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.

Lanthanide(III) Ions and 5-Methylisophthalate Ligand Based Coordination Polymers: An Insight into Their Photoluminescence Emission and Chemosensing for Nitroaromatic Molecules.

The work presented herein reports on the synthesis, structural and physico-chemical characterization, luminescence properties and luminescent sensing activity of a family of isostructural coordination polymers (CPs) with the general formula [Ln2(µ4-5Meip)3(DMF)]n (where Ln(III) = Sm (1Sm), Eu (2Eu), Gd (3Gd), Tb (4Tb) and Yb (5Yb) and 5Meip = 5-methylisophthalate, DMF = N,N-dimethylmethanamide). Crystal structures consist of 3D frameworks tailored by the linkage between infinite lanthanide(III)-carboxylate rods by means of the tetradentate 5Meip ligands. Photoluminescence measurements in solid state at variable temperatures reveal the best-in-class properties based on the capacity of the 5Meip ligand to provide efficient energy transfers to the lanthanide(III) ions, which brings intense emissions in both the visible and near-infrared (NIR) regions. On the one hand, compound 5Yb displays characteristic lanthanide-centered bands in the NIR with sizeable intensity even at room temperature. Among the compounds emitting in the visible region, 4Tb presents a high QY of 63%, which may be explained according to computational calculations. At last, taking advantage of the good performance as well as high chemical and optical stability of 4Tb in water and methanol, its sensing capacity to detect 2,4,6-trinitrophenol (TNP) among other nitroaromatic-like explosives has been explored, obtaining high detection capacity (with Ksv around 105 M-1), low limit of detection (in the 10-6-10-7 M) and selectivity among other molecules (especially in methanol).

Sensing Capacity in Dysprosium Metal-Organic Frameworks Based on 5-Aminoisophthalic Acid Ligand.

Two novel metal-organic frameworks (MOFs), based on dysprosium as the metal and the 5-aminoisophthalic acid (5aip) ligand, have been solvothermally synthesized, with the aim of studying and modulating their luminescence properties according to the variation of solvent in the structure. These materials display intense photo-luminescence properties in the solid state at room temperature. Interestingly, one fascinating sensory capacity of compound 2 regards obtaining a variation of the signal, depending on the solvent to which it is exposed. These results pave the way for a new generation of sensitive chemical sensors.

Selectivity of Relative Humidity Using a CP Based on S-Block Metal Ions.

Herein, we present the syntheses of a novel coordination polymer (CP) based on the perylene-3,4,9,10-tetracarboxylate (pery) linkers and sodium metal ions. We have chosen sodium metal center with the aim of surmising the effect that the modification of the metal ion may have on the relative humidity (RH) experimental measurements of the material. We confirm the role of the ions in the functionalization of the deposited layer by modifying their selectivity towards moisture content, paving the way to the generation of sensitive and selective chemical sensors.

A gliclazide complex based on palladium towards Alzheimer's disease: promising protective activity against Aß-induced toxicity in C. elegans.

A new palladium coordination compound based on gliclazide with the chemical formula [Pd(glz)2] (where glz = gliclazide) has been synthesized and characterised. The structural characterization reveals that this material consists of mononuclear units formed by a Pd2+ ion coordinated to two molecules of the glz ligand, in which palladium ions exhibit a distorted plane-square coordination sphere. This novel material behaves like a good and selective inhibitor of butyrylcholinesterase, one of the most relevant therapeutic targets against Alzheimer's disease. Analysis of the enzyme kinetics showed a mixed mode of inhibition, the title compound being capable of interacting with both the free enzyme and the enzyme-substrate complex. Finally, the palladium compound shows promising protective activity against Aß-induced toxicity in the Caenorhabditis elegans model, which has never been reported.

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.

Synthesis of a thermoresponsive crosslinked MEO2MA polymer coating on microclusters of iron oxide nanoparticles.

Encapsulation of magnetic nanoparticles (MNPs) of iron (II, III) oxide (Fe3O4) with a thermopolymeric shell of a crosslinked poly(2-(2-methoxyethoxy)ethyl methacrylate) P(MEO2MA) is successfully developed. Magnetic aggregates of large size, around 150-200 nm are obtained during the functionalization of the iron oxide NPs with vinyl groups by using 3-butenoic acid in the presence of a water soluble azo-initiator and a surfactant, at 70 °C. These polymerizable groups provide a covalent attachment of the P(MEO2MA) shell on the surface of the MNPs while a crosslinked network is achieved by including tetraethylene glycol dimethacrylate in the precipitation polymerization synthesis. Temperature control is used to modulate the swelling-to-collapse transition volume until a maximum of around 21:1 ratio between the expanded: shrunk states (from 364 to 144 nm in diameter) between 9 and 49 °C. The hybrid Fe3O4@P(MEO2MA) microgel exhibits a lower critical solution temperature of 21.9 °C below the corresponding value for P(MEO2MA) (bulk, 26 °C). The MEO2MA coating performance in the hybrid microgel is characterized by dynamic light scattering and transmission electron microscopy. The content of preformed MNPs [up to 30.2 (wt%) vs. microgel] was established by thermogravimetric analysis while magnetic properties by vibrating sample magnetometry.

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.

Optimization of Cost-Effective and Reproducible Flexible Humidity Sensors Based on Metal-Organic Frameworks.

In this letter, we present the extension of a previous work on a cost-effective method for fabricating highly sensitive humidity sensors on flexible substrates with a reversible response, allowing precise monitoring of the humidity threshold. In that work we demonstrated the use of three-dimensional metal-organic framework (MOF) film deposition based on the perylene-3,4,9,10-tetracarboxylate linker, potassium as metallic center and the interspacing of silver interdigitated electrodes (IDEs) as humidity sensors. In this work, we study one of the most important issues in efficient and reproducible mass production, which is to optimize the most important processes' parameters in their fabrication, such as controlling the thickness of the sensor's layers. We demonstrate this method not only allows for the creation of humidity sensors, but it also is possible to change the humidity value that changes the actuator state.

Carbon Dots as Sensing Layer for Printed Humidity and Temperature Sensors.

This work presents an innovative application of carbon dots (Cdots) nanoparticles as sensing layer for relative humidity detection. The developed sensor is based on interdigitated capacitive electrodes screen printed on a flexible transparent polyethylene terephthalate (PET) film. Cdots are deposited on top of these electrodes. An exhaustive characterization of the nanoparticles has been conducted along with the fabrication of the sensor structure. The accompanied experiments give all the sensibility to the Cdots, showing its dependence with temperature and exciting frequency. To the best of our knowledge, this work paves the path to the use of these kind of nanoparticles in printed flexible capacitive sensors aimed to be employed in the continuously expanding Internet of Things ecosystem.

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.

Portable Instrument for Hemoglobin Determination Using Room-Temperature Phosphorescent Carbon Dots.

A portable reconfigurable platform for hemoglobin determination based on inner filter quenching of room-temperature phosphorescent carbon dots (CDs) in the presence of H2O2 is described. The electronic setup consists of a light-emitting diode (LED) as the carbon dot optical exciter and a photodiode as a light-to-current converter integrated in the same instrument. The reconfigurable feature provides adaptability to use the platform as an analytical probe for CDs coming from different batches with some variations in luminescence characteristics. The variables of the reaction were optimized, such as pH, concentration of reagents, and response time; as well as the variables of the portable device, such as LED voltage, photodiode sensitivity, and adjustment of the measuring range by a reconfigurable electronic system. The portable device allowed the determination of hemoglobin with good sensitivity, with a detection limit of 6.2 nM and range up to 125 nM.

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.

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.

Acid anhydride coated carbon nanodots: activated platforms for engineering clicked (bio)nanoconstructs.

Activated carbon nanodots functionalized with acid anhydride groups (AA-CNDs) are prepared by one-pot water-free green thermolysis of citric acid. As a proof of concept of their capabilities as appealing and versatile platforms for accessing engineering nanoconstructs, the as-prepared AA-CNDs have been reacted to yield clickable CNDs. Their click bioconjugation with relevant recognizable complementary clickable sugars has led to multivalent CND-based glyconanoparticles that are non-toxic and biorecognizable. The accessibility and intrinsic reactivity of AA-CNDs expand the current toolbox of covalent surface grafting methodologies and provide a wide range of potential applications for engineering (bio)nanoconstructs.

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.

A Potassium Metal-Organic Framework based on Perylene-3,4,9,10-tetracarboxylate as Sensing Layer for Humidity Actuators.

We have synthesized a novel three-dimensional metal-organic-framework (MOF) based on the perylene-3,4,9,10-tetracarboxylate linker and potassium as metallic centre. We report the formation of this K-based MOF using conventional routes with water as solvent. This material displays intense green photoluminescence at room temperature, and displays an aggregation dependent quenching. Correlation of the optical properties with the crystalline packing was confirmed by DFT calculations. We also demonstrate its potential to build humidity actuators with a reversible and reproducible response, with a change of 5 orders of magnitudes in its impedance at about 40% relative humidity (RH). This 3D-MOF is based on an interesting perylene derivative octadentate ligand, a moiety with interesting fluorescent properties and known component in organic semiconductors. To the best of our knowledge, this is the first time to build such a printed and flexible actuator towards humidity with a reversible response, enabling precise humidity threshold monitoring.