This report describes for the first time the use of microchip electrophoresis (ME) devices integrated with capacitively coupled contactless conductivity detection (C D) to investigate the authenticity of seized whiskey samples, which were probably adulterated by simple dilution with tap water. The proposed microfluidic platform was explored for the monitoring of anionic species (Cl and F ) in both original and tampered samples. The best separations were achieved within 70 s using a running buffer composed of lactic acid and histidine (pH = 5.9). ME-C D devices were used to analyze samples from three different brands (five samples each). Based on the presence of inorganic anions like Cl , F , SO and NO in different amounts, the authenticity of seized whiskeys was compared to original samples. According to the reported data, the proposed microfluidic platform can be useful to help regulatory authorities in the investigation and monitoring of authenticity of commercialized whiskey beverages.

Here we report for the first time the use of an electronic micropipette as hydrodynamic (HD) injector for microchip electrophoresis (ME) devices. The micropipette was directly coupled to a PDMS device, which had been fabricated in a simple cross format with two auxiliary channels for sample volume splitting. Sample flow during the injection procedure was controlled in automatic dispenser mode using a volume of 0.6µL. Channel width and device configuration were optimized and the best results were achieved using a simple cross layout containing two auxiliary channels with 300µm width for sample splitting. The performance of the HD injector was evaluated using a model mixture of high-mobility cationic species. The results obtained were compared to the data obtained via electrokinetic (EK) injection. Overall, the HD provided better analytical performance in terms of resolution and injection-to-injection repeatability. The relative standard deviation (RSD) values for peak intensities were lower than 5% (n=10) when the micropipette was employed. In comparison with EK injection, the use of the proposed HD injector revealed an unbiased profile for a mixture containing K and Li(300 µmol L each) over various buffer concentrations. For EK injection, the peak areas decreased from 2.92 ± 0.20-0.72 ± 0.14Vs for K and from 1.30 ± 0.10-0.38 ± 0.10Vs for Li when the running buffer increased from 20 to 50mmolL. For HD injection, the peak areas for K and Li exhibited average values of 2.48±0.07 and 2.10±0.06Vs, respectively. The limits of detection (LDs) for K, Na and Li ranged from 18 to 23µmolL. HD injection through an electronic micropipette allows to automatically dispense a bias-free amount of sample inside microchannels with acceptable repeatability. The proposed approach also exhibited instrumental simplicity, portability and minimal microfabrication requirements.

This study describes the development of an analytical methodology based on the use of microchip electrophoresis (ME) devices integrated with capacitively coupled contactless conductivity detection (C4D) for the separation and detection of inorganic anions in post‐blast explosive residues. The best separation condition was achieved using a running buffer composed of 35 mmol/L lactic acid, 10 mmol/L histidine and 0.070 mmol/L cetyl(trimethyl ammonium) bromide. For C4D measurements, the highest sensitivity was obtained applying a 700 kHz sinusoidal wave with excitation voltage of 20 Vpp. The separation of Cl−, NO3−, NO2−, SO42−, ClO4− and ClO3− was performed within ca. 150 s with baseline resolution and efficiencies between 4.4 × 104 and 1.7 × 105 plates/m. The found limits of detection ranged between 2.5 and 9.5 μmol/L. Last, real samples of post‐blast explosive residues were analyzed on the ME‐C4D devices obtaining successfully the determination of Cl−, NO3− and SO42−. The achieved concentration values varied between 12.8–72.5 mg/L for Cl−, 1.7–293.1 mg/L for NO3− and 1.3–201.3 mg/L for SO42−. The data obtained using ME‐C4D devices were in good agreement with the concentrations found by ion chromatography. The approach reported herein has provided short analysis time, instrumental simplicity, good analytical performance and low cost. Furthermore, the ME‐C4D devices emerge as a powerful and portable analytical platform for on‐site analysis demonstrating to be a promising tool for the crime scene investigation.

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Nitrite is considered an important target analyte for environmental monitoring. In water resources, nitrite is the result of the nitrogen cycle and the leaching processes of pesticides based on nitrogenous compounds. A high concentration of nitrite can be associated with intoxication processes and metabolic disorders in humans. The present study describes the development of a portable analytical methodology based on microchip electrophoresis coupled with amperometric detection for the determination of nitrite in environmental water samples. Electrophoretic and detection conditions were optimized, and the best separations were achieved within 60 s by employing a mixture of 30 mmol L−1 lactic acid and 15 mmol L−1 histidine (pH = 3.8) as a running buffer applying 0.7 V to the working electrode (versus Pt) for amperometric measurements. The developed methodology revealed a satisfactory linear behavior in the concentration range between 20 and 80 μmolL−1 (R2 = 0.999) with a limit of detection of 1.3 μmolL−1. The nitrite concentration was determined in five water samples and the achieved values ranged from (28.7 ± 1.6) to (67.1 ± 0.5) µmol L−1. The data showed that using the proposed methodology revealed satisfactory recovery values (83.5–103.8%) and is in good agreement with the reference technique. Due to its low sample consumption, portability potential, high analytical frequency, and instrumental simplicity, the developed methodology may be considered a promising strategy to monitor and quantitatively determine nitrite in environmental samples.

SAMPLE INJECTION METHODS IN ELECTROPHORETIC MICROSYSTEMS. Electrophoresis is by far the most popular separation method implemented in microscale, most probably due to its instrumental simplicity, low cost and portability. Due to the increasing use of miniaturized electrophoretic systems, the study of fundamental aspects can improve the development of methodologies for several applications. One of the major challenges related to electrophoresis chips refers to the sample injection mode, in this way, this study presents a review on sample injection methods for microchip electrophoresis covering electrokinetic and hydrodynamic approaches, describing theoretic and instrumental aspects. Since the sample volume affects the analytical performance, the precise and reproducible control of the sample amount to be introduced into the separation channel is highly desirable to ensure reliable chemical analysis. Electrokinetic modes based on floating, pinched and gated protocols are presented and discussed providing an overview about the electrokinetic control of the sample through three methodologies. In the same way, hydrodynamic techniques including the use of microfabricated valves and pumps, syringe pumps, electronic micropipettes, rubber suction bulb and acupuncture needle are approached, thus expanding the view of hydrodynamic injectors based on classical and alternative methods.

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