Application of Paper-Based Microfluidic Analytical Devices (µPAD) in Forensic and Clinical Toxicology: A Review

The need for providing rapid and, possibly, on-the-spot analytical results in the case of intoxication has prompted researchers to develop rapid, sensitive, and cost-effective methods and analytical devices suitable for use in nonspecialized laboratories and at the point of need (PON). In recent years, the technology of paper-based microfluidic analytical devices (μPADs) has undergone rapid development and now provides a feasible, low-cost alternative to traditional rapid tests for detecting harmful compounds. In fact, μPADs have been developed to detect toxic molecules (arsenic, cyanide, ethanol, and nitrite), drugs, and drugs of abuse (benzodiazepines, cathinones, cocaine, fentanyl, ketamine, MDMA, morphine, synthetic cannabinoids, tetrahydrocannabinol, and xylazine), and also psychoactive substances used for drug-facilitated crimes (flunitrazepam, gamma- hydroxybutyric acid (GHB), ketamine, metamizole, midazolam, and scopolamine). The present report critically evaluates the recent developments in paper-based devices, particularly in detection methods, and how these new analytical tools have been tested in forensic and clinical toxicology, also including future perspectives on their application, such as multisensing paper-based devices, microfluidic paper-based separation, and wearable paper-based sensors

A simple method for patterning poly(dimethylsiloxane) barriers in paper using contact-printing with low-cost rubber stamps

3siThis paper presents a simple and low-cost method for patterning poly(dimethylsiloxane) (PDMS) barriers in porous support such as paper for the construction of flexible microfluidic paper-based analytical devices (μPADs). The fabrication method consisted of contact-printing a solution of PDMS and hexane (10:1.5 w/w) onto chromatographic paper using custom-designed rubber stamps containing the patterns of μPADs. After penetrating the paper (∼30 s), the PDMS is cured to form hydrophobic barriers. Under optimized conditions, hydrophobic barriers and hydrophilic channels with dimensions down to 949±88 μm and 771±90 μm (n=5), respectively, were obtained. This resolution is well-suitable for most applications in analytical chemistry. Chemical compatibility studies revealed that the PDMS barriers were able to contain some organic solvents, including acetonitrile and methanol, and aqueous solutions of some surfactants. This find is particularly interesting given that acetonitrile and methanol are the most used solvents in chromatographic separations, non-aqueous capillary electrophoresis and electroanalysis, as well as aqueous solutions of surfactants are suitable mediums for cell lyses assays. The utility of the technique was evaluated in the fabrication of paper-based electrochemical devices (PEDs) with pencil-drawn electrodes for experiments in static cyclic voltammetry and flow injection analysis (FIA) with amperometric detection, in both aqueous and organic mediums.nonenoneDornelas, Karina Lopes; Dossi, Nicolo'; Piccin, EvandroDornelas, Karina Lopes; Dossi, Nicolo'; Piccin, Evandr

Deep Eutectic Solvents (DESs) and Their Application in Biosensor Development

Deep Eutectic Solvents (DESs) are a new class of solvents characterized by a remarkable decrease in melting point compared to those of the starting components. The eutectic mixtures can be simply prepared by mixing a Hydrogen Bond Acceptor (HBA) with a Hydrogen Bond Donor (HBD) at a temperature of about 80 °C. They have found applications in different research fields; for instance, they have been employed in organic synthesis, electrochemistry, and bio-catalysis, showing improved biodegradability and lower toxicity compared to other solvents. Herein, we review the use of DESs in biosensor development. We consider the emerging interest in different fields of this green class of solvents and the possibility of their use for the improvement of biosensor performance. We point out some promising examples of approaches for the assembly of biosensors exploiting their compelling characteristics. Furthermore, the extensive ability of DESs to solubilize a wide range of molecules provides the possibility to set up new devices, even for analytes that are usually insoluble and difficult to quantify

An Effective Label-Free Electrochemical Aptasensor Based on Gold Nanoparticles for Gluten Detection

Nanomaterials can be used to modify electrodes and improve the conductivity and the performance of electrochemical sensors. Among various nanomaterials, gold-based nanostructures have been used as an anchoring platform for the functionalization of biosensor surfaces. One of the main advantages of using gold for the modification of electrodes is its great affinity for thiol-containing molecules, such as proteins, forming a strong Au-S bond. In this work, we present an impedimetric biosensor based on gold nanoparticles and a truncated aptamer for the quantification of gluten in hydrolyzed matrices such as beer and soy sauce. A good relationship between the Rct values and PWG-Gliadin concentration was found in the range between 0.1–1 mg L−1 of gliadin (corresponding to 0.2–2 mg L−1 of gluten) with a limit of detection of 0.05 mg L−1 of gliadin (corresponding to 0.1 mg L−1 of gluten). The label-free assay was also successfully applied for the determination of real food samples

Volatile Aldehydes Sensing in Headspace Using a Room Temperature Ionic Liquid-Modified Electrochemical Microprobe

The cyclic voltammetric behaviour of propionaldehyde (PA) and hexanaldehyde (HA), in 1- butyl-3-methylimidazolium bis(trifluoromethyl-sulfonyl) imide ([BMIM][NTF2]), 1-butyl-3- methylimidazolium hydrogen sulphate ([BMIM][HSO4]) and 1-butyl-3-methylimidazolium hydroxide ([BMIM][OH]) was investigated at a platinum microelectrode. A clear oxidation process for both aldehydes was recorded only in [BMIM][OH]. On the basis of these evidences, an electrochemical microprobe (EMP), incorporating [BMIM][OH] as electrolyte, was assembled for sensing these aldehydes in gaseous phases. The EMP exposed in the headspace of the liquid aldehydes displayed voltammetric and amperometric responses, which depended on the aldehyde vapour pressures and, consequently, on the temperature employed. The usefulness of the [BMIM][OH] coated EMP for practical applications was assessed in the detection of HA vapour released from squalene (i.e., a lipid simulant matrix) samples spiked with known amounts of the aldehyde. Calibration plots were constructed at 40 °C, 50 °C and 60 °C, using both voltammetry and chronoamperometry. In both cases, good linearity between current and HA concentration in squalene was obtained over the range 3 - 300 ppm, with correlation coefficients higher than 0.991. Reproducibility, evaluated from at least three replicates, was within 5 %. Detection limits, evaluated for a signal-to-noise ratio of 3, were in any case lower than 1.7 ppm. These analytical performances are suitable for monitoring VAs coming from lipid oxidation processes in food. An application concerning the determination of VAs in headspace of sunflower oil during an induced oxidative test to establish its thermal stability was also performed

Amperometric sniffer for volatile amines based on paper-supported room temperature ionic liquids enabling rapid assessment for fish spoilage

A gas sensors based on a room temperature ionic liquid (RTIL) supported on paper is proposed as amperometric sniffer for monitoring volatile amines (VAs) released from fish samples, in order to gain indication of their state of turning spoiled. It was used as a paper electrochemical detector (PED) for a flow injection system in which controlled headspace volumes in equilibrium with ice-stored fish samples were directly injected. The performance of this RTIL-PED sensor was preliminarily tested on synthetic samples of trimethylamine (TMA), dimethylamine (DMA), methylamine (MA) and ammonia (i.e. the main species responsible for the typical flavor of spoiled fish), thus verifying that only TMA, DMA and MA can be detected because NH3 oxidation occurred beyond the solvent discharge. This notwithstanding, detection of the sole TMA, DMA and MA as a whole turned out to be well suited for the rapid assessment of fish spoilage, since during storage the release enhancement for these amines is largely predominant over that of NH3. Repeatable (8% RSD) sharp peaks were detected for all amines above over a wide range (5-1000 nmol) and a detection limit of a little more than 3 nmol was inferred for a signal-to-noise ratio of 3. This approach was applied to the detection of VAs released from real fish samples (sardines), in parallel to the determination of their total volatile basic nitrogen (TVBN), which is a conventional indicator frequently adopted for the chemical quality assessment of fish. A substantially satisfactory agreement was found by comparing the data achieved by these two approaches

Amperometric Detection of Ethanol Vapors by Screen Printed Electrodes Modified by Paper Crowns Soaked with Room Temperature Ionic Liquids

A convenient assembly recently proposed for screen printed gold electrodes (SPEs) suitable for measurements in gaseous samples is here tested for the analysis of the ethanol content in alcoholic drinks. This assembly involves the use of a circular crown of filter paper, soaked in the room temperature ionic liquid (RTIL) 1-butyl-3-methylimidazolium hydrogen sulfate, which is simply placed upon a disposable screen printed cell, so as to contact the outer edge of the gold disc working electrode, as well as peripheral counter and reference electrodes. The electrical contact between the paper crown soaked in RTIL and the SPE electrode is assured by a gasket and all components are installed in a polylactic acid holder. This assembly provides a portable and disposable electrochemical platform, assembled by the easy immobilization onto a porous and inexpensive supporting material such as paper of a RTIL characterized by profitable electrical conductivity and negligible vapor pressure. The electroanalytical performance of this device was assayed for the flow injection analysis of the ethanol concentration in some real samples of wine and beer and the results obtained are compared with the alcoholic degree reported in the relevant bottle-labels, thus highlighting a substantially satisfactory agreement. Repeatable sharp peaks (RSD=6–8 %) were detected for ethanol over a wide linear range (1–20 % v/v in water) and a detection and quantitation limit of 0.55 % v/v and 1.60 % v/v were inferred for a signal-to-noise ratio of 3 and 10, respectively

Use of an electrochemical room temperature ionic liquid-based microprobe for measurements in gaseous atmospheres

A simple electrochemical microprobe (EMP) is proposed for the detection of analytes in gaseous atmospheres. The EMP consists of two platinum fibres of 25 and 300 μm in diameter encased into a theta glass pipette to form an electrochemical cell in a two-electrode configuration. Ion conductivity between the two electrodes is ensured by a thin film of the room temperature ionic liquid (RTIL), 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, which is applied onto the EMP tip surface by a simple dip-coating procedure. The ionic liquid-coated microprobe (RTIL-EMP) was preliminarily investigated by using ferrocene as an electroactive species to ascertain the mass transport properties of the analytes that influence the voltammetric responses as well as the stability and reproducibility of the RTIL-EMP in the gas phase. The performance of the RTIL-EMP to gas analysis was afterward evaluated by using oxygen as electroactive species. The RTIL-EMP was exposed to different synthetic O2/N2 (v/v) mixtures and current responses were recorded as a function of O2 concentration, using either cyclic voltammetry (CV) or chronoamperometry (CA). Regression analysis of the experimental current against % O2 was linear over the range 0–100% with correlation coefficient and sensitivity of, respectively, 0.996 and 0.29 nA/(v/v) % O2 in CV and 0.998 and 0.27 nA/(v/v) % O2 in CA measurements. Long term stability, reproducibility of the RTIL-EMP recovery of the RTIL film layers to the initial conditions and effects of humidity on the current responses were investigated in detail

Voltammetric behaviour of Cu alloys toward hydrogen peroxide and organic species

The communication reports on the electrocatalytic properties exhibited by five Cu alloys (Cu-Zn, Cu-Sn, Cu-Ni, Cu-Zn-Ni, Cu-Al) and of pure Cu, Ni and Al in the reduction or oxidation of a number of representative species. A prototypical strong oxidising agent, namely hydrogen peroxide, and some of the most important oxidisable species, namely methanol, ethanol, and formaldehyde, are tested. Both cathodic and anodic processes are facilitated by using specific alloys in the case of strong oxidants and different organic molecules, respectively. Keywords: Copper alloys electrodes, Aluminium electrode, Electrocatalysis, Hydrogen peroxide, Oxidisable specie