Murilo Santhiago

Separation and electrochemical detection of paracetamol and 4-aminophenol in a paper-based microfluidic device.

The present work describes the construction and application of a simple, low cost and sensitive microfluidic paper-based device with electrochemical detection for the detection of paracetamol and 4-aminophenol. The separation channels of a width of 2.0 mm were created on paper using a wax printing process to define the regions of the device. A baseline separation level of the analytes can be obtained in 0.1 mol L(-1) acetate buffer solution at pH 4.5 and by injecting 500 nL of the standard solutions at 12 mm from the working electrode. The electrochemical detection system was created at the end of the channels through a process known as sputtering. The previously separated analytes were detected at the end of the hydrophilic separation channel by applying a potential of 400 mV vs. pseudo Au on the working electrode. Experimental variables such as type of paper (cation exchanger and n1), pH, sample volume, applied potential and distance of sample injection were evaluated and, under the conditions of higher response, it was possible to obtain detection limits of 25.0 and 10.0 μmol L(-1) for paracetamol and 4-aminophenol, respectively.

Construction and Electrochemical Characterization of Microelectrodes for Improved Sensitivity in Paper-Based Analytical Devices

This work presents a simple, low cost method for creating microelectrodes for electrochemical paper-based analytical devices (ePADs). The microelectrodes were constructed by backfilling small holes made in polyester sheets using a CO2 laser etching system. To make electrical connections, the working electrodes were combined with silver screen-printed paper in a sandwich type two-electrode configuration. The devices were characterized using linear sweep voltammetry, and the results are in good agreement with theoretical predictions for electrode size and shape. As a proof-of-concept, cysteine was measured using cobalt phthalocyanine as a redox mediator. The rate constant (k(obs)) for the chemical reaction between cysteine and the redox mediator was obtained by chronoamperometry and found to be on the order of 10(5) s(-1) M(-1). Using a microelectrode array, it was possible to reach a limit of detection of 4.8 μM for cysteine. The results show that carbon paste microelectrodes can be easily integrated with paper-based analytical devices.

Microfluidic paper-based devices for bioanalytical applications.

Paper has become increasingly recognized as a very interesting substrate for the construction of microfluidic devices, with potential application in a variety of areas, including health diagnosis, environmental monitoring, immunoassays and food safety. The aim of this review is to present a short history of analytical systems constructed from paper, summarize the main advantages and disadvantages of fabrication techniques, exploit alternative methods of detection such as colorimetric, electrochemical, photoelectrochemical, chemiluminescence and electrochemiluminescence, as well as to take a closer look at the novel achievements in the field of bioanalysis published during the last 2 years. Finally, the future trends for production of such devices are discussed.

Novel electrochemical sensor for the selective recognition of chlorogenic acid

In this study, a novel sensitive molecularly imprinted electrochemical sensor was constructed for the selective detection of chlorogenic acid (CGA) by deposition of a molecularly imprinted siloxane (MIS) film, prepared by sol-gel process, onto Au bare electrode surface. Initially, a (3-mercaptopropyl)siloxane layer (MSL) was formed on the Au bare surface, followed by a siloxane layer obtained from the acid-catalyzed hydrolysis/condensation of a solution constituted by tetraethoxysilane (TEOS), phenyltriethoxysilane (PTEOS), 3-(aminopropyl)trimethoxysilane (APTMS) and CGA, as a molecular template. After the GCA extraction the MIS imprinted film was electrochemically characterized using differential pulse voltammetry (DPV). The MIS/Au sensor was tested in a solution of the CGA template and other similar molecules. This electrode displayed excellent selectivity towards CGA when compared with structurally similar molecules. Under optimized experimental conditions, the peak current response of the sensor for CGA was linear from 5.0 × 10(-7)mol L(-1) to 1.4 × 10(-5)mol L(-1), and the detection limit was 1.48 × 10(-7)mol L(-1). The MIS/Au sensor was successfully applied for the determination of CGA in coffee and tea samples.

Direct Drawing Method of Graphite onto Paper for High-Performance Flexible Electrochemical Sensors

A simple and fast fabrication method to create high-performance pencil-drawn electrochemical sensors is reported for the first time. The sluggish electron transfer observed on bare pencil-drawn surfaces was enhanced using two electrochemical steps: first oxidizing the surface and then reducing it in a subsequent step. The heterogeneous rate constant was found to be 5.1 × 10-3 cm s-1, which is the highest value reported so far for pencil-drawn surfaces. We mapped the origin of such performance by atomic force microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. Our results suggest that the oxidation process leads to chemical and structural transformations on the electrode surface. As a proof-of-concept, we modified the pencil-drawn surface with Meldolas blue to electrocatalytically detect nicotinamide adenine dinucleotide (NADH). The electrochemical device exhibited the highest catalytic constant (1.7 × 105 L mol-1 s-1) and the lowest detection potential for NADH reported so far in paper-based electrodes.

Flexible and Foldable Fully-Printed Carbon Black Conductive Nanostructures on Paper for High-Performance Electronic, Electrochemical, and Wearable Devices

In this work, we demonstrate the first example of fully printed carbon nanomaterials on paper with unique features, aiming the fabrication of functional electronic and electrochemical devices. Bare and modified inks were prepared by combining carbon black and cellulose acetate to achieve high-performance conductive tracks with low sheet resistance. The carbon black tracks withstand extremely high folding cycles (>20 000 cycles), a new record-high with a response loss of less than 10%. The conductive tracks can also be used as 3D paper-based electrochemical cells with high heterogeneous rate constants, a feature that opens a myriad of electrochemical applications. As a relevant demonstrator, the conductive ink modified with Prussian-blue was electrochemically characterized proving to be very promising toward the detection of hydrogen peroxide at very low potentials. Moreover, carbon black circuits can be fully crumpled with negligible change in their electrical response. Fully printed motion and wearable sensors are additional examples where bioinspired microcracks are created on the conductive track. The wearable devices are capable of efficiently monitoring extremely low bending angles including human motions, fingers, and forearm. Here, to the best of our knowledge, the mechanical, electronic, and electrochemical performance of the proposed devices surpasses the most recent advances in paper-based devices.

Construction of a new versatile point-of-care testing device with electrochemical detection employing paper as a microfluidic platform

A portable, low-cost, versatile and non-disposable electrochemical device has been proposed based on a simple design allowing easy changing of the working electrode and piece of paper, for point-of-care testing.

Versatile and robust integrated sensors to locally assess humidity changes in fully-enclosed paper-based devices

The synergic combination of materials and interfaces to create novel functional devices is a crucial approach for various applications, including low-cost paper-based point-of-care systems. In this work, we demonstrate the implementation of surface-modified polypyrrole (PPy) structures, monolithically integrated into a three-dimensional multilayered paper-based microfluidic device, to locally assess humidity changes. The fabrication and integration of the system include the deterministic incorporation of PPy into the paper-based structure by gas-phase polymerization and the modification of the polymer properties to allow local humidity monitoring. The functionalization of PPy changes both the wettability and the chemical composition of the interface, what is of fundamental importance for the sensors operation. The PPy structure has excellent mechanical stability, enduring at least 600 bending cycles, what is of relevance on flexible electronics. The electrical resistance correlates with the local relative humidity (RH) inside of the sealed microfluidic system, and the sensor response is fully reversible. The integrated system capable of locally monitoring the RH allowed us to verify that inside the microfluidic channel, water molecules can diffuse across the wax barriers-a possibility disregarded so far. Our results attest that RH variations of 5-10% can affect the flow of extended channels (>5 cm) even when they are fully enclosed.