Francisco J. Andrade

Epidermal tattoo potentiometric sodium sensors with wireless signal transduction for continuous non-invasive sweat monitoring

This article describes the fabrication, characterization and application of an epidermal temporary-transfer tattoo-based potentiometric sensor, coupled with a miniaturized wearable wireless transceiver, for real-time monitoring of sodium in the human perspiration. Sodium excreted during perspiration is an excellent marker for electrolyte imbalance and provides valuable information regarding an individuals physical and mental wellbeing. The realization of the new skin-worn non-invasive tattoo-like sensing device has been realized by amalgamating several state-of-the-art thick film, laser printing, solid-state potentiometry, fluidics and wireless technologies. The resulting tattoo-based potentiometric sodium sensor displays a rapid near-Nernstian response with negligible carryover effects, and good resiliency against various mechanical deformations experienced by the human epidermis. On-body testing of the tattoo sensor coupled to a wireless transceiver during exercise activity demonstrated its ability to continuously monitor sweat sodium dynamics. The real-time sweat sodium concentration was transmitted wirelessly via a body-worn transceiver from the sodium tattoo sensor to a notebook while the subjects perspired on a stationary cycle. The favorable analytical performance along with the wearable nature of the wireless transceiver makes the new epidermal potentiometric sensing system attractive for continuous monitoring the sodium dynamics in human perspiration during diverse activities relevant to the healthcare, fitness, military, healthcare and skin-care domains.

Paper-Based Ion-Selective Potentiometric Sensors

A new approach to develop ultra low-cost, robust, rugged, and disposable potentiometric sensors is presented. A suspension of carbon nanotubes in a water-surfactant mixture (carbon nanotubes ink) is applied on conventional filter papers to turn them into conductive papers, which are then used as a substrate to build ion-selective electrodes. The electrodes are made by drop casting a membrane on a small circular area of the conductive paper. In this way, the carbon nanotubes act as both electric conductors and ion-to-electron transducers of the potentiometric signal. Electrodes for sensing K(+), NH(4)(+), and pH were built and tested using this approach, and the results were compared with classical solid-state ion selective electrodes using carbon nanotubes as transducers and glassy carbon as a substrate. In all cases, the analytical performance (sensitivity, linear ranges, limits of detection, selectivity, etc.) of these disposable paper electrodes was similar to that obtained for the more conventional type of ion-selective-electrodes. This opens new avenues for very low-cost platforms for generation of chemical information.

A Textile-Based Stretchable Multi-Ion Potentiometric Sensor

A textile-based wearable multi-ion potentiometric sensor array is described. The printed flexible sensors operate favorably under extreme mechanical strains (that reflect daily activity) while offering attractive real-time noninvasive monitoring of electrolytes such as sodium and potassium.

A reference electrode based on polyvinyl butyral (PVB) polymer for decentralized chemical measurements.

A new solid-state reference electrode using a polymeric membrane of polyvinyl butyral (PVB), Ag/AgCl and NaCl to be used in decentralized chemical measurements is presented. The electrode is made by drop-casting the membrane cocktail onto a glassy carbon (GC) substrate. A stable potential (less than 1 mV dec(-1)) over a wide range of concentrations for the several chemical species tested is obtained. No significant influence to changes in redox potential, light and pH are observed. The response of this novel electrode shows good correlation when compared with a conventional double-junction reference electrode. Also good long-term stability (90±33 μV/h) and a lifetime of approximately 4 months are obtained. Aspects related to the working mechanisms are discussed. Atomic Force Microscopy (AFM) studies reveal the presence of nanopores and channels on the surface, and electrochemical impedance spectroscopy (EIS) of optimized electrodes show low bulk resistances, usually in the kΩ range, suggesting that a nanoporous polymeric structure is formed in the interface with the solution. Future applications of this electrode as a disposable device for decentralized measurements are discussed. Examples of the utilization on wearable substrates (tattoos, fabrics, etc) are provided.

Recognition and Sensing of Creatinine

Current methods for creatinine quantification suffer from significant drawbacks when aiming to combine accuracy, simplicity, and affordability. Here, an unprecedented synthetic receptor, an aryl-substituted calix[4]pyrrole with a monophosphonate bridge, is reported that displays remarkable affinity for creatinine and the creatininium cation. The receptor works by including the guest in its deep and polar aromatic cavity and establishing directional interactions in three dimensions. When incorporated into a suitable polymeric membrane, this molecule acts as an ionophore. A highly sensitive and selective potentiometric sensor suitable for the determination of creatinine levels in biological fluids, such as urine or plasma, in an accurate, fast, simple, and cost-effective way has thus been developed.

Flow dissolution of 1,5-diphenylcarbazide for the determination of chromium(VI)

An alternative procedure for the flow injection spectrophotometric determination of CrVI with 1,5-diphenylcarbazide (DPC), involving on-line dissolution of the reagent, is presented. Solid DPC (25% m/m in silica) is packed in a PTFE column, which is then incorporated in a single-line flow system so that reagent dissolution is effected as the sample passes through the column. This procedure reduces the chemical contribution to the dispersion value to a minimum and gives a low detection limit owing to the absence of refractive index peaks. An improvement of the figures of merit compared with those reported previously is shown. The calibration graph is linear up to 0.800 mg l–1 CrVI, with a slope of 0.49 l mg–1; the detection limit is 0.005 mg l–1. The relative standard deviation is better than 1%.

Paper-based chemiresistor for detection of ultralow concentrations of protein.

A new paper-based chemiresistor composed of a network of single-wall carbon nanotubes (SWCNTs) and anti-human immunoglobulin G (anti-HIgG) is reported herein. SWCNTs act as outstanding transducers because they provide high sensitivity in terms of resistance changes due to immunoreaction. As a result, the resistance-based biosensor reaches concentration detection as low as picomolar. The resulting paper-based biosensor is sensitive, selective and employs low-cost substrate and simple manufacturing stages. Since chemiresistors require low-power equipment and are able to detect low concentrations with inexpensive materials, the present approach may pave the way for the development of resistive biosensors at very low-cost with high performances.

Paper-based enzymatic electrode with enhanced potentiometric response for monitoring glucose in biological fluids

A novel paper-based potentiometric sensor with an enhanced response for the detection of glucose in biological fluids is presented. The electrode consists on platinum sputtered on a filter paper and a Nafion membrane to immobilize the enzyme glucose oxidase. The response obtained is proportional to the logarithm of the concentration of glucose, with a sensitivity of -119±8mV·decade-1, a linear range that spans from 10-4M to 10-2.5 M and a limit of detection of 10-4.5 M of glucose. It is shown that Nafion increases the sensitivity of the technique while minimizing interferences. Validation with human serum samples shows an excellent agreement when compared to standard methods. This approach can become an interesting alternative for the development of simple and affordable devices for point of care and home-based diagnostics.

Characterization of a new ionophore-based ion-selective electrode for the potentiometric determination of creatinine in urine

The optimization, analytical characterization and validation of a novel ion-selective electrode for the highly sensitive and selective determination of creatinine in urine is presented. A newly synthesized calix[4]pyrrole-based molecule is used as an ionophore for the enhanced recognition of creatininium cations. The calculation of the complex formation constants in the polymeric membrane with creatininium, potassium and sodium confirms the strong selective interactions between the ionophore and the target. The optimization of the potentiometric sensor presented here yields an outstanding analytical performance, with a linear range that spans from 1µM to 10mM and limit of detection of 10-6.2M. The calculation of the selectivity coefficients against most commonly found interferences also show significant improvements when compared to other sensors already reported. The performance of this novel sensor is tested by measuring creatinine in real urine samples (N=50) and comparing the values against the standard colorimetric approach (Jaffés reaction). The results show that this sensor allows the fast and accurate determination of creatinine in real samples with minimal sample manipulation.

Computer-operated analytical platform for the determination of nutrients in hydroponic systems.

Hydroponics is a water, energy, space, and cost efficient system for growing plants in constrained spaces or land exhausted areas. Precise control of hydroponic nutrients is essential for growing healthy plants and producing high yields. In this article we report for the first time on a new computer-operated analytical platform which can be readily used for the determination of essential nutrients in hydroponic growing systems. The liquid-handling system uses inexpensive components (i.e., peristaltic pump and solenoid valves), which are discretely computer-operated to automatically condition, calibrate and clean a multi-probe of solid-contact ion-selective electrodes (ISEs). These ISEs, which are based on carbon nanotubes, offer high portability, robustness and easy maintenance and storage. With this new computer-operated analytical platform we performed automatic measurements of K(+), Ca(2+), NO3(-) and Cl(-) during tomato plants growth in order to assure optimal nutritional uptake and tomato production.