Flexible and Conductive Bioelectrodes Based on Chitosan-Carbon Black Membranes: Towards the Development of Wearable Bioelectrodes.

Wearable sensors for non-invasive monitoring constitute a growing technology in many industrial fields, such as clinical or sport monitoring. However, one of the main challenges in wearable sensing is the development of bioelectrodes via the use of flexible and stretchable materials capable of maintaining conductive and biocompatible properties simultaneously. In this study, chitosan-carbon black (CH-CB) membranes have been synthesized using a straightforward and versatile strategy and characterized in terms of their composition and their electrical and mechanical properties. In this sense, CH-CB membranes showed good conductivity and mechanical resistance thanks to the presence of carbon black, which decreases the insulating behavior of chitosan, while flexibility and biocompatibility are maintained due to the dual composition of the membrane. Thus, flexible and biocompatible conductive bioelectrodes have been developed by the combined use of CH and CB without the use of toxic reagents, extra energy input, or long reaction times. The membranes were modified using the enzymes Glucose Oxidase and Laccase in order to develop flexible and biocompatible bioelectrodes for enzymatic glucose biofuel cells (BFCs) and glucose detection. A BFC assembled using the flexible bioelectrodes developed was able to deliver 15 µW cm-2, using just 1 mM glucose as biofuel, and up to 21.3 µW·cm-2 with higher glucose concentration. Additionally, the suitability of the CH-CB membranes to be used as a glucose sensor in a linear range from 100 to 600 µM with a limit of detection (LOD) of 76 µM has been proven. Such demonstrations for energy harvesting and sensing capabilities of the developed membrane pave the way for their use in wearable sensing and energy harvesting technologies in the clinical field due to their good mechanical, electrical, and biocompatible properties.

Enzymatic Glucose-Based Bio-batteries: Bioenergy to Fuel Next-Generation Devices.

This article consists of a review of the main concepts and paradigms established in the field of biological fuel cells or biofuel cells. The aim is to provide an overview of the current panorama, basic concepts, and methodologies used in the field of enzymatic biofuel cells, as well as the applications of these bio-systems in flexible electronics and implantable or portable devices. Finally, the challenges needing to be addressed in the development of biofuel cells capable of supplying power to small size devices with applications in areas related to health and well-being or next-generation portable devices are analyzed. The aim of this study is to contribute to biofuel cell technology development; this is a multidisciplinary topic about which review articles related to different scientific areas, from Materials Science to technology applications, can be found. With this article, the authors intend to reach a wide readership in order to spread biofuel cell technology for different scientific profiles and boost new contributions and developments to overcome future challenges.

Pacifier Biosensor: Toward Noninvasive Saliva Biomarker Monitoring.

Wearable sensors for noninvasive monitoring of physiological parameters is a growing technology in the clinical field. Especially in neonates, the development of portable and nonharmful monitoring devices is urgently needed because they cannot provide any feedback about discomfort or health complaints. However, in infant monitoring, only wearable sensors measuring physical parameters for vital signs have been developed. Here, we describe the first chemical wearable sensor for newborn monitoring. This fully integrated pacifier operates as a portable wireless device toward noninvasive chemical monitoring in the infant's saliva. The infant's mouth movements on the pacifier result in efficient saliva pumping and promote unidirectional flow from the mouth to the electrochemical chamber. The integrated electrochemical detection chamber, containing the enzymatic biosensor, is located outside of the oral cavity. The capabilities of the platform were studied for glucose detection in diabetic adults and compared to their blood levels with good correlation, demonstrating the sensor's good performance. This baby-friendly device integrates saliva sampling with electrochemical sensing, along with miniaturized wireless electronics on a single pacifier platform. Such integration simplifies the infant's health monitoring in a real-time and selective fashion, representing the first wearable sensor focusing on chemical saliva sensing in newborns. This initial demonstration of glucose monitoring introduces new possibilities for metabolites monitoring in infants and neonates using saliva as a noninvasive sample.

Eyeglasses-based tear biosensing system: Non-invasive detection of alcohol, vitamins and glucose.

We report on a wearable tear bioelectronic platform, integrating a microfluidic electrochemical detector into an eyeglasses nose-bridge pad, for non-invasive monitoring of key tear biomarkers. The alcohol-oxidase (AOx) biosensing fluidic system allowed real-time tear collection and direct alcohol measurements in stimulated tears, leading to the first wearable platform for tear alcohol monitoring. Placed outside the eye region this fully wearable tear-sensing platform addresses drawbacks of sensor systems involving direct contact with the eye as the contact lenses platform. Integrating the wireless electronic circuitry into the eyeglasses frame thus yielded a fully portable, convenient-to-use fashionable sensing device. The tear alcohol sensing concept was demonstrated for monitoring of alcohol intake in human subjects over multiple drinking courses, displaying good correlation to parallel BAC measurements. We also demonstrate for the first time the ability to monitor tear glucose outside the eye and the utility of wearable devices for monitoring vitamin nutrients in connection to enzymatic flow detector and rapid voltammetric scanning, respectively. These developments pave the way to build an effective eyeglasses system capable of chemical tear analysis.

Correction: Microchip in situ electrosynthesis of silver metallic oxide clusters for ultra-FAST detection of galactose in galactosemic newborns' urine samples.

Correction for 'Microchip in situ electrosynthesis of silver metallic oxide clusters for ultra-FAST detection of galactose in galactosemic newborns' urine samples by Laura García-Carmona et al., Analyst, 2016, 141, 6002-6007.

Class enzyme-based motors for "on the fly" enantiomer analysis of amino acids.

Here, two class-enzyme motors are properly designed allowing the rapid dispersion of the class-enzyme D-amino acid oxidase (DAO) and L-amino acid oxidase (LAO) for selective "on the fly" biodetection of D and L-amino acids (AAs), respectively. The efficient movement together with the continuous release of fresh class-enzyme leads to a greatly accelerated enzymatic reaction processes without the need of external stirring or chemical and physical attachment of the enzyme. Ultra-fast detection (<2min) and accurate quantifications of L-phenylalanine (L-Phe) in plasma and whole-blood newborns samples diagnosed with Phenylketonuria and total D-AAs in Vibrio cholera cultures are pioneer illustrated as relevant examples of each enantiomer determination. These results opens clearly novel avenues in biosensing for fast screening diagnostics, decentralized monitoring and design of future points of care.

Aligned copper nanowires as a cut-and-paste exclusive electrochemical transducer for free-enzyme highly selective quantification of intracellular hydrogen peroxide in cisplatin-treated cells.

The role and reliable quantification of intracellular hydrogen peroxide during cancer therapy constitutes an unexplored and fascinating application. In this work, we report the fabrication of vertically aligned copper nanowires (v-CuNWs) using electrosynthesis on templates, and their application as a cut-and-paste exclusive and flexible electrochemical transducer. This easily adaptable electrodic platform is demonstrated for a fast, simple and free-enzyme selective quantification of intracellular hydrogen peroxide in Cisplatin-treated human renal HK-2 cells. The v-CuNWs sensor was compared with an HRP-enzyme-based biosensor showing excellent correlation and indicates the good selectivity and analytical performance of the v-CuNWs. This sensing approach opens novel avenues for monitoring cell death processes and shows the potential of H2O2 as a cellular damage biomarker, with a clear potency for further developments for in vitro diagnosis and its implication in cancer therapy.

Vertically-Oriented and Shape-Tailored Electrocatalytic Metal Nanowire Arrays for Enzyme-Free Galactosemia Rapid Diagnosis.

Metallic catalytic nanowires such as nickel and copper nanowires (NWs) for electrochemical detection of carbohydrates involved in metabolic rare diseases are proposed. NWs were electrodeposited using a polycarbonate membrane template, which was cut with the desired shape, stuck in double-sided adhesive tape, pasted into a non-conductive substrate and in situ removed. This simple and versatile approach allowed to obtain NWs vertically oriented (v-NWs), which are contained in the double-sided adhesive tape, becoming highly versatile. The high specific surface of working electrode in which the transduction is supported exclusively by the nanomaterial yielded a high analytical performance [extremely low fouling for galactose (RSD<2 %; n=25)]. Likewise, v-NWs exhibited a superior analytical performance with respect to commercial sputtered thick-film electrodes showing also a clear advantage related with the price, as well as with non-need clean room facilities. The analytical potency of the new approach was clearly demonstrated towards the fast and reliable diagnosis of galactosemia using precious newborn urine samples compared to standard clinical diagnosis. These results revealed new opportunities for future enzyme-free diagnosis and development of future point-of-care applications.

Electrochemical detectors based on carbon and metallic nanostructures in capillary and microchip electrophoresis.

Carbon and metallic-based nanostructures have been progressively implemented as innovative electrochemical detectors in CE and microchip electrophoresis (ME). For both type of nanomaterials and toward selected examples, this review details the impact of these nanomaterials for enhanced detection performance in CE, ME, and paper-based microfluidic devices. The analytical performance and the analytical potential in real world applications is also presented and discussed.

Microchip in situ electrosynthesis of silver metallic oxide clusters for ultra-FAST detection of galactose in galactosemic newborns' urine samples.

This work describes for the first time the coupling of microfluidic chips (MC) to electrosynthetized silver metallic oxide clusters (AgMOCs). As an early demonstration of this novel approach, the ultrafast detection of galactose in galactosemic newborns' urine samples is proposed. AgMOCs were in situ electrosynthetized on integrated microchip platinum electrodes using a double pulse technique and characterized in full using scanning electronic microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS) and electrochemical techniques revealing the presence of silver oxides and electrocatalysis towards galactose as a galactosemia biomarker. Galactose detection in galactosemic newborns' urine samples proceeded in less than 30 s, differentiating between ill and healthy urine samples and requiring negligible urine sample consumption. The significance of the newborns' urine samples confirmed the analytical potency of the MC-AgMOCs approach for future implementation of screening for rare disease diagnosis such as galactosemia.