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.

Chloride-selective electrodes based on "two-wall" aryl-extended calix[4]pyrroles: combining hydrogen bonds and anion-π interactions to achieve optimum performance.

The performance of chloride-selective electrodes based on "two-wall" aryl-extended calix[4]pyrroles and multiwall carbon nanotubes is presented. The calix[4]pyrrole receptors bear two phenyl groups at opposite meso-positions. When the meso-phenyl groups are decorated with strong electron-withdrawing substituents, attractive anion-π interactions may exist between the receptor's aromatic walls and the sandwiched anion. These anion-π interactions are shown to significantly affect the selectivity of the electrodes. Calix[4]pyrrole, bearing a p-nitro withdrawing group on each of the meso-phenyl rings, afforded sensors that display anti-Hofmeister behavior against the lipophilic salicylate and nitrate anions. Based on the experimental data, a series of principles that help in predicting the suitability of synthetic receptors for use as anion-specific ionophores is discussed. Finally, the sensors deliver excellent results in the direct detection of chloride in bodily fluids.

A potentiometric tattoo sensor for monitoring ammonium in sweat.

The development and analytical characterization of a novel ion-selective potentiometric cell in a temporary-transfer tattoo platform for monitoring ammonium levels in sweat is presented. The fabrication of this skin-worn sensor, which is based on a screen-printed design, incorporates all-solid-state potentiometric sensor technology for both the working and reference electrodes, in connection to ammonium-selective polymeric membrane based on the nonactin ionophore. The resulting tattooed potentiometric sensor exhibits a working range between 10(-4) M to 0.1 M, well within the physiological levels of ammonium in sweat. Testing under stringent mechanical stress expected on the epidermis shows that the analytical performance is not affected by factors such as stretching or bending. Since the levels of ammonium are related to the breakdown of proteins, the new wearable potentiometric tattoo sensor offers considerable promise for monitoring sport performance or detecting metabolic disorders in healthcare. Such combination of the epidermal integration, screen-printed technology and potentiometric sensing represents an attractive path towards non-invasive monitoring of a variety of electrolytes in human perspiration.

A novel miniaturized radiofrequency potentiometer tag using ion-selective electrodes for wireless ion sensing.

Instrumental approaches to remotely and wirelessly monitoring chemical species are increasingly needed. Together with the electronic developments, efforts to optimize and validate the performance of these new devices are required. In this work, the analytical performance of a recently developed potentiometer-radiofrequency tag connected to ion-selective electrodes is evaluated. This credit card sized and extremely low power consumption device yield results that are comparable to those obtained with more sophisticated, lab-based tools. Advantages such as portability and autonomy, together with unique features, such as the ability to be read through the walls in a closed vessel are demonstrated. Future perspectives opened by this new generation of devices, such as their use in wearable devices and in decentralized settings are discussed.

Potentiometric sensors using cotton yarns, carbon nanotubes and polymeric membranes.

A simple and generalized approach to build electrochemical sensors for wearable devices is presented. Commercial cotton yarns are first turned into electrical conductors through a simple dyeing process using a carbon nanotube ink. These conductive yarns are then partially coated with a suitable polymeric membrane to build ion-selective electrodes. Potentiometric measurements using these yarn-potentiometric sensors are demonstrated. Examples of yarns that can sense pH, K(+) and NH4(+) are presented. In all cases, these sensing yarns show limits of detection and linear ranges that are similar to those obtained with lab-made solid-state ion-selective electrodes. Through the immobilization of these sensors in a band-aid, it is shown that this approach could be easily implemented in a wearable device. Factors affecting the performance of the sensors and future potential applications are discussed.

A Wearable Paper-Based Sweat Sensor for Human Perspiration Monitoring.

The fabrication and performance of a wearable paper-based chemiresistor for monitoring perspiration dynamics (sweat rate and sweat loss) are detailed. A novel approach is introduced to measure the amount of aqueous solution in the order of microliters delivered to the sensor by monitoring a linear change in resistance along a conducting paper. The wearable sensor is based on a single-walled carbon nanotubes and surfactant (sodium dodecylbenzenesulfonate) nanocomposite integrated within cellulose fibers of a conventional filter paper. The analytical performance and the sensing mechanism are presented. Monitoring sweat loss in the human body while exercising is demonstrated using the integration of a wireless reader and a user-friendly interface. By addressing the barriers of cost, simplicity, and the truly in situ demanding measurements, this unique wearable sensor is expected to serve in the future in many different applications involving the on-body detection of biofluids, such as a monitoring tool of dehydration levels for athletes as well as a tool for enhancing the sport performance by providing an accurate recovery of the hydration status in daily exercises.

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 (Jaffé's reaction). The results show that this sensor allows the fast and accurate determination of creatinine in real samples with minimal sample manipulation.

Sulphate-selective optical microsensors: overcoming the hydration energy penalty.

Novel membrane-free chemically modified polystyrene microspheres for the optical detection of sulphate in aqueous media are introduced. The working principle of this sensor is based on the surface mass-extraction equilibrium of the target species. This allows overcoming the strong hydration energy penalty, a typical problem for the detection of divalent anions. This optical sensor exhibits both enhanced sensitivity and selectivity, which allows the accurate detection of sulphate in biological samples. To illustrate these features the determination of sulphate in urine is presented.

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.

A paper-based potentiometric cell for decentralized monitoring of Li levels in whole blood.

A novel approach to monitor Li levels in blood in decentralized (out of the lab) settings is presented. The approach uses a potentiometric cell fully made with filter paper as a support. Electrodes were built using carbon nanotubes ink to create a conductive path and a suitable polymeric membrane. Solid-state ion-selective electrodes for Li and a reference electrode were built and optimized. The results obtained on real samples of serum and whole blood are comparable with those obtained by conventional standard approaches. This platform shows an outstanding performance for the direct, fast and low-cost monitoring of Li levels in blood.

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 individual's 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.