Phosphonium dicyanamide ionogel incorporating bromophenol blue dye as a versatile platform for monitoring pH in solution

Online monitoring of pH levels in different environments such as bio-engineering and chemistry is vital for effective control of many critical industrial processes. The most common chemical parameter monitored is pH, and there is an increasing interest in the fabrication of robust, cheap and versatile pH sensing materials that can be easily integrated within existing industrial technologies. Ideally these materials present low fouling and do not require calibration, thus minimising manual attention over long operational intervals. In this work we present an innovative material (ionogel) that integrates pH-sensing capabilities for continuously measuring pH during chemical or biological processes. The ionogel is a solid, flexible and easily to pattern material generated using tetrabutylphosponium dicyanamide ionic liquid, hydrogel polymer (N-isopropylacrylamide and N,N-methylene-bis(acrylamide)) and a pH sensitive dye (Bromophenol Blue). Figure 1 shows the UV spectra of the ionogel-dye in an acidic and a basic pH environment as well as the pictures of the ionogels. A substantial colour variation is observed as the pH changes that can be monitored visually or optically. We incorporated the photoresponsive dye during photo-polymerisation of the monomer to improve stability, for example, by preventing leaching of the dye from the ionogel into the sample phase. This strategy was not found to inhibit the sensitivity of the optical response

Wearable chemo/bio-sensors for sweat sensing in sports applications: combining micro-fluidics and novel materials

In the last decade, we have witnessed an exponential growth in the area of clinical diagnostic but surprisingly little has been done on the development of wearable chemo/bio-sensors in the field of sports science. In particular, the use of wearable wireless sensors capable of analysing sweat during physical exercise can provide access to new information sources that can be used to optimise and manage athletes’ performance. Lab-on-a-Chip technology provides a fascinating opportunity for the development of such wearable sensors. In this thesis two different colorimetric wearable microfluidic devices for real- time pH sensing were developed and used during athlete training activity. In one case a textile-based microfluidic platform employing cotton capillarity to drive sweat toward the pH sensitive area is presented that avoids the use of bulky fluid handling apparatus, i.e. pumps. The second case presents a wearable micro-fluidic device based on the use of pH responsive ionogels to obtain real-time sweat pH measurements through photo analysis of their colour variation. The thesis also presents the first example of sweat lactate sensing using an organic electrochemical transistor incorporating an ionogel as solid-state electrolyte. In this chapter, optimization of the lactate oxidase stability when dissolved in number of hydrated ionic liquids is investigated. Finally, a new fabrication protocol for paper-based microfluidic technology is presented, which may have important implications for future applications such as low-cost diagnostics and chemical sensing technologies

Concept and development of an autonomous wearable micro-fluidic platform for real time pH sweat analysis

In this work the development of an autonomous, robust and wearable micro-fluidic platform capable of performing on-line analysis of pH in sweat is discussed. Through the means of an optical detection system based on a surface mount light emitting diode (SMD LED) and a light photo sensor as a detector, a wearable system was achieved in which real-time monitoring of sweat pH was performed during 55 minutes of cycling activity. We have shown how through systems engineering, integrating miniaturised electrical components, and by improving the micro-fluidic chip characteristics, the wearability, reliability and performance of the micro-fluidic platform was significantly improved

Organic electrochemical transistor incorporating an ionogel as solid state electrolyte for lactate sensing

Room temperature Ionic liquids (RTILs) have evolved as a new type of solvent for biocatalysis, mainly due to their unique and tunable physical properties.[1] In addition, within the family of organic semiconductor-based sensors, organic electrochemical transistors (OECTs) have attracted particular interest.[2] Here, we present a simple and robust biosensor, based on a OECT, capable of measuring lactic acid using a gel-like polymeric materials that endow RTIL (ionogel)[3] as solid-state electrolyte both to immobilise the enzyme and to serve as a supporting electrolyte.[4] This represents the first step towards the achievement of a fast, flexible, miniaturised and cheap way of measuring lactate concentration in sweat

Real-time sweat analysis: Concept and development of an autonomous wearable micro-fluidic platform

In this work the development of an autonomous, robust and wearable micro-fluidic platform capable of performing on-line analysis of pH in sweat is discussed. Through the means of an optical detection system based on a surface mount light emitting diode (smLED) and a photodiode as a detector, a wearable system was achieved in which realtime monitoring of sweat pH can be performed during sport activity. We show how through systems engineering, integrating miniaturised electrical components, and by improving the micro-fluidic chip characteristics, the wearability, reliability and performance of a sweat analysis platform has been significantly improved

“Sweat-on-a-Chip”: Analysing Sweat in Real Time with Disposable Micro-devices

Here we present the fabrication and the performance of a novel, wearable, robust, flexible and disposable micro-fluidic device which incorporates miniature optical components as a detection system, for wireless monitoring in real time mode of sweat pH during an exercise session. This micro-fluidic platform is completely non-invasive, with the great advantage of providing a continuous flow of fresh sweat for continuous real time analysis, ensuring immediate feedback regarding sweat composition to an athlete and/or coach. To the best of our knowledge, this is the first wearable and wireless micro-fluidic device suitable for real time analysis and reporting of the wearer’s physiological state

Modular microfluidic valve structures based on reversible thermoresponsive ionogel actuators

This paper reports for the first time the use of a crosslinked poly(N- isopropylacrylamide) ionogel encapsulating the ionic liquid 1-Ethyl-3- methylimidazolium ethyl sulphate as a thermoresponsive and modular microfluidic valve. The ionogel presents superior actuation behaviour over its equivalent hydrogel. The ionogel swelling and shrinking mechanisms and kinetics are investigated as well as the performance of the ionogel when integrated as a valve in a microfluidic device. The modular microfluidic valve demonstrates fully reversible on-off behaviour without failure for up to eight actuation cycles and a pressure resistance of 1100 mbar