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.

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.

Real time monitoring of glucose in whole blood by smartphone.

A combined thread-paper microfluidic device (µTPAD) is presented for the determination of glucose in blood. The device is designed to include all the analytical operations needed: red blood cell separation, conditioning, enzymatic recognition, and colorimetric transduction. The signal is captured with a smartphone or tablet working in video mode and processed by custom Android-based software in real-time. The automatic detection of the region of interest on the thread allows for the use of either initial rate or equilibrium signal as analytical parameters. The time needed for analysis is 12 s using initial rate, and 100 s using the equilibrium measurement with a LOD of 48 µM and 12 µM, respectively, and a precision around 7%. The µTPAD allows a rapid determination of glucose in real samples using only 3 µL of whole blood.

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.

Surface Modified Thread-Based Microfluidic Analytical Device for Selective Potassium Analysis.

This paper presents a thread-based microfluidic device (µTAD) that includes ionophore extraction chemistry for the optical recognition of potassium. The device is 1.5 cm × 1.0 cm and includes a cotton thread to transport the aqueous sample via capillary wicking to a 5 mm-long detection area, where the recognition chemistry is deposited that reaches equilibrium in 60 s, changing its color between blue and magenta. A complete characterization of the cotton thread used as well as the sensing element has been carried out. The imaging of the µTAD with a digital camera and the extraction of the H coordinate of the HSV color space used as the analytical parameter make it possible to determine K(I) between 2.4 × 10(-5) and 0.95 M with a precision better than 1.3%.

A compact optical instrument with artificial neural network for pH determination.

The aim of this work was the determination of pH with a sensor array-based optical portable instrument. This sensor array consists of eleven membranes with selective colour changes at different pH intervals. The method for the pH calculation is based on the implementation of artificial neural networks that use the responses of the membranes to generate a final pH value. A multi-objective algorithm was used to select the minimum number of sensing elements required to achieve an accurate pH determination from the neural network, and also to minimise the network size. This helps to minimise instrument and array development costs and save on microprocessor energy consumption. A set of artificial neural networks that fulfils these requirements is proposed using different combinations of the membranes in the sensor array, and is evaluated in terms of accuracy and reliability. In the end, the network including the response of the eleven membranes in the sensor was selected for validation in the instrument prototype because of its high accuracy. The performance of the instrument was evaluated by measuring the pH of a large set of real samples, showing that high precision can be obtained in the full range.