Enhanced Electrochemiluminescence at the Gas/Liquid Interface of Bubbles Propelled into Solution.

Electrochemiluminescence (ECL) is typically confined to a micrometric region from the electrode surface. This study demonstrates that ECL emission can extend up to several millimeters away from the electrode employing electrogenerated chlorine bubbles. The mechanism behind this bubble-enhanced ECL was investigated using an Au microelectrode in chloride-containing and chloride-free electrolyte solutions. We discovered that ECL emission at the gas/solution interface is driven by two parallel effects. First, the bubble corona effect facilitates the generation of hydroxyl radicals capable of oxidizing luminol while the bubble is attached to the surface. Second, hypochlorite generated from chlorine sustains luminol emission for over 200 s and extends the emission range up to 5 mm into the solution, following bubble detachment. The new approach can increase the emission intensity of luminol-based assays 5-fold compared to the conventional method. This is demonstrated through a glucose bioassay, using a midrange mobile phone camera for detection. These findings significantly expand the potential applications of ECL by extending its effective range in time and space.

Integrated Photonic System for Early Warning of Cyanobacterial Blooms in Aquaponics.

Cyanobacterial blooms produce hazardous toxins, deplete oxygen, and secrete compounds that confer undesirable organoleptic properties to water. To prevent bloom appearance, the World Health Organization has established an alert level between 500 and 2000 cells·mL-1, beyond the capabilities of most optical sensors detecting the cyanobacteria fluorescent pigments. Flow cytometry, cell culturing, and microscopy may reach these detection limits, but they involve both bulky and expensive laboratory equipment or long and tedious protocols. Thus, no current technology allows fast, sensitive, and in situ detection of cyanobacteria. Here, we present a simple, user-friendly, low-cost, and portable photonic system for in situ detection of low cyanobacterial concentrations in water samples. The system integrates high-performance preconcentration elements and optical components for fluorescence measurement of specific cyanobacterial pigments, that is, phycocyanin. Phycocyanin has demonstrated to be more selective to cyanobacteria than other pigments, such as chlorophyll-a, and to present an excellent linear correlation with bacterial concentration from 102 to 104 cell·mL-1 (R2 = 0.99). Additionally, the high performance of the preconcentration system leads to detection limits below 435 cells·mL-1 after 10 min in aquaponic water samples. Due to its simplicity, compactness, and sensitivity, we envision the current technology as a powerful tool for early warning and detection of low pathogen concentrations in water samples.

Suspended Silicon Microphotodiodes for Electrochemical and Biological Applications.

Local electric stimulation of tissues and cells has gained importance as therapeutic alternative in the treatment of many diseases. These alternatives aim to deliver a less invasively stimuli in liquid media, making imperative the development of versatile micro- and nanoscale solutions for wireless actuation. Here, a simple microfabrication process to produce suspended silicon microphotodiodes that can be activated by visible light to generate local photocurrents in their surrounding medium is presented. Electrical characterization using electrical probes confirms their diode behavior. To demonstrate their electrochemical performance, an indirect test is implemented in solution through photoelectrochemical reactions controlled by a white-LED lamp. Furthermore, their effects on biological systems are observed in vitro using mouse primary neurons in which the suspended microphotodiodes are activated periodically with white-LED lamp, bringing out observable morphological changes in neuronal processes. The results demonstrate a simplified and cost-effective wireless tool for photovoltaic current generation in liquid media at the microscale.

Self-healing, piezoresistive and temperature responsive behaviour of chitosan/polyacrylic acid dynamic hydrogels.

Flexible electronics have introduced new challenges for efficient human-machine interactions. Hydrogels have emerged as prominent materials for electronic wearable applications due to their exceptional mechanical deformability and lightweight characteristics combined in some cases with conductive properties, and softness. Additionally, bio-interphases require multisensory response to stress, strain, temperature, and self-healing capacity. To mimic these properties, this work developed interpenetrated hydrogel networks composed of chitosan (CHI) and polyacrylic acid (PAA), combined with Fe (III) ions and varying amounts of NMBA (0-0.25 %), to achieve tailored conductivity (0.8-2.5 mS/cm), self-healing, self-standing and mechanical properties (E = 11.7-110 Pa and fracture strain = 64.9-1923 %) suitable for strain sensor applications. The results revealed a significant influence of the restrictive effect on the mobility of uncrosslinked chain segments, caused by Fe ions and NMBA, on the piezoresistance (GF 2.1-1.3) and self-healing capability of the gels. Interestingly, a transparent/turbid transition, driven by microphase separation that is characteristic of systems with high dynamic interactions, was encountered for the first time in these hydrogels. This transition was analyzed in relation to external temperature, water content, pH, and the influence of Fe ions and NMBA. The simultaneous sensitivity of these materials to temperature and pH, along with their piezoresistive and self-healing behaviour, can be highly valuable for multifunctional sensors in a wide range of applications.

Toward Next-Generation Mobile Diagnostics: Near-Field Communication-Powered Electrochemiluminescent Detection.

Mobile phones have been used in combination with point of care (PoC) devices for over a decade now. However, their use seems restricted to the detection of sensing events using the video and camera functions. In contrast, the complementary ability to use mobile phones to power such PoC devices has been largely unexplored. This work demonstrates the proof-of-principle that a smartphone can be used to both power and analyze an electrochemiluminescence (ECL) detection system. A printed device is presented featuring an electrochemical cell connected in series to a rectenna that is able to use the Near Field Communication (NFC, 13.56 MHz) signal to provide the energy needed to generate ECL from Ru(bpy)32+/tri-n-propylamine. The emitted light, the intensity of which is directly proportional to the concentration of the ruthenium complex, can then be captured by the mobile phone camera and analyzed. This work presents the fabrication and the electrical and electrochemical characterization of the device. Effective voltages ranging from 0.90 to 4.50 V have been recorded, depending on the coupling between emitter and receiver, which translate into working electrode potentials ranging from 0.76 up to 1.79 V vs Ag. Detection and quantification limits of 0.64 and 1.52 µM, respectively, have been achieved for Ru(bpy)32+, and linear ranges up to 0.1 mM (red channel) and no less than 1.0 mM (green channel) have been found.

Solid Polymer Electrolytes Based on Gellan Gum and Ionic Liquid for Sustainable Electrochromic Devices.

Materials sustainability is becoming increasingly relevant in every developed technology and, consequently, environmentally friendly solid polymer electrolytes (SPEs) based on gellan gum and different quantities of ionic liquid (IL) 1-ethyl-3-methyl-imidazolium-thiocyanate [Emim][SCN] have been prepared and applied in electrochromic devices (ECDs). The addition of the IL does not affect the crystalline phase of gellan gum, and the samples show a compact morphology, surface uniformity, no phase separation, and good distribution of the IL within the carrageenan matrix. The developed SPE are thermally stable up to ∼100 °C and show suitable mechanical properties. The most concentrated sample (39 wt % IL content) reaches a maximum ionic conductivity value of 6.0 × 10-3 S cm-1 and 1.8 × 10-2 S cm-1 at 30 and 90 °C, respectively. The electrochromic device (ECD) was fabricated with poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS) as working electrode and the developed SPE was compared with an aqueous 0.1 M KNO3 solution. The electrochromic performance of the electrolyte was assessed in terms of spectroelectrochemistry, demonstrating a fully flexible ECD operating at voltages below 1.0 V. This novel electrolyte opens the door to the preparation of high performance sustainable ECD.

Integration of a zero dead-volume PDMS rotary switch valve in a miniaturised (bio)electroanalytical system.

This work features the design, fabrication and characterisation of a miniaturised electroanalytical lab on a chip that allows the performance of a complete bioassay, from the capture of magnetic particles through their functionalisation and sample incubation to the detection of electroactive reaction products. The system is built using mainly polymeric materials such as PMMA and PDMS and fast prototyping techniques such as milling and moulding. The system also includes a set of microelectrodes, photo-lithographed on a silicon chip. The novelty lies in the design of the rotary microvalve, which contains a microreactor so that various reaction and incubation steps can be carried out in isolation from the detection event with zero dead volume. This avoids contamination and fouling of the electrodes by proteins or other organic matter, and extends the useful lifetime of the detector. The system operation is demonstrated by a model example, consisting in the functionalisation of streptavidin-coated magnetic particles with biotinylated beta-galactosidase over periods ranging from 5 to 15 min, at which point the particles saturate. Although the system is intended for the development of enzyme-based electrochemical bioassays, the concept of its rotary microreactor can be applied more broadly.

Thick-film voltammetric pH-sensors with internal indicator and reference species.

The following paper describes the development of a screen-printed voltammetric pH-sensor based on graphite electrodes incorporating both internal indicator (i.e., phenanthraquinone) and reference species (i.e., dimethylferrocene). The key advantages of this type of system stem from its simplicity, low cost and ease of fabrication. More importantly, as opposed to conventional voltammetric systems where the height of the voltammetric peaks is taken into account to quantify the amount of a species of interest, here, the difference between the peak potential of the indicator species and the peak potential of the reference species is used. Thus, this measurement principle makes the electrochemical system presented here less dependent on the potential of the reference electrode (RE), as is often the case in other electrochemical systems. The developed system displays very promising performances, with a reproducible Super Nernstian response to pH changes and a lifetime of at least nine days.

Amperometric detection of Enterobacteriaceae in river water by measuring ß-galactosidase activity at interdigitated microelectrode arrays.

Two simple methodologies are compared for the detection of faecal contamination in water using amperometry at gold interdigitated microelectrodes. They rely on the detection of ß-galactosidase (ß-gal) by redox cycling amperometry of the p-aminophenol (PAP) produced by the enzyme from the 4-aminophenyl ß-d-galactopyranoside (PAPG) substrate. The use of phages as specific agents for the release of the bacteria-enclosed enzyme allowed the detection of 6×10(5) CFU mL(-1)Escherichia coli in 2 h without any pre-enrichment or preconcentration steps. Better limits of detection were achieved for the second strategy in the absence of phages. In this case, bacteria were enriched in the presence of both ß-d-1-thiogalactopyranoside (IPTG) and substrate but in the absence of phages. Under such experimental conditions, 5×10(4) CFU mL(-1) E. coli could be detected after 2 h of incubation, while 7 h of incubation were enough to detect down to 10 CFU mL(-1) in river water samples. This represents a straightforward one-step method for the detection of faecal contamination that can be conducted in a single working day with minimal sample manipulation by the user.