, fused deposition modeling (FDM) has been highlighted due to its affordability, scalability, and possibility of processing an extensive range of materials (thermoplastics, composites, biobased materials, etc.). The possibility of obtaining electrochemical cells, arrays, pieces, and more recently, electrodes, exactly according to the demand, in varied shapes and sizes, and employing the desired materials has made from 3D printing technology an indispensable tool in electroanalysis. In this regard, the obtention of an FDM 3D printer has great advantages for electroanalytical laboratories, and its use is relatively simple. Some care has to be taken to aid the user to take advantage of the great potential of this technology, avoiding problems such as solution leakages, very common in 3D printed cells, providing well-sealed objects, with high quality. In this sense, herein, we present a complete protocol regarding the use of FDM 3D printers for the fabrication of complete electrochemical systems, including (bio)sensors, and how to improve the quality of the obtained systems. A guide from the initial printing stages, regarding the design and structure obtention, to the final application, including the improvement of obtained 3D printed electrodes for different purposes, is provided here. Thus, this protocol can provide great perspectives and alternatives for 3D printing in electroanalysis and aid the user to understand and solve several problems with the use of this technology in this field.

Asunto(s)

RESUMEN

The combination of arginine and ibuprofen is widely used for pain relief with a faster onset of action than conventional ibuprofen. Therefore, the determination of both compounds in a single run is highly desirable for rapid quality control applications. This paper reports an ultra-fast method (100 injections/h) for simultaneous determination of arginine and ibuprofen using capillary electrophoresis with capacitively coupled contactless conductivity detection. The separation of arginine as cation and ibuprofen as anion was achieved using a background electrolyte composed by an equimolar mixture of 10 mmol/L of 2-(cyclohexylamino) ethanesulfonic acid and boric acid with pH adjusted to 8.4 using potassium hydroxide. The limits of detections were 5.3 and 10.0 µmol/L for arginine and ibuprofen, respectively. The proposed method is simple, fast (one analysis every 35 s), environmentally friendly (minimal waste generation) and accurate (recovery values between 95 and 98%).

Asunto(s)

RESUMEN

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.

RESUMEN

This study describes the development of a new analytical method for the separation and detection of cocaine (COC) and its adulterants, or cutting agents, using microchip electrophoresis (ME) devices coupled with capacitively coupled contactless conductivity detection (C4 D). All the experiments were carried out using a glass commercial ME device containing two pairs of integrated sensing electrodes. The running buffer composed of 20 mmol/L amino-2-(hydroxymethyl) propane-1,3-diol and 10 mmol/L 3,4-dimethoxycinnamic acid provided the best separation conditions for COC and its adulterants with baseline resolution (R > 1.6), separation efficiencies ranging from (2.9 ± 0.1) to (3.2 ± 0.2) × 105 plates/m, and estimated LOD values between 40 and 150 µmol/L. The quantification of COC was successfully performed in four samples seized by the Brazilian Federal Police Department and all predicted values agree with values estimated by the reference method. Some other interfering species were detected in the seized samples during the screening procedure on ME-C4 D devices. While lidocaine was detected in sample 3, the presence of levamisole was observed in samples 2 and 4. However, their concentrations were estimated to be below the LOQ. ME-C4 D devices have proved to be quite efficient for the identification and quantification of COC with errors lower than 10% when compared to the data obtained by a reference method. The approach herein reported offers great potential to be used for on-site COC screening in seized samples.

Asunto(s)

RESUMEN

Ammonium and diphenhydramine are active ingredients commonly found in the same pharmaceutical preparations. We report, for the first time, a sub-minute method for the simultaneous determination of ammonium and diphenhydramine. The method is based on capillary electrophoresis with capacitively coupled contactless conductivity detection. Both analytes can be quantified in a single run (∼80 injections/h) using 30 mmol/L 2-(N-morpholino)ethanesulfonic acid and 15 mmol/L lithium hydroxide (pH 6.0) as background electrolyte. The separation by capillary electrophoresis was achieved on a fused-silica capillary (50 cm total length, 10 cm effective length, and 50 µm inside diameter). The limits of detection were 0.04 and 0.02 mmol/L for ammonium and diphenhydramine, respectively. The proposed method also provided adequate recovery values for spiked samples (100-106 and 97-104% for ammonium and diphenhydramine, respectively). The results obtained with the new capillary electrophoresis method were compared with those of the high-performance liquid chromatography method for diphenhydramine and the Kjeldahl method for ammonium and no statistically significant differences were found (95% confidence level).

RESUMEN

The possibility of using pyrolyzed paper as disposable working electrodes for trace metals determination is reported for the first time. A small piece of pyrolyzed paper (0.7×0.7cm) was positioned at the bottom side of the electrochemical cell using a rubber O-ring, which defined the electrode area (0.48cm; 0.18cm2). A large number of electrodes can be obtained from a single piece of standard dimensions (2.5cm×7.5cm) of paper, therefore minimizing the cost per unit. The electrochemical performance of the pyrolyzed paper was demonstrated by cyclic voltammetry, electrochemical impedance spectroscopy and by the determination of Zn, Cd, and Pb by square-wave anodic stripping voltammetry. The unmodified pyrolyzed paper showed excellent performance for Pb and Cd detection (LOD =0.19 and 0.16 ppb, respectively). In the presence of Bi3+(in-situ film formation), the simultaneous determination of Zn, Cd and Pb was also possible (LOD=0.26, 0.25, and 0.39 ppb, respectively).

RESUMEN

In this work, a batch-injection analysis system with square-wave voltammetric (BIA-SWV) detection was applied for the first time to the simultaneous determination of inorganic (zinc) and organic (naphazoline) species. Both compounds were detected in a single run (70 injections h(-1)) with a small injection volume (∼100 µL). The calibration curves exhibited linear response range between 3.0 and 21.0 µmol L(-1) (r=0.999) for naphazoline and between 10.0 and 60.0 µmol L(-1) (r=0.992) for zinc. The detection limits were 0.13 and 0.04 µmol L(-1) for zinc and naphazoline, respectively. Good reproducibility was achieved for multiple measurements of a solution containing both species (RSD<1.0%; n=20). The results obtained with the BIA-SWV method for the simultaneous determination of naphazoline and zinc were compared to those obtained by HPLC (naphazoline) and by FAAS (zinc); no statistically significant differences were observed (95% confidence level).

RESUMEN

In this work, the possibility of simultaneous determination of three compounds with a single-injection step using batch injection analysis with multiple pulse amperometric detection (BIA-MPA) is demonstrated for the first time. A sequence of three potential pulses (+1.25 V, +1.60 V, and +1.80 V) was applied with the acquisition of three separate amperograms. 8-Chlorotheophylline was detected selectively at +1.25 V, both 8-chlorotheophylline and pyridoxine at +1.60V and 8-chlorotheophylline, pyridoxine, and diphenhydramine at +1.80 V. Subtraction between the currents detected at the three amperograms (with the help of correction factors) was used for the selective determination of pyridoxine and diphenhydramine. The proposed method is simple, inexpensive, fast (60 injections h(-1)), and present selectivity for the determination of the three compounds in pharmaceutical samples, with results similar to those obtained by HPLC (95% confidence level).

Asunto(s)

RESUMEN

Capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C(4)D) was used for fast, simultaneous determination of dipyrone (DIP), caffeine (CAF), and acetylsalicylic acid (ASA). In the same run and in less than 1min, the degradation products from DIP and ASA were also detected. In addition, the usage of the CE-C(4)D system allowed, for the first time, the detection of methylamine as a degradation product of DIP. Capillary electrophoresis with electrospray mass spectrometry experiments were carried out in order to confirm the formation of methylamine. The limits of detection by CE-C(4)D were 5, 5, and 6µmolL(-1) for CAF, DIP, and ASA, respectively. The proposed method was applied to the analysis of these compounds in pharmaceutical formulations with similar results to those achieved by HPLC (p<0.05).

Asunto(s)

RESUMEN

In this paper, we present two new electrochemical methods for fast and simultaneous determination of codeine (CO) and diclofenac (DCF). The first one is based on batch injection analysis with amperometric detection (BIA-MPA) and the second one is based on capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C(4)D). The proposed BIA-MPA method is highly-precise (RSD of 1.1% and 0.9% for DCF and CO, respectively; n=10), fast (300 injections h(-1)) and has low detection limits (1.1 and 1.0 µmol L(-1) for DCF and CO, respectively). The proposed CE-C(4)D method allows the determination of CO and DFC in less than 1 min with high precision (RSD of 0.3% and 0.7% for DCF and CO, respectively; n=10) and low detection limits (11 and 21 µmol L(-1) for DCF and CO, respectively). Both proposed methods were applied to the determination of CO and DCF in pharmaceutical samples with similar results to those achieved by high-performance liquid chromatography (HPLC) at a 95% confidence level.

Asunto(s)

RESUMEN

We report here, for the first time, application of batch injection analysis (BIA) with amperometric detection for determination of the phenolic antioxidant butylated hydroxyanisole (BHA) in biodiesel. A sample plug was directly injected onto a boron-doped diamond electrode immersed in 50% v/v hydroethanolic solution with 0.1 mol L(-1) HClO(4) using an electronic micropipette. Importantly, the only preparation step required for biodiesel analysis is dilution in the same hydroethanolic electrolyte solution. Our proposed method has several advantages for routine biodiesel analysis, including: a low relative standard deviation between injections (0.29%, n=20), high analytical frequency (120 h(-1)), adequate recovery values (93-101%) for spiked samples, satisfactory accuracy (based on comparative determinations by high-performance liquid-chromatography), and a low detection limit (100 ng of BHA per g of biodiesel). Finally, our method can be adapted for the determination of other antioxidants in biodiesel samples.

Asunto(s)

RESUMEN

The use of two additional reservoirs to accommodate the electrodes of the power source is proposed to improve the stability of the running electrolyte in capillary electrophoresis. The basic idea is to use salt bridges to connect those reservoirs to the ones containing the capillary ends. Although simple, there are several issues that can be considered in the design and implementation of such system in order to prevent undesired transference of material between the electrolysis and the main reservoirs. The use of a sealed electrolysis reservoir without a gas phase, the use of materials that ensure volume stability, and the use of bridges as long as possible are three basic directions. A compromise is involved in the dimensions of the sectional area of the bridge, because a small area diminishes the amount of a species transferred by diffusion but leads to an undesirable increase of the electrical field during the electrophoretic running. Thus, a bridge composed of a main wide-bore tube connected to a small-bore capillary seems to give the best performance for practical use. A simple electrolysis-separated system was adapted to a preexisting capillary electrophoresis system, and its performance was evaluated with a mixture of tartaric, malic, and succinic acids that was separated in sodium benzoate solution (pH 5.5) using the original equipment and the modified one. Due to the water electrolysis and the small buffering capacity of the electrolyte, there was a significant pH change and consequently changes in the effective mobilities of the analytes and loss of resolution after a few runs using the original equipment. Using the electrolysis-separated system, no significant change in the migration time and resolution was observed even after 15 runs. Besides the freedom to prepare running electrolytes with electroactive species or unbuffered solution, high throughput and the use of small reservoirs, such as the ones used in microfluidic devices, are the main advantages of the system.

RESUMEN

A simple and reliable FIA-potentiometric system for rapid assays of chloride in certain food samples is described and evaluated. The system is constituted by an aquarium air pump to propel the carrier solution, a manually operated injector, a homemade dialysis flow cell, a solid-state chloride detector (Ag/AgCl), a reference electrode and a multimeter connected to a microcomputer for data acquisition. The dialysis unit enables direct analysis of liquid food samples without any other previous treatment. The principal novelties are the precision (R.S.D. of 1.2% for whole milk) and rapidity (90 determinations/h) of FIA measurements near and below the lower end of the linear (Nernstian) response region of the chloride ion-selective electrode (ISE), with an estimated detection limit (3s) of 0.4mgL(-1) Cl(-) in the sample injected in donor stream. Data of peak potential versus sample chloride concentration (donor stream) was accurately fitted with a quadratic polynomial over the range between 4 and 1000mgL(-1) (r(2)=0.9999) and used as a calibration curve. The method was applied to the determination of chloride in milk and in coconut water samples. The validation of the results was done by comparison with a NIST reference material (milk) or by capillary electrophoresis (coconut water). For all analysis, no significant difference at a 95% confidence level was observed.