Comparative analysis of a bulk optode based on a valinomycin ionophore and a nano-optode in micelles with pluronic F-127 for the quantification of potassium in aqueous solutions.

In this work, two types of optical sensors were prepared for the quantification of potassium: the bulk optode (BO) and nano-optode (NO). The BO was prepared using three main components: the ionophore valinomycin, the ion exchanger tetrakis(4-chlorophenyl) potassium borate (K-TCPB), and the chromoionophore ETH 5294 (CHI). The optimal composition was found to be in a ratio of [1 : 1 : 1]. The NO was prepared by miniaturizing the BO through sonication in surfactant Pluronic F-127. The working range for the linear calibration model of BO was from 10-6 to 1.0 M K+ with a LODBO = 0.31 µM, meanwhile for NO was from 10-4 to 1.0 M K+ with a LODNO = 30.3 µM. Both optodes were tested for selectivity towards K+ in the presence of alkaline and alkaline earth ions, with a selectivity coefficient > 1.0. Furthermore, precision and stability studies of BO and NO were performed for three levels of K+ concentrations, 10-6, 10-3, 1.0 M for BO and 10-4, 10-2, 1.0 M for NO, showing a good homogeneity of the NO in the whole concentration range. However, an excessive variability was obtained for BO at 1.0 M K+. Therefore, the NO represents a potential tool for quantification of K+.

Smartphone-Based Rapid Quantitative Detection Platform with Imprinted Polymer for Pb (II) Detection in Real Samples.

This paper reports the successful development and application of an efficient method for quantifying Pb2+ in aqueous samples using a smartphone-based colorimetric device with an imprinted polymer (IIP). The IIP was synthesized by modifying the previous study; using rhodizonate, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), N,N'-methylenebisacrylamide (MBA), and potassium persulfate (KPS). The polymers were then characterized. An absorption study was performed to determine the optimal conditions for the smartphone-based colorimetric device processing. The device consists of a black box (10 × 10 × 10 cm), which was designed to ensure repeatability of the image acquisition. The methodology involved the use of a smartphone camera to capture images of IIP previously exposed at Pb2+ solutions with various concentrations, and color channel values were calculated (RGB, YMK HSVI). PLS multivariate regression was performed, and the optimum working range (0-10 mg L-1) was determined using seven principal components with a detection limit (LOD) of 0.215 mg L-1 and R2 = 0.998. The applicability of a colorimetric sensor in real samples showed a coefficient of variation (% RSD) of less than 9%, and inductively coupled plasma mass spectrometry (ICP-MS) was applied as the reference method. These results confirmed that the quantitation smartphone-based colorimetric sensor is a suitable analytical tool for reliable on-site Pb2+ monitoring.

Development of an Optical Sensor Using a Molecularly Imprinted Polymer as a Selective Extracting Agent for the Direct Quantification of Tartrazine in Real Water Samples.

This study presents a new optical sensor for tartrazine (TAR) quantification developed using a molecularly imprinted polymer (MIP) as the recognition element, with optical fiber serving as the supporting substrate. The fiber surface was functionalized with 3-(trimethoxysilyl)propyl methacrylate (MPS), and the fiber was coated with MIP using the precipitation polymerization method. The analysis of MIP immobilization on the functionalized optical fiber (FF) was conducted through the use of scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) techniques. Experimental parameters, such as contact time and fiber length, were adjusted in order to obtain the highest sensitive response signal for the functionalized optical fiber (FF-MIP). The fiber sensor, FF-MIP, exhibited a relatively higher response signal for tartrazine compared to other interfering dyes. The rapid and total desorption of the analyte from FF-MIP allowed the immediate reemployment of FF-MIP, which also presented an acceptable repeatability for the reflectance signal. The imprinting factors for the studied dyes were between 0.112 and 0.936 in front of TAR, 1.405, and selectivity factors were between 1.501 and 12.545, confirming the sensor selectivity. The FF-MIP sensor was successfully applied for tartrazine quantification in real water samples, where it yielded satisfactory results comparable to those of the HPLC reference method.

Development and Characterization of a Molecularly Imprinted Polymer for the Selective Removal of Brilliant Green Textile Dye from River and Textile Industry Effluents.

In this paper, we present an alternative technique for the removal of Brilliant Green dye (BG) in aqueous solutions based on the application of molecularly imprinted polymer (MIP) as a selective adsorbent for BG. The MIP was prepared by bulk radical polymerization using BG as the template; methacrylic acid (MAA) as the functional monomer, selected via computer simulations; ethylene glycol dimethacrylate (EGDMA) as cross-linker; and 2,2'-azobis(2-methylpropionitrile) (AIBN) as the radical initiator. Scanning electron microscopy (SEM) analyses of the MIP and non-molecularly imprinted polymer (NIP)-used as the control material-showed that the two polymers exhibited similar morphology in terms of shape and size; however, N2 sorption studies showed that the MIP displayed a much higher BET surface (three times bigger) compared to the NIP, which is clearly indicative of the adequate formation of porosity in the former. The data obtained from FTIR analysis indicated the successful formation of imprinted polymer based on the experimental procedure applied. Kinetic adsorption studies revealed that the data fitted quite well with a pseudo-second order kinetic model. The BG adsorption isotherm was effectively described by the Langmuir isotherm model. The proposed MIP exhibited high selectivity toward BG in the presence of other interfering dyes due to the presence of specific recognition sites (IF = 2.53) on its high specific surface area (112 m2/g). The imprinted polymer also displayed a great potential when applied for the selective removal of BG in real river water samples, with recovery ranging from 99 to 101%.

Biomimetic Material for Quantification of Methotrexate Using Sensor Based on Molecularly Imprinted Polypyrrole Film and MWCNT/GCE.

This study investigates biomimetic sensors for the detection of methotrexate contaminants in environmental samples. Sensors inspired by biological systems are the focus of this biomimetic strategy. Methotrexate is an antimetabolite that is widely used for the treatment of cancer and autoimmune diseases. Due to the widespread use of methotrexate and its rampant disposal into the environment, the residues of this drug are regarded as an emerging contaminant of huge concern, considering that exposure to the contaminant has been found to lead to the inhibition of some essential metabolic processes, posing serious risks to humans and other living beings. In this context, this work aims to quantify methotrexate through the application of a highly efficient biomimetic electrochemical sensor constructed using polypyrrole-based molecularly imprinted polymer (MIP) electrodeposited by cyclic voltammetry on a glassy carbon electrode (GCE) modified with multi-walled carbon nanotubes (MWCNT). The electrodeposited polymeric films were characterized by infrared spectrometry (FTIR), scanning electron microscopy (SEM), and cyclic voltammetry (CV). The analyses conducted using differential pulse voltammetry (DPV) yielded a detection limit of 2.7 × 10-9 mol L-1 for methotrexate, a linear range of 0.01-125 µmol L-1, and a sensitivity of 0.152 µA L mol-1. The results obtained from the analysis of the selectivity of the proposed sensor through the incorporation of interferents in the standard solution pointed to an electrochemical signal decay of only 15.4%. The findings of this study show that the proposed sensor is highly promising and suitable for use in the quantification of methotrexate in environmental samples.

Synthesis and colloidal characterization of folic acid-modified PEG-b-PCL Micelles for methotrexate delivery.

Hydrophobic drugs, such as methotrexate, are not easily delivered into the human body. Therefore, the use of amphiphilic nanoplatforms to the transport of these drugs through the bloodstream is a challenge. While the hydrophobic region interacts with the drug, the hydrophilic outer layer enhances its bioavailability and circulation time. Poly (ethylene glycol)-block-poly(ε-caprolactone) PEG-b-PCL micelles are biodegradable and biocompatible, allowing its use as a nanocarrier for drug delivery systems. The stealth property of PEG that composes the outer layer of nanoplatforms, makes the micelle unperceivable to phagocytic cells, increasing the circulation time in the human body. In addition, folic acid functionalization enables micelle selectively targeting to cancer cells, improving treatment efficiency and reducing side effects. In this work, PEG-b-PCL copolymer was synthesized by ring opening polymerization (ROP) of the ε-caprolactone with Poly(ethylene glycol) as a macroinitiator and tin(II) 2-ethyl hexanoate as a catalyst. Functionalization of such micelles with folic acid occurred through the modification of the PEG terminal group. The surface modification of the copolymer micelles resulted in higher critical micellar concentration (CMC), increasing approximately 100 times. The synthesis of the copolymers resulted in molecular weight around 3000 g mol-1 with low polydispersity. The polymer micelles have a hydrodynamic diameter in the range of 100-200 nm and the functionalized sample doesn't show aggregation in the considered pH range. High incorporation efficiency was obtained with a minimum percentage of 85%. The drug release profile and linearization from the Peppas model confirmed the interaction of methotrexate with the hydrophobic segment of the copolymer and its release mechanism by relaxation and/or degradation of the chains, making PEG-b-PCL micelles suitable candidates for hydrophobic drug delivery systems.

A simple electrochemical method to monitor an azo dye reaction with a liver protein.

Disperse Orange 37 (DO37) is an efficient azo dye for dyeing synthetic textile materials owing to its resistance to degradation that may also be harmful to humans as DO37 is not entirely eliminated in wastewater treatment. In this paper, we demonstrate that DO37 is bleached by reduced glutathione (GSH) in a reaction catalyzed by glutathione-s-transferase (GST), a phase II detoxification enzyme. The reaction included a nucleophilic attack involving sulfhydryl groups, confirmed using density functional theory (DFT) calculations. DO37 also induced quenching in the fluorescence of GST through static suppression. The reaction was determined using differential pulse voltammetry (DPV) by monitoring the oxidation peak at 0.65 V of GSH sulfhydryl group. Quantitative estimation of the product reaction could be made by measuring an additional oxidation peak at 0.91 V which increased linearly with DO37 concentration. These electrochemical determinations were made possible by preconcentrating the reaction product on a graphite-epoxy electrode with immobilization of GST onto magnetite nanoparticles. Straightforward biological implications from the results are associated with the known toxicity of azo dyes such as DO37, which has been proven here to interact strongly with both GSH and the liver enzyme GST, and may induce hepatocarcinogenesis or other types of cancer.

pH-responsive poly(aspartic acid) hydrogel-coated magnetite nanoparticles for biomedical applications.

A novel multifunctional nanosystem formed by magnetite nanoparticles coated with pH-responsive poly(aspartic acid) hydrogel was developed. Magnetite nanoparticles (Fe3O4) have been intensively investigated for biomedical applications due to their magnetic properties and dimensions similar to the biostructures. Poly(aspartic acid) is a water-soluble, biodegradable and biocompatible polymer, which features makes it a potential candidate for biomedical applications. The nanoparticles surface modification was carried out by crosslinking polysuccinimide on the magnetite nanoparticles surface and hydrolyzing the succinimide units in mild alkaline medium to obtain the magnetic poly(aspartic acid) hydrogel. The surface modification in each step was confirmed by DRIFTS, TEM and zeta potential measurements. The hydrodynamic diameter of the nanosystems decreases as the pH value decreases. The nanosystems showed high colloidal stability in water and no cytotoxicity was detected, which make these nanosystems suitable for biomedical applications.