Miriam Martín

Preparation of core–shell Fe3O4@poly(dopamine) magnetic nanoparticles for biosensor construction

Novel core-shell Fe3O4@poly(dopamine) magnetic nanoparticles were prepared through an in situ self-polymerization method. The hybrid nanomaterial showed an average core diameter of 11 ± 3 nm and a polymer thin film thickness of 1.8 ± 0.2 nm. The core-shell nanoparticles were employed as solid supports for the covalent immobilization of horseradish peroxidase (HRP), and the resulting biofunctionalized magnetic nanoparticles were employed to construct an amperometric biosensor for H2O2. The enzyme biosensor showed a high sensitivity of 442.14 mA M-1 cm-2, a low limit of detection of 182 nM, a wide linear range from 6.0 × 10-7 to 8.0 × 10-4 M and high stability for 1 month.

Partial least-squares method in analysis by differential pulse polarography. Simultaneous determination of amiloride and hydrochlorothiazide in pharmaceutical preparations

A method is proposed for the simultaneous determination of amiloride and hydrochlorothiazide in pharmaceutical preparations using differential pulse polarography in the presence of oxygen and partial least-squares (PLS) for calibration. The experimental variables that influence the system (pulse height, pulse delay and pH) are optimized by using response surface methodology to relate the variables to be optimized to the mean relative square error of prediction (RSEP), which is minimized. The proposed method was used to determine the two drugs in synthetic mixtures and pharmaceutical preparations. The results were validated by comparison with HPLC, with errors less than 10% in all instances.

Core-shell polydopamine magnetic nanoparticles as sorbent in micro-dispersive solid-phase extraction for the determination of estrogenic compounds in water samples prior to high-performance liquid chromatography-mass spectrometry analysis.

In this work, core-shell Fe3O4@poly(dopamine) magnetic nanoparticles (m-NPs) were prepared and characterized in our laboratory and applied as sorbents for the magnetic-micro solid phase extraction (m-μSPE) of twelve estrogenic compounds of interest (i.e. 17α-estradiol, 17β-estradiol, estrone, hexestrol, 17α-ethynylestradiol, diethylstibestrol, dienestrol, zearalenone, α-zearalanol, β-zearalanol, α-zearalenol and β-zearalenol) from different water samples. Separation, determination and quantification were achieved by high-performance liquid chromatography coupled to ion trap mass spectrometry with electrospray ionization. NPs@poly(dopamine) were synthesized by a chemical coprecipitation procedure and characterized by different surface characterization techniques (X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis, transmission and scanning electron microscopy, infrared and Raman spectroscopy, vibrating sample magnetometry, microelectrophoresis and adsorption/desorption isotherms). Parameters affecting the extraction efficiency of m-μSPE (i.e. polymerization time, pH of the sample, extraction and elution conditions) were studied and optimized. The methodology was validated for Milli-Q, mineral, tap and wastewater using 2-methoxyestradiol as internal standard, obtaining recoveries ranging from 70 to 119% with relative standard deviation values lower than 20% and limits of quantification in the range 0.02-1.1 μg/L.

Surfactant-promoted Prussian Blue-modified carbon electrodes: Enhancement of electro-deposition step, stabilization, electrochemical properties and application to lactate microbiosensors for the neurosciences

We report here for the first time a comparison of the beneficial effects of different cationic surfactants - cetyl trimethyl ammonium bromide (CTAB), benzethonium chloride (BZT) and cetylpyridinium chloride (CPC) - for the electrochemical synthesis of Prussian Blue (PB) films, using cyclic voltammetry (CV), on screen-printed carbon electrodes (SPCEs). Their electrochemical properties were investigated, paying special attention to parameters such as the amount of PB deposited, film thickness, charge transfer rate, permeability, reversibility, stability and sensitivity to hydrogen peroxide detection. All surfactant-enhanced PB-modified SPCEs displayed a significant improvement in their electrochemical properties compared with PB-modified SPCEs formed in the absence of surfactants. Surfactant-modified electrodes displayed a consistently higher PB surface concentration value of 2.1±0.4×10(-8) mol cm(-2) (mean±SD, n=3) indicating that PB deposition efficiency was improved 2-3 fold. K(+) and Na(+) permeability properties of the films were also studied, as were kinetic parameters, such as the surface electron transfer rate constant (k(s)) and the transfer coefficient (α). The hydrogen peroxide sensitivity of surfactant-modified PB films generated by 10 electro-deposition CV cycles gave values of 0.63 A M(-1) cm(-2), which is higher than those reported previously for SPCEs by other authors. Finally, the first lactate microbiosensor described in the literature based on BZT-modified PB-coated carbon fiber electrodes is presented. Its very small cross-section (~10 μm diameter) makes it particularly suitable for neuroscience studies in vivo.

Quinone-rich poly(dopamine) magnetic nanoparticles for biosensor applications.

Novel core-shell quinone-rich poly(dopamine)-magnetic nanoparticles (MNPs) were prepared by using an in situ polymerization method. Catechol groups were oxidized to quinone by using a thermal treatment. MNPs were characterized by using X-ray diffraction, X-ray photoelectron spectroscopy, atomic force microscopy, magnetic force microscopy, UV/Vis, Fourier-transform infrared spectroscopy, and electrochemical techniques. The hybrid nanomaterial showed an average core diameter of 17 nm and a polymer-film thickness of 2 nm. The core-shell nanoparticles showed high reactivity and were used as solid supports for the covalent immobilization of glucose oxidase (Gox) through Schiff base formation and Michael addition. The amount of Gox immobilized onto the nanoparticle surface was almost twice that of the nonoxidized film. The resulting biofunctionalized MNPs were used to construct an amperometric biosensor for glucose. The enzyme biosensor has a sensitivity of 8.7 mA M(-1)  cm(-2) , a low limit of detection (0.02 mM), and high stability for 45 days. Finally, the biosensor was used to determine glucose in blood samples and was checked against a commercial glucometer.

Rapid Legionella pneumophila determination based on a disposable core-shell Fe₃O₄@poly(dopamine) magnetic nanoparticles immunoplatform.

A novel amperometric magnetoimmunoassay, based on the use of core-shell magnetic nanoparticles and screen-printed carbon electrodes, was developed for the selective determination of Legionella pneumophila SG1. A specific capture antibody (Ab) was linked to the poly(dopamine)-modified magnetic nanoparticles (MNPs@pDA-Ab) and incubated with bacteria. The captured bacteria were sandwiched using the antibody labeled with horseradish peroxidase (Ab-HRP), and the resulting MNPs@pDA-Ab-Legionella neumophila-Ab-HRP were captured by a magnetic field on the electrode surface. The amperometric response measured at -0.15 V vs. Ag pseudo-reference electrode of the SPCE after the addition of H2O2 in the presence of hydroquinone (HQ) was used as transduction signal. The achieved limit of detection, without pre-concentration or pre-enrichment steps, was 10(4) Colony Forming Units (CFUs) mL(-1). The method showed a good selectivity and the MNPs@pDA-Ab exhibited a good stability during 30 days. The possibility of detecting L. pneumophila at 10 CFU mL(-1) level in less than 3 h, after performing a membrane-based preconcentration step, was also demonstrated.

Application of Prussian Blue electrodes for amperometric detection of free chlorine in water samples using Flow Injection Analysis.

The performance for free chlorine detection of surfactant-modified Prussian Blue screen printed carbon electrodes (SPCEs/PB-BZT) have been assessed by cyclic voltammetry and constant potential amperometry. The characterization of SPCEs/PB-BZT by X-ray photoemission, Raman and infrared spectroscopies confirmed the correct electrodeposition of the surfactant-modified PB film. These electrodes were incorporated in a Flow Injection device and the optimal working conditions determined as a function of experimental variables such as detection potential, electrolyte concentration or flow-rate. The sensor presented a linear response in the range 0-3 ppm free chlorine, with a sensitivity of 16.2 μA ppm(-1) cm(-2). The limit of detection (LOD) (S/N=3.3) and the limit of quantification (S/N=10) amounted to 8.25 and 24.6 ppb, respectively, adequate for controlling tap and drinking waters. To demonstrate the feasibility of using this free chlorine sensor for real applications possible interferences such as nitrate, nitrite and sulfate ions were successfully tested and discarded. Real free chlorine analysis was carried out in spiked tap water samples and commercial bleaches.

Amperometric magnetobiosensors using poly(dopamine)-modified Fe3O4 magnetic nanoparticles for the detection of phenolic compounds

The synthesis of poly(dopamine)-modified magnetic nanoparticles (MNPs) and their application in preparing electrochemical enzyme biosensors that are useful to detect phenolic compounds is reported in this work. MNPs of about 16 nm were synthesized by a co-precipitation method and conveniently modified with poly(dopamine). Non-modified and modified MNPs were characterized using X-ray photoelectron spectroscopy (XPS), Raman and infrared spectroscopy, X-ray diffraction (XRD) and atomic force microscopy (AFM). Horseradish peroxidase (HRP) was covalently immobilized onto the surface of the poly(dopamine)-modified MNPs via Michael addition and/or Schiff base formation and used to construct a biosensor for phenolic compounds by capturing the HRP-modified-nanoparticles onto the surface of a magnetic-modified glassy carbon electrode (GCE). Cyclic voltammetry and amperometry were used to study the electrochemical and analytical properties of the biosensor using hydroquinone (HQ) as a redox probe. Among the different phenolic compounds studied, the biosensor exhibited higher sensitivity for HQ, 1.38 A M−1 cm−2, with limits of detection and quantification of 0.3 and 1.86 μM, respectively. The analytical biosensor performance for HQ and 2-aminophenol compared advantageously with those of previous phenolic biosensors reported in the literature.