Development of a "turn off" fluorescent molecularly imprinted nanoparticle-based sensor for selective captopril quantification in synthetic urine and wastewater samples.

The combination of silica nanoparticles with fluorescent molecularly imprinted polymers (Si-FMIPs) prepared by a one-pot sol-gel synthesis method to act as chemical sensors for the selective and sensitive determination of captopril is described. Several analytical parameters were optimized, including reagent ratio, solvent, concentration of Si-FMIP solutions, and contact time. Fourier-transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), and the ninhydrin assay were used for characterization. The selectivity was evaluated against molecules belonging to other drug classes, such as fluoroquinolones, nonacid nonopioids, benzothiadiazine, alpha amino acids, and nitroimidazoles. Under optimized conditions, the Si-FMIP-based sensor exhibited a working range of 1-15 µM, with a limit of detection (LOD) of 0.7 µM, repeatability of 6.4% (n = 10), and suitable recovery values at three concentration levels (98.5% (1.5 µM), 99.9% (3.5 µM), and 99.2% (7.5 µM)) for wastewater samples. The sensor provided a working range of 0.5-15 µM for synthetic urine samples, with an LOD of 0.4 µM and a repeatability of 7.4% (n = 10) and recovery values of 93.7%, 92.9%, and 98.0% for 1.0 µM, 3.5 µM, and 10 µM, respectively. In conclusion, our single-vessel synthesis approach for Si-FMIPs proved to be highly effective for the selective determination of captopril in wastewater and synthetic urine samples.

Synthesis, characterization and application of a novel ion hybrid imprinted polymer to adsorb Cd(II) in different samples.

Two new ionic imprinted hybrid polymers (IIHP) and their corresponding non imprinted hybrid polymers (NIHP) were synthesized. The prepared IIHP was highly selective to Cd2+. To prepare the IIHP, 1-vinylimidazole (VIN) was used as the functional monomer, (3-mercaptopropyl) trimethoxysilane (MP) or (3-aminopropyl) trimethoxysilane (AMP) was used as the functional organosilane, trimethylolpropane (TRIM) was used as the crosslinking agent, AIBN was used as a radical initiator and TEOS was used as a functional precursor. The functional monomer was selected considering calculations based on the density functional theory (DFT). The fabricated materials were characterized via field emission gun scanning electron microscopy (FEG-SEM), Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray spectroscopy (EDX) and thermogravimetric analysis (TGA). The maximum adsorption capacity of Cd2+ was achieved at a pH of 7.2 in the tris-HCl medium. The adsorption test indicated that the reaction followed pseudo second order kinetics, and the equilibrium sorption data fitted well into the Langmuir isotherm model. The relative selectivity coefficients of polymers IIHP-VIN-AMP and IIHP-VIN-MP, as evaluated in binary mixtures of Cd2+ and interferent cations (Pb2+, Zn2+, Hg2+, Cu2+, Ni2+, Ca2+, Mg2+, and Na+) at different molar ratios, were greater than one due to the presence of specific recognition sites for Cd2+ ions. Moreover, the selective materials exhibited a high reusability and reproducibility in the context of Cd2+ adsorption. These adsorbent materials, specifically IIHP-VIN-MP, exhibited a % removal efficiency of more than 90% for the Cd2+ in river water samples.

Preparation of crosslinked chitosan magnetic membrane for cations sorption from aqueous solution.

A chitosan magnetic membrane was prepared in order to confer magnetic properties to the membrane, which could be used for the removal of cations from aqueous solution. The crosslinked magnetic membrane was compared with pristine chitosan membrane in term of stability, morphology and cation adsorption capacity. The fabricated magnetic materials are thermally stable as shown by thermogravimetric curves. The membrane containing nickel magnetic particles (CHNiF-G) shows high thermal stability compared to the other membranes. The Fourier transform infrared spectroscopy showed successful preparation of chitosan magnetic membrane. Scanning electron microscopy micrographs showed the rough surface of the membrane with increased porosity. The prepared chitosan membranes were applied to cations of copper, nickel and lead in dilute aqueous solution. The chitosan membrane showed the following adsorption order for metallic cations: Cu2+ > Ni2+ > Pb2+, while CHNiF-G showed higher capacity, 3.51 mmol g-1 for copper, reflecting the improvement in adsorption capacity, since the amount of copper on pristine chitosan gave 1.40 mmol g-1. The time required for adsorption to reach to the equilibrium was 6 h for the selected cations using different chitosan membranes. The kinetic study showed that adsorption followed pseudo-second order kinetics. The most commonly used isotherm models, Freundlich, Langmuir and Temkin, were applied to experimental data using linear regression technique. However, The Temkin model fits better to experimental data.

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.

Peptide-based biosensing approaches for targeting breast cancer-derived exosomes.

Exosomes are nanovesicles present in all the biological fluids, making them attractive as non-invasive biomarkers for diseases like cancer, among many others. However, exosomes are complex to separate and detect, requiring comprehensive molecular characterization for their routine use in diagnostics. This study explores the use of peptides as cost-effective and stable alternatives to antibodies for exosome binding. To achieve that, phage display technology was employed to select peptides with high specificity for target molecules in exosomes. Specifically, a selected peptide was evaluated for its ability to selectively bind breast cancer-derived exosomes. Proteomic analysis identified 38 protein candidates targeted by the peptide on exosome membranes. The binding of the peptide to breast cancer-derived exosomes was successfully demonstrated by flow cytometry and magneto-actuated immunoassays. Furthermore, an electrochemical biosensor was also tested for breast cancer-derived exosome detection and quantification. The peptide demonstrated effective binding to exosomes from aggressive cancer cell lines, offering promising results in terms of specificity and recovery. This research shows potential for developing rapid, accessible diagnostic tools for breast cancer, especially in low-resource healthcare settings.

Biomimetic Electrochemical Sensors Based on Core-Shell Imprinted Polymers for Targeted Sunset Yellow Estimation in Environmental Samples.

Magnetic molecularly imprinted polymers (MMIPs) contain the predesigned specialized recognition capability that can be chosen to build credible functional materials, that are easy to handle and have a good degree of specificity. Hence, the given piece of work is intended to design a novel electrochemical sensor incorporating magnetite-based molecularly imprinted polymers. The building materials consisted of a cross-linker (EGDMA), reaction-initiator (AIBN), monomer (methylene succinic acid-MSA), and template molecule (Sunset Yellow-SY dye). MMIPs exhibited a diameter of 57 nm with an irregular shape due to the presence of cavities based on SEM analysis. XRD patterns exhibited crystallinity, as well as amorphous peaks that are attributed to polymeric and non-polymeric frameworks of MMIPs. The crystallite size of the MMIPs from XRD analysis was found to be 16.28 nm based on the Debye-Scherrer's equation. Meanwhile, the FTIR bands showed the synthesis of MMIPs using monomer and methylene succinic acid. The sorption data at the optimized operating conditions (pH 2, sorbent dosage 3 mg, time 18 min) showed the highest sorption capacity of 40 mg/g. The obtained data best fitted to the Langmuir sorption isotherm and followed the pseudo-second-order kinetics. The magneto-sensors were applied for ultrasensitive, rapid, and simple sensing of SY dye. The electrochemical experiments were run at the operating condition range of (scan rate 10-50 mV/s, tads 0-120 s, pH 5-9, potential range 1-1.5 V for CV and 1-1.3 V for SWAdASV). The linear range of detection was set to 1.51 × 10-6 M to 1.51 × 10-6 M posing LOD and LOQ values of 8.6242 × 10-5 M and 0.0002874 M, respectively. The regression analysis value for the calibration was found to be 0.950. Additionally, high adsorption efficiency, selectivity, reusability, and strong structural stability of the magneto-sensors showed potential use for SY detection in real samples. These characteristics make MMIPs a viable electrochemical substrate for the detection of chemical contaminants in the environment and in health-related products.

Development of a New Electrochemical Sensor Based on Mag-MIP Selective Toward Amoxicillin in Different Samples.

This work describes an electrochemical sensor for the selective recognition and quantification of amoxicillin and a ß-lactam antibiotic in real samples. This sensor consists of a carbon paste electrode (CPE) modified with mag-MIP (magnetic molecularly imprinted polymer), which was prepared by precipitation method via free radical using acrylamide (AAm) as functional monomer, N,N'-methylenebisacrylamide (MBAA) as a crosslinker, and potassium persulfate (KPS) as initiator, to functionalized magnetic nanoparticles. The magnetic non-imprinted polymers (mag-NIP) were prepared using the same experimental procedure without analyte and used for the preparation of a CPE for comparative studies. The morphological, structural, and electrochemical characteristics of the nanostructured material were evaluated using Field emission gun scanning electron microscopy (FEG-SEM), Transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), Vibrating sample magnetometry (VSM), X-ray diffraction (XRD), and voltammetric technique. Electrochemical experiments performed by square wave voltammetry show that the mag-MIP/CPE sensor had a better signal response compared to the non-imprinted polymer-modified electrode (mag-NIP/CPE). The sensor showed a linear range from 2.5 to 57 µmol L-1 of amoxicillin (r 2 = 0.9964), with a limit of detection and a limit of quantification of 0.75 and 2.48 µmol L-1, respectively. No significant interference in the electrochemical signal of amoxicillin was observed during the testing experiments in real samples (skimmed milk and river water). The proposed mag-MIP/CPE sensor could be used as a good alternative method to confront other techniques to determine amoxicillin in different samples.

Magnetic MIPs: Synthesis and Applications.

Magnetic molecularly imprinted polymers (MMIPs) are constructed based on the blending of inorganic nanoparticles with molecularly imprinted polymers (MIPs). MMIPs are synthesized in a core-shell format in which inorganic nanoparticles are applied as the core part of the material while selective polymeric layers are used as the shell covering the surface of the core area. In essence, MMIPs thus reflect a combination of the best characteristics of both inorganic nanoparticles and MIPs, where the specificity of cavities imprinted on the MIP is merged with superparamagnetic properties of the nano-magnetite. The synergic combination of the two distinct materials facilitates the process of extracting analytes from complex samples. Owing to their suitable characteristics, MMIPs have become widely used in different areas of analysis.

Selective UV-filter detection with sensors based on stainless steel electrodes modified with polyaniline doped with metal tetrasulfonated phthalocyanine films.

This work describes the construction and application of two amperometric sensors for sensitive UV-filter determination. The sensors were prepared using stainless steel electrodes in which polyaniline (PANI) was electrochemically polymerized in the presence of nickel (NiPcTS) or iron (FePcTS) tetrasulfonated phthalocyanines. The sensor surface characterizations were carried out using atomic force microscopy (AFM). The PANI/NiPcTS sensor was selective for the chemical UV-filter p-aminobenzoic acid (PABA) and the PANI/FePcTS sensor was selective for octyldimethyl-PABA (ODP), both in a mixture of tetrahydrofuran (THF) and 0.1 mol L(-1) H2SO4 at a volume ratio of 30 : 70, and with an applied potential of 0.0 mV vs. Ag|AgCl. A detailed investigation of the selectivity was carried out for both sensors, in order to determine their responses for ten different UV filters. Finally, each sensor was successfully applied to PABA or ODP quantification in sunscreen formulations and water from swimming pools.

Electrochemical sensors based on biomimetic magnetic molecularly imprinted polymer for selective quantification of methyl green in environmental samples.

A new biomimetic sensor was prepared on carbon paste with magnetic molecularly imprinted polymer (mag-MIP) for sensitive and selective detection of methyl green dye. The mag-MIP was synthesized using a functional monomer that was selected before by computational simulation. A mag-NIP (magnetic non-imprinted polymer) control material was also prepared for comparative purposes. Modeling adsorption studied revealed that the dye-polymer interface followed pseudo-first order kinetics and that maximum adsorption (Qm) of the dye on mag-MIP was 3.13 mg g-1, while the value for mag-NIP was 1.58 mg g-1. The selective material was used as a sensing spot in fabrication of an electrochemical sensor based on modified carbon paste. For electrochemical analysis, the best achievement of the sensor was acquire by tack together a paste with 6.7% (w/w) of mag-MIP and using square-wave adsorptive anodic stripping voltammetry (SWAdASV) in 0.1 mol L-1 phosphate buffer (pH 7.0), with an applied potential (Eappl) of 0.3 V vs. Ag|AgClsat during an adsorption time (Tads) of 120 s. The results were obtained under optimized conditions in which sensor provided a linear concentration range of methyl green from 9.9 × 10-8 to 1.8 × 10-6 mol L-1, with a limit of detection (LOD) of 1.0 × 10-8 mol L-1 and a satisfactory relative standard deviation (RSD) of 4.3% (n = 15). The proposed sensor was applying using two spiked river water samples, obtaining recoveries ranging from 93% to 103%. The proposed method exhibits excellent precision also high reliability and proved to be an alternative method for the quantification of methyl green in real samples.

Biomimetic magnetic sensor for electrochemical determination of scombrotoxin in fish.

This work addresses a novel, rapid and cost-effective approach for the electrochemical sensing of scombrotoxin (histamine) in fish based on magnetic molecularly imprinted polymer (magnetic-MIP). The histamine magnetic-MIP was synthesized by the core-shell method using histamine as a template, and 2-vinyl pyridine as functional monomer. The magnetic-MIP was characterized by TEM, SEM, and confocal microscopy. Additionally, the binding capacity of magnetic-MIP towards histamine was investigated and compared with magnetic non-molecularly imprinted polymer (magnetic-NIP). This biomimetic material merged the advantages of MIPs and magnetic particles (MPs), including low cost of production, stability, high binding capacity and can be easily separated by the aid of a permanent magnet. The magnetic-MIP was integrated into magneto-actuated electrodes for the direct electrochemical detection of histamine preconcentrated from fish samples. The results revealed that this approach succeeded in the preconcentration and determination of histamine with a LOD as low as 1.6 × 10-6 mg L-1, much lower than the index for fish spoilage (50 mg kg-1) accordingly to the legislation. Furthermore, the analytical performance was validated for the determination of histamine in scombroid fish samples with recovery values ranging from 96.8 to 102.0 %, confirm so it can be applied easily for routine food examination.

Theoretical and experimental study for the biomimetic recognition of levothyroxine hormone on magnetic molecularly imprinted polymer.

This study addresses the rational design of a magnetic molecularly imprinted polymer (magnetic-MIP) for the selective recognition of the hormone levothyroxine. The theoretical study was carried out by the density functional theory (DFT) computations considering dispersion interaction energies, and using the D2 Grimme's correction. The B97-D/def2-SV(P)/PCM method is used not only for studying the structure of the template the and monomer-monomer interactions, but also to assess the stoichiometry, noncovalent binding energies, solvation effects and thermodynamics properties such as binding energy. Among the 13 monomers studied in silico, itaconic acid is the most suitable according to the thermodynamic values. In order to assess the efficiency of the computational study, three different magnetic-MIPs based on itaconic acid, acrylic acid and acrylamide were synthesized and experimentally compared. The theoretical results are in agreement with experimental binding studies based on laser confocal microscopy, magneto-actuated immunoassay and electrochemical sensing. Furthermore, and for the first time, the direct electrochemical sensing of L-thyroxine preconcentrated on magnetic-MIP was successfully performed on magneto-actuated electrodes within 30 min with a limit of detection of as low as 0.0356 ng mL-1 which cover the clinical range of total L-thyroxine. Finally, the main analytical features were compared with the gold standard method based on commercial competitive immunoassays. This work provides a thoughtful strategy for magnetic molecularly imprinted polymer design, synthesis and application, opening new perspectives in the integration of these materials in magneto-actuated approaches for replacing specific antibodies in biosensors and microfluidic devices.

Synthesis and evaluation of a molecularly imprinted polymer for selective adsorption and quantification of Acid Green 16 textile dye in water samples.

An alternative for determining environmental pollutants, like textile dyes, is the use of molecularly imprinted polymers (MIPs) as solid phase extraction (SPE) or as sensor recognition systems. MIPs are tailor-made artificial receptor sites in a polymer, which present good affinity and selectivity. This work shows the synthesis of MIPs for the Acid Green 16 (AG16) textile dye and the results of rebinding, selectivity and application of this MIP in water samples. MIP synthesis was performed using AG16 dye (template), 1-vinylimidazole (functional monomer), ethylene-glycol-dimethacrylate (cross-link), 2,2'-azobis(2-methylpropionitrile) (initiator) and methanol (solvent) by bulk synthesis. The imprinted polymer presented excellent rebinding of 83%, an imprinted factor of 6.91 and great selectivity in comparison with other textile dyes. Additionally, the MIP showed high efficiency in the extraction of this dye in water samples, presenting a recovery rate close to 100% and a better performance when compared to commercial SPE cartridges. Due to this excellent performance for AG16, the application of this MIP to determine dyes in different matrices of environmental importance is promising.

Magnetically separable polymer (Mag-MIP) for selective analysis of biotin in food samples.

This work presents an efficient method for the preparation of magnetic nanoparticles modified with molecularly imprinted polymers (Mag-MIP) through core-shell method for the determination of biotin in milk food samples. The functional monomer acrylic acid was selected from molecular modeling, EGDMA was used as cross-linking monomer and AIBN as radical initiator. The Mag-MIP and Mag-NIP were characterized by FTIR, magnetic hysteresis, XRD, SEM and N2-sorption measurements. The capacity of Mag-MIP for biotin adsorption, its kinetics and selectivity were studied in detail. The adsorption data was well described by Freundlich isotherm model with adsorption equilibrium constant (KF) of 1.46 mL g(-1). The selectivity experiments revealed that prepared Mag-MIP had higher selectivity toward biotin compared to other molecules with different chemical structure. The material was successfully applied for the determination of biotin in diverse milk samples using HPLC for quantification of the analyte, obtaining the mean value of 87.4% recovery.

Amperometric biosensor based on horseradish peroxidase for biogenic amine determinations in biological samples.

An amperometric biosensor for total biogenic amine determinations, using a carbon paste electrode modified with horseradish peroxidase (HRP) enzyme is described. The HRP immobilization on graphite was made using bovine serum albumin, carbodiimide and glutaraldehyde. The biosensor response was optimized using serotonin and it presented the best performance in 0.1 mol l(-1) phosphate buffer (pH=7.0) containing 10 micromol l(-1) of hydrogen peroxide. Under optimized operational conditions at -50 mV versus SCE, a linear response range from 40 to 470 ng ml(-1) was obtained. The detection limit was 17 ng ml(-1) and the response time was 0.5s. The proposed sensor presented a stable response during 4h under continuous monitoring. The difference of the response between six sensor preparations was <2%. The sensor was applied in the determination of total biogenic amines (neurotransmitters) in rat blood samples with success, obtaining a recovery average of 102%.

Glutathione-s-transferase modified electrodes for detecting anticancer drugs.

With the fast growth of cancer research, new analytical methods are needed to measure anticancer drugs. This is usually accomplished by using sophisticated analytical instruments. Biosensors are attractive candidates for measuring anticancer drugs, but currently few biosensors can achieve this goal. In particular, it is challenging to have a general method to monitor various types of anticancer drugs with different structures. In this work, a biosensor was developed to detect anticancer drugs by modifying carbon paste electrodes with glutathione-s-transferase (GST) enzymes. GST is widely studied in the metabolism of xenobiotics and is a major contributing factor in resistance to anticancer drugs. The measurement of anticancer drugs is based on competition between 1-chloro-2,4-dinitrobenzene (CDNB) and the drugs for the GST enzyme in the electrochemical potential at 0.1V vs. Ag/AgCl by square wave voltammetry (SWV) or using a colorimetric method. The sensor shows a detection limit of 8.8µM cisplatin and exhibits relatively long life time in daily measurements.

Fast assembly of non-thiolated DNA on gold surface at lower pH.

In a typical protocol for attaching DNA to a gold electrode, thiolated DNA is incubated with the electrode at neutral pH overnight. Here we report fast adsorption of non-thiolated DNA oligomers on gold electrodes at acidic pH (i.e., pH ~3.0). The peak-to-peak potential difference and the redox peak currents in typical cyclic voltammetry of [Fe(CN)6](3-) are investigated to monitor the attachment. Compared with incubation at neutral pH, the lower pH can significantly promote the adsorption processes, enabling efficient adsorption even in 30 min. The adsorption rate is DNA concentration-dependent, while the ionic strength shows no influence. Moreover, the adsorption is base-discriminative, with a preferred order of A>C>>G, T, which is attributed to the protonation of A and C at low pH and their higher binding affinity to gold surface. The immobilized DNA is functional and can hybridize with its complementary DNA but not a random DNA. This work is promising to provide a useful time-saving strategy for DNA assembly on gold electrodes, allowing fast fabrication of DNA-based biosensors and devices.

Cobalt phthalocyanine as a biomimetic catalyst in the amperometric quantification of dipyrone using FIA.

A biomimetic sensor for the determination of dipyrone was prepared by modifying carbon paste with cobalt phthalocyanine (CoPc), and used as an amperometric detector in a flow injection analysis (FIA) system. The results of cyclic voltammetry experiments suggested that CoPc behaved as a biomimetic catalyst in the electrocatalytic oxidation of dipyrone, which involved the transfer of one electron. The optimized FIA procedure employed a flow rate of 1.5 mL min(-1), a 75 µL sample loop, a 0.1 mol L(-1) phosphate buffer carrier solution at pH 7.0 and amperometric detection at a potential of 0.3 V vs. Ag/AgCl. Under these conditions, the proposed method showed a linear response for dipyrone concentrations in the range 5.0 × 10(-6)-6.3 × 10(-3) mol L(-1). Selectivity and interference studies were carried out in order to validate the system for use with pharmaceutical and environmental samples. In addition to being environmentally friendly, the proposed method is a sensitive and selective analytical tool for the determination of dipyrone.

Iron(III) tetra-(N-methyl-4-pyridyl)-porphyrin as a biomimetic catalyst of horseradish peroxidase on the electrode surface: an amperometric sensor for phenolic compound determinations.

The use of iron(III) tetra-(N-methyl-4-pyridyl) porphyrin (FeIIIT4MpyP) and histidine (His) in the construction of an amperometric sensor for phenolic compound determinations is reported, based on horseradish peroxidase (HRP) chemistry. The sensor was prepared by modifying a glassy carbon electrode with Nafion membrane doped with FeIIIT4MpyP and His, in a mass ratio of 1:2. The sensor presented its best performance at 50 mV vs. SCE in 0.1 mol l(-1) succinate buffer (pH = 4.0) containing 125 micromol l(-1) H2O2. Under optimized operational conditions, a linear response range from 0.6 to 6.0 micromol l(-1) was obtained with a sensitivity of 61 nA cm(-2) micromol l(-1). The detection limit for catechol determination was 0.35 micromol l(-1). The response time was less than 0.5 s. The proposed sensor presented stable responses for 100 successive determinations, while satisfactory responses were observed even after 200 measurements. The repeatability, evaluated in terms of relative standard deviation, was 4% for n = 7. The signal responses for other phenolic compounds, including those of environmental and clinical interest, were also investigated.