Near-Field Communication Tag for Colorimetric Glutathione Determination with a Paper-Based Microfluidic Device.

Here, we propose a microfluidic paper-based analytical device (µPAD) implemented with a near-field communication (NFC) tag as a portable, simple and fast colorimetric method for glutathione (GSH) determination. The proposed method was based on the fact that Ag+ could oxidize 3,3',5,5'-tetramethylbenzidine (TMB) into oxidized blue TMB. Thus, the presence of GSH could cause the reduction of oxidized TMB, which resulted in a blue color fading. Based on this finding, we developed a method for the colorimetric determination of GSH using a smartphone. A µPAD implemented with the NFC tag allowed the harvesting of energy from a smartphone to activate the LED that allows the capture of a photograph of the µPAD by the smartphone. The integration between electronic interfaces into the hardware of digital image capture served as a means for quantitation. Importantly, this new method shows a low detection limit of 1.0 µM. Therefore, the most important features of this non-enzymatic method are high sensitivity and a simple, fast, portable and low-cost determination of GSH in just 20 min using a colorimetric signal.

Reversal of a Fluorescent Fluoride Chemosensor from Turn-Off to Turn-On Based on Aggregation Induced Emission Properties.

Here we present a new approach for the development of fluoride chemosensors taking advantage of aggregation induced emission (AIE) properties. Although AIE-based chemosensors have been described, they rely primarily on the analyte causing aggregation and hence fluorescence. We propose a new concept in the use of AIE for the development of fluorescent sensors. Our hypothesis is based on the fact that a turn-off chemosensor in solution can be transformed into turn-on in the solid state if the properties of ACQ and AIE are properly combined between the fluorescent molecules involved. To demonstrate this hypothesis, we have selected a fluorescent chemosensor for the fluoride anion with a conjugated structure of bis(styryl)pyrimidine that, while showing turn-off behavior in solution, becomes turn-on when it is brought to the solid state. We have also combined it with the advantages of a detection system based on the microfluidic paper-based analytical devices (µPAD). The system is fully characterized spectroscopically both in solution and in the solid state, and quantum mechanical calculations were performed to explain how the sensor works. The prepared device presents a high sensitivity, with no interference and with an LoD and LoQ that allow determination of fluoride concentrations in water 2 orders of magnitude below the maximum allowed by WHO.

Laser-Induced Graphene Electrodes Modified with a Molecularly Imprinted Polymer for Detection of Tetracycline in Milk and Meat.

Tetracycline (TC) is a widely known antibiotic used worldwide to treat animals. Its residues in animal-origin foods cause adverse health effects to consumers. Low-cost and real-time measuring systems of TC in food samples are, therefore, extremely needed. In this work, a three-electrode sensitive and label-free sensor was developed to detect TC residues from milk and meat extract samples, using CO2 laser-induced graphene (LIG) electrodes modified with gold nanoparticles (AuNPs) and a molecularly imprinted polymer (MIP) used as a synthetic biorecognition element. LIG was patterned on a polyimide (PI) substrate, reaching a minimum sheet resistance (Rsh) of 17.27 ± 1.04 Ω/sq. The o-phenylenediamine (oPD) monomer and TC template were electropolymerized on the surface of the LIG working electrode to form the MIP. Surface morphology and electrochemical techniques were used to characterize the formation of LIG and to confirm each modification step. The sensitivity of the sensor was evaluated by differential pulse voltammetry (DPV), leading to a limit of detection (LOD) of 0.32 nM, 0.85 nM, and 0.80 nM in buffer, milk, and meat extract samples, respectively, with a working range of 5 nM to 500 nM and a linear response range between 10 nM to 300 nM. The sensor showed good LOD (0.32 nM), reproducibility, and stability, and it can be used as an alternative system to detect TC from animal-origin food products.

Highly stable luminescent europium-doped calcium phosphate nanoparticles for creatinine quantification.

The determination of creatinine levels is essential for the detection of renal and muscular dysfunction. Luminescent nanoparticles are emerging as fast, cheap and highly selective sensors for the detection and quantification of creatinine. Nevertheless, current nanosensors only have a short shelf life due to their poor chemical and colloidal stability, which limits their clinical functionality. In this work, we have developed a highly stable, selective and sensitive nanosensor based on europium-doped, amorphous calcium phosphate nanoparticles (Eu-ACP) for the determination of creatinine by luminescence spectroscopy. The colloidal stability of Eu-ACP nanoparticles in aqueous solutions was optimised to ensure a constant signal after up to 4 months in storage. The luminescence intensity of Eu-ACP decreased linearly with the creatinine concentration over the range of 1-120 µM (R2 = 0.995). This concentration-response relationship was used to determine creatinine levels in real urine samples resulting in good recovery percentages. Significantly, selectivity assays indicated that none of the potential interfering species provoked discernible changes in the luminescence intensity.

A vinyl sulfone clicked carbon dot-engineered microfluidic paper-based analytical device for fluorometric determination of biothiols.

A microfluidic paper-based analytical device integrating carbon dot (CDs) is fabricated and used for a fluorometric off-on assay of biothiols. Vinyl sulfone (VS) click immobilization of carbon dots (CDs) on paper was accomplished by a one-pot simplified protocol that uses divinyl sulfone (DVS) as a homobifunctional reagent. This reagent mediated both the click oxa-Michael addition to the hydroxyl groups of cellulose and ulterior covalent grafting of the resulting VS paper to NH2-functionalized CDs by means of click aza-Michael addition. The resulting cellulose nanocomposite was used to engineer an inexpensive and robust microfluidic paper-based analytical device (µPAD) that is used for a reaction-based off-on fluorometric assay of biothiols (GSH, Cys, and Hcy). The intrinsic blue fluorescence of CDs (with excitation/emission maxima at 365/450 nm) is turned off via the heavy atom effect of an introduced iodo group. Fluorescence is turned on again due to the displacement of iodine by reaction with a biothiol. The increase in fluorescence is related to the concentration over a wide range (1 to 200 µM for GSH and 5-200 µM for Cys and Hcy, respectively), and the assay exhibits a low detection limit (0.3 µM for GSH and Cys and 0.4 µM for Hcy). The method allows for rapid screening and can also be used in combination with a digital camera readout. Graphical abstract Schematic representation of a µPAD based on click immobilized carbon dots and used for a reaction-based fluorometric off-on assay of biothiols. The intrinsic blue fluorescence of carbon dots is turned off via the heavy atom effect of an introduced iodo group and turned on by the displacement of this atom by reaction with a biothiol.

Comparison of Laser-Synthetized Nanographene-Based Electrodes for Flexible Supercapacitors.

In this paper, we present a comparative study of a cost-effective method for the mass fabrication of electrodes to be used in thin-film flexible supercapacitors. This technique is based on the laser-synthesis of graphene-based nanomaterials, specifically, laser-induced graphene and reduced graphene oxide. The synthesis of these materials was performed using two different lasers: a CO2 laser with an infrared wavelength of λ = 10.6 µm and a UV laser (λ = 405 nm). After the optimization of the parameters of both lasers for this purpose, the performance of these materials as bare electrodes for flexible supercapacitors was studied in a comparative way. The experiments showed that the electrodes synthetized with the low-cost UV laser compete well in terms of specific capacitance with those obtained with the CO2 laser, while the best performance is provided by the rGO electrodes fabricated with the CO2 laser. It has also been demonstrated that the degree of reduction achieved with the UV laser for the rGO patterns was not enough to provide a good interaction electrode-electrolyte. Finally, we proved that the specific capacitance achieved with the presented supercapacitors can be improved by modifying the in-planar structure, without compromising their performance, which, together with their compatibility with doping-techniques and surface treatments processes, shows the potential of this technology for the fabrication of future high-performance and inexpensive flexible supercapacitors.

Carbon dots-inspired fluorescent cyclodextrins: competitive supramolecular "off-on" (bio)sensors.

Chromophore-appended cyclodextrins combine the supramolecular loading capabilities of cyclodextrins (CDs) with the optical properties of the affixed chromophores. Among fluorescent materials, carbon dots (CNDs) are attractive and the feasibility of CND-appended CDs as sensors has been demonstrated by different authors. However, CNDs are intrinsically heterogeneous materials and their ulterior functionalization yields hybrid composites that are not well defined in terms of structure and composition. Inspired by the fluorescence properties of 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-carboxylic acid (IPCA), the most paradigmatic of the molecular fluorophores detected in CNDs, herein we report two highly efficient synthetic chemical strategies for the preparation of IPCA-appended CDs that behave as CND-based CD "turn off-on" biosensors suitable for the analysis of cholesterol and ß-galactosidase activity. We have deconstructed the CND-CD systems to demonstrate that (i) the role of CNDs is limited to acting as a support for the molecular fluorophores produced during their synthesis and (ii) the molecular fluorophores suffice for the determination of the enzymatic activity based on the quenching by p-nitrophenol as a sacrificial quencher.

Inexpensive Graphene Oxide Heaters Lithographed by Laser.

In this paper, we present a simple and inexpensive method for the fabrication of high-performance graphene-based heaters on different large-scale substrates through the laser photothermal reduction of graphene oxide (laser-reduced graphene-oxide, LrGO). This method allows an efficient and localized high level of reduction and therefore a good electrical conductivity of the treated films. The performance of the heaters is studied in terms of steady-state temperature, power consumption, and time response for different substrates and sizes. The results show that the LrGO heaters can achieve stable steady-state temperatures higher than 200 °C when a voltage of 15 V is applied, featuring a time constant of around 4 s and a heat transfer coefficient of ~200 °C cm2/W. These characteristics are compared with other technologies in this field, demonstrating that the fabrication approach described in this work is competitive and promising to fabricate large-scale flexible heaters with a very fast response and high steady-state temperatures in a cost-effective way. This technology can be easily combined with other fabrication methods, such as screen printing or spray-deposition, for the manufacturing of complete sensing systems where the temperature control is required to adjust functionalities or to tune sensitivity or selectivity.

Wearable Potentiometric Ion Patch for On-Body Electrolyte Monitoring in Sweat: Toward a Validation Strategy to Ensure Physiological Relevance.

Herein, the reproducibility and a double validation of on-body measurements provided by new wearable potentiometric ion sensors (WPISs) is presented. Sweat collected during sport practice was first analyzed using the developed device, the pH-meter, and ion chromatography (IC) prior to on-body measurements (off-site validation). Subsequently, the accuracy of on-body measurements accomplished by the WPISs was evaluated by comparison with pH-meter readings and IC after collecting sweat (every 10-12.5 min) during sport practice. The developed device contains sensors for pH, Cl-, K+, and Na+ that are embedded in a flexible sampling cell for sweat analysis. The electrode array was fabricated employing MWCNTs (as an ion-to-electron transducer) and stretchable materials that have been exhaustively characterized in terms of analytical performance, presenting Nernstian slopes within the expected physiological range of each ion analyte (Cl-, 10-100 mM; K+, 10-10 mM; and Na+, 10-100 mM and pH, 4.5-7.5), drift suitable for midterm exercise practice (0.3 ± 0.2 mV h-1), fast response time, adequate selectivity for sweat measurements, and excellent reversibility. Besides that, the designed sampling cell avoids any sweat contamination and evaporation issues while supplying a passive sweat flow encompassing specifically the individual's perspiration. The interpretation of ion concentration profiles may permit the identification of personal dynamic patterns in sweat composition while practicing sport.

Ionophore-Based Optical Sensor for Urine Creatinine Determination.

Creatinine is a metabolite present in urine, and its concentration is used to diagnose and monitor kidney performance. For that reason, the development of new sensors to analyze this metabolite and obtain accurate results in a short period of time is necessary. An optical disposable sensor for monitoring creatinine levels in urine is described. The system, based on a new aryl-substituted calix[4]pyrrole synthetic receptor, has an unusual coextraction scheme. Due to the low p Ka values of creatininium (p Ka 4.8), a careful selection of a lipophilic pH indicator that works in acid medium is required. The sensor components were optimized, and the new sensor displays a good response time to creatinine (approximately 3 min) over a wide dynamic range (from 1 × 10-5 to 1 × 10-2 M). Moreover, the optical selectivity coefficients obtained for creatinine over common cations present in urine meet the requirements for real sample measurements. With a good sensor-to-sensor reproducibility (RSD, 5.1-6.9% in the middle of the range), this method provides a simple, quick, cost-effective, and selective alternative to the conventional methodology based on Jaffé's reaction.

Microfluidic paper-based device for colorimetric determination of glucose based on a metal-organic framework acting as peroxidase mimetic.

This work presents a microfluidic paper-based analytical device (µPAD) for glucose determination using a supported metal-organic framework (MOF) acting as a peroxidase mimic. The catalytic action of glucose oxidase (GOx) on glucose causes the formation of H2O2, and the MOF causes the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB) by H2O2 to form a blue-green product with an absorption peak at 650 nm in the detection zone. A digital camera and the iOS feature of a smartphone are used for the quantitation of glucose with the S coordinate of the HSV color space as the analytical parameter. Different factors such as the concentration of TMB, GOx and MOF, pH and buffer, sample volume, reaction time and reagent position in the µPAD were optimized. Under optimal conditions, the value for the S coordinate increases linearly up to 150 µmol·L-1 glucose concentrations, with a 2.5 µmol·L-1 detection limit. The µPAD remains stable for 21 days under conventional storage conditions. Such an enzyme mimetic-based assay to glucose determination using Fe-MIL-101 MOF implemented in a microfluidic paper-based device possesses advantages over enzyme-based assays in terms of costs, durability and stability compared to other existing glucose determination methods. The procedure was applied to the determination of glucose in (spiked) serum and urine. Graphical abstract Schematic representation of microfluidic paper-based analytical device using metal-organic framework as a peroxidase mimic for colorimetric glucose detection with digital camera or smartphone and iOS app readout.

Tetrazine-based chemistry for nitrite determination in a paper microfluidic device.

We present a new chemistry to determine nitrites implemented in a microfluidic paper-based analytical device (µPAD). The device is fabricated in cellulose paper with a sample reception area and three replicate detection areas with recognition chemistry immobilized by adsorption. The method involves the use of nitrite in an acid medium reaction to generate nitrous acid, which produces the oxidation of s-dihydrotetrazine: 1,2-dihydro-3,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1,2,4,5-tetrazine (DHBPTz), which change the detection zone from colorless to pink. We used a digital camera and smartphone for the quantitative analysis of nitrite with the color coordinate S of the HSV color space as the analytical parameter. Parameters such as concentration and volume of s-dihydrotetrazine, pH, sample volume and reaction time were studied. The detection limit for this method is 1.30µM nitrite. To estimate the selectivity of the method an interference study of common ions in water samples was performed. The procedure was applied to natural water and compared with reference procedures.