Multi-walled carbon nanotubes functionalized with a new Schiff base containing phenylboronic acid residues: application to the development of a bienzymatic glucose biosensor using a response surface methodology approach.

An innovative supramolecular architecture is reported for bienzymatic glucose biosensing based on the use of a nanohybrid made of multi-walled carbon nanotubes (MWCNTs) non-covalently functionalized with a Schiff base modified with two phenylboronic acid residues (SB-dBA) as platform for the site-specific immobilization of the glycoproteins glucose oxidase (GOx) and horseradish peroxidase (HRP). The analytical signal was obtained from amperometric experiments at - 0.050 V in the presence of 5.0 × 10-4 M hydroquinone as redox mediator. The concentration of GOx and HRP and the interaction time between the enzymes and the nanohybrid MWCNT-SB-dBA deposited at glassy carbon electrodes (GCEs) were optimized through a central composite design (CCD)/response surface methodology (RSM). The optimal concentrations of GOx and HRP were 3.0 mg mL-1 and 1.50 mg mL-1, respectively, while the optimum interaction time was 3.0 min. The bienzymatic biosensor presented a sensitivity of (24 ± 2) × 102 µA dL mg-1 ((44 ± 4) × 102 µA M-1), a linear range between 0.06 mg dL-1 and 21.6 mg dL-1 (3.1 µM-1.2 mM) (R2 = 0.9991), and detection and quantification limits of 0.02 mg dL-1 (1.0 µM) and 0.06 mg dL-1 (3.1 µM), respectively. The reproducibility for five sensors prepared with the same MWCNT-SB-dBA nanohybrid was 6.3%, while the reproducibility for sensors prepared with five different nanohybrids and five electrodes each was 7.9%. The GCE/MWCNT-SB-dBA/GOx-HRP was successfully used for the quantification of glucose in artificial human urine and commercial human serum samples.

Ultrasensitive multiwall carbon nanotube-mesoporous MCM-41 hybrid-based platform for the electrochemical detection of ascorbic acid.

This work presents for the first time the systematic preparation of a novel carbon nanotube-MCM-41 hybrid employing the mesoporous material MCM-41 as a successful dispersant for multiwall carbon nanotubes (MWCNTs). Relevant dispersion variables such as the amount of MWCNTs, MCM-41 concentration, and sonication time were optimized through a central composite design (CDD)/response surface methodology (RSM). Several solvents were evaluated and N,N-dimethylformamide (DMF) was selected because it allowed reaching stable dispersions with very good electrochemical response. The electrochemical performance of glassy carbon electrodes (GCE) modified with different hybrids was evaluated by cyclic voltammetry (CV) using ascorbic acid (AA) as redox marker, while their surface morphology was characterized by SEM microscopy. The optimal MWCNT-MCM-41 dispersion condition was 0.75 mg mL-1 MWCNTs, 0.25 mg mL-1 MCM-41, and 30 min sonication. Both, electrochemical results and SEM images correlate with a percolation behavior from MWCNT-MCM-41 hybrid. Electrooxidation of AA at GCE modified with the optimal hybrid occurred under diffusion control and exhibited an enhanced current response (65 µA) and a lower overvoltage (-0.005 V) compared to bare GCE (ip = 22 µA, Ep = 0.255 V). The amperometric response of AA at GCE/MWCNT-MCM-41 exhibited remarkable figures of merit, including an ultralow detection limit (1.5 nM), high sensitivity (45.4 × 103 µA M-1), excellent short- and long-term stability, and very good anti-interference ability for AA detection. The analytical applicability of the developed electrochemical sensor was evaluated by sensing AA in several real samples, showing excellent correlation with the values reported by manufacturers in both pharmaceutical and food samples.

Interfacial behaviour and quantitative analysis of hexadecyl phosphocholine drug at a polarized liquid/liquid interface.

The interfacial behaviour of the amphiphilic drug hexadecyl phosphocholine (HePC, also called miltefosine) was analysed by cyclic voltammetry applied at the water/1,2-dichloroethane interface. HePC is the only oral drug currently approved for the treatment of visceral, mucosal  and cutaneous leishmaniasis. Because of its amphiphilic character, it can interact with biological membranes, solubilizing their compounds and leading to cell disruption. These interactions are responsible for its side effects and toxicity; therefore, HePC quantification in biological fluids and pharmaceutical preparations is extremely important. However, the lack of a chromophore in its structure prevents its spectroscopic determination. For this reason, the main challenge of this work was to propose an electroanalytical method for the quantification of this drug, which constitutes a simpler alternative than liquid chromatography-tandem mass spectrometry already reported. With this aim, in the first part of this work, the mechanism of the electrochemical process occurring after polarizing the interface was studied. By varying the experimental conditions, it was possible to determine that in a first step, at open circuit or at low potential values, HePC spontaneously adsorbed to the interface. Later, as the potential increased, the transfer of the anions present in the organic phase towards the aqueous side of the interface, where the HePC polar head groups were present, occurred thus forming adsorbed "ion pairs" and producing an increase in positive current. Subsequently, in the negative sweep, the "ion pairs" dissociated and desorbed giving rise to a negative peak. In this way, both negative and positive currents were considered useful for quantitative purposes. In the second part of this work, an appropriate experimental procedure was designed and proposed as a quantitative methodology for the HePC determination, which consisted of cleaning the interface and controlling the time at open circuit, followed by the voltammetric analysis. A linear response of both, positive or negative, peak currents with drug concentration was obtained within an acceptable range, providing a simple solution for the HePC quantification problem. Future studies will be carried out to evaluate the quantification and selectivity in real matrices containing polymer micelles working as HePC nanocarriers with the aim of avoiding the adverse effects of HePC when it is orally or intravenously administered.

Detection of perfluorooctane sulfonate by ion-transfer stripping voltammetry at an array of microinterfaces between two immiscible electrolyte solutions.

Per- and polyfluoroalkyl substances (PFAS) are a category of persistent environmental contaminants that have been linked to health issues in humans. In this work, we investigate the detection of perfluorooctanesulfonate (PFOS-), one such PFAS, by ion-transfer voltammetry at an array of microinterfaces between two immiscible electrolyte solutions (µITIES). Cyclic voltammetry, differential pulse voltammetry and differential pulse stripping voltammetry (DPSV) indicated the ion-transfer behaviour and detection of PFOS-, with the latter enabling detection at picomolar concentrations. Using a 5 min preconcentration time, during which PFOS- was preconcentrated into the organic phase of the µITIES array, a limit of detection (LOD) of 0.03 nM (0.015 µg L-1) in aqueous electrolyte was achieved. This performance is attributed to the enhanced mass transport (radial diffusion) to the µITIES that occurs during preconcentration. To investigate the potentiality for applications of this analytical approach to environmental samples, measurements in a range of water matrices were investigated. Drinking water, laboratory tap water and seawater matrices were assessed by spiking with PFOS- over the 0.1-1 nM range. A matrix effect was observed, with changes in sensitivity and LOD relative to those in pure aqueous electrolyte solutions. Such matrix effects need to be considered in designing applications of these PFOS- measurements to environmental samples. The results presented here indicate that DPSV at a µITIES array can form the basis for a fast and sensitive screening method for PFOS- contamination that is suited to portable and on-site applications.

Destabilizing effect of perfluorodecanoic acid on simple membrane models.

Perfluoroalkyl acids (PFA) are amphiphilic surfactants widely used in industry with several commercial applications. An important feature of these compounds is their non-biodegradability and their tendency to bio-accumulate in the environment, which has led to these compounds being considered among the most persistent pollutants worldwide. Many studies have provided evidence of their toxic effect on humans and wildlife. For this reason, more and more efforts have been made to better understand the effect of these compounds on living organisms. The aim of the present study is to understand how the electrostatic interactions and film compactness of biological membrane models modulate their interaction with PFA, more specifically with perfluorodecanoic acid (PFD). Langmuir isotherms and Brewster angle microscopy (BAM) are used to evaluate the effect of PFD on lipid membrane models (air/water monolayers and vesicles), analyzing the behavior of PFD : lipid mixtures. The lipids used in this study are distearoyl phosphatidic acid (DSPA), dilauroyl phosphatidic acid (DLPA) and distearoyl phosphatidylethanolamine (DSPE). PFD induces an increase in the mean molecular area per lipid in monolayers, mainly at lower surface pressures. BAM images demonstrate that PFD mixes with DLPA, inducing a decrease in gray level, while it forms a non-miscible mixture with DSPA, segregating PFD domains. Insertion studies of PFD within monolayers and dynamic light scattering experiments demonstrate that PFD can penetrate into monolayers and bilayers above 30 mN m-1, which is the lateral pressure value accepted for a cellular bilayer.