Mariana Araújo

Sensitive bi-enzymatic biosensor based on polyphenoloxidases–gold nanoparticles–chitosan hybrid film–graphene doped carbon paste electrode for carbamates detection

A bi-enzymatic biosensor (LACC-TYR-AuNPs-CS/GPE) for carbamates was prepared in a single step by electrodeposition of a hybrid film onto a graphene doped carbon paste electrode (GPE). Graphene and the gold nanoparticles (AuNPs) were morphologically characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, dynamic light scattering and laser Doppler velocimetry. The electrodeposited hybrid film was composed of laccase (LACC), tyrosinase (TYR) and AuNPs entrapped in a chitosan (CS) polymeric matrix. Experimental parameters, namely graphene redox state, AuNPs:CS ratio, enzymes concentration, pH and inhibition time were evaluated. LACC-TYR-AuNPs-CS/GPE exhibited an improved Michaelis-Menten kinetic constant (26.9±0.5M) when compared with LACC-AuNPs-CS/GPE (37.8±0.2M) and TYR-AuNPs-CS/GPE (52.3±0.4M). Using 4-aminophenol as substrate at pH5.5, the device presented wide linear ranges, low detection limits (1.68×10(-9)±1.18×10(-10)-2.15×10(-7)±3.41×10(-9)M), high accuracy, sensitivity (1.13×10(6)±8.11×10(4)-2.19×10(8)±2.51×10(7)%inhibitionM(-1)), repeatability (1.2-5.8% RSD), reproducibility (3.2-6.5% RSD) and stability (ca. twenty days) to determine carbaryl, formetanate hydrochloride, propoxur and ziram in citrus fruits based on their inhibitory capacity on the polyphenoloxidases activity. Recoveries at two fortified levels ranged from 93.8±0.3% (lemon) to 97.8±0.3% (orange). Glucose, citric acid and ascorbic acid do not interfere significantly in the electroanalysis. The proposed electroanalytical procedure can be a promising tool for food safety control.

Laccase-Prussian blue film-graphene doped carbon paste modified electrode for carbamate pesticides quantification.

A novel enzymatic biosensor for carbamate pesticides detection was developed through the direct immobilization of Trametes versicolor laccase on graphene doped carbon paste electrode functionalized with Prussian blue films (LACC/PB/GPE). Graphene was prepared by graphite sonication-assisted exfoliation and characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. The Prussian blue film electrodeposited onto graphene doped carbon paste electrode allowed considerable reduction of the charge transfer resistance and of the capacitance of the device. The combined effects of pH, enzyme concentration and incubation time on biosensor response were optimized using a 2(3) full-factorial statistical design and response surface methodology. Based on the inhibition of laccase activity and using 4-aminophenol as redox mediator at pH 5.0, LACC/PB/GPE exhibited suitable characteristics in terms of sensitivity, intra- and inter-day repeatability (1.8-3.8% RSD), reproducibility (4.1 and 6.3% RSD), selectivity (13.2% bias at the higher interference:substrate ratios tested), accuracy and stability (ca. twenty days) for quantification of five carbamates widely applied on tomato and potato crops. The attained detection limits ranged between 5.2×10(-9)molL(-1) (0.002mgkg(-1) w/w for ziram) and 1.0×10(-7)molL(-1) (0.022mgkg(-1) w/w for carbofuran). Recovery values for the two tested spiking levels ranged from 90.2±0.1 (carbofuran) to 101.1±0.3% (ziram) for tomato and from 91.0±0.1% (formetanate) to 100.8±0.1% (ziram) for potato samples. The proposed methodology is appropriate to enable testing pesticide levels in food samples to fit with regulations and food inspections.

High-Performance Electrochromic Devices Based on Poly[Ni(salen)]-Type Polymer Films

We report the application of two poly[Ni(salen)]-type electroactive polymer films as new electrochromic materials. The two films, poly[Ni(3-Mesalen)] (poly[1]) and poly[Ni(3-MesaltMe)] (poly[2]), were successfully electrodeposited onto ITO/PET flexible substrates, and their voltammetric characterization revealed that poly[1] showed similar redox profiles in LiClO4/CH3CN and LiClO4/propylene carbonate (PC), while poly[2] showed solvent-dependent electrochemical responses. Both films showed multielectrochromic behavior, exhibiting yellow, green, and russet colors according to their oxidation state, and promising electrochromic properties with high electrochemical stability in LiClO4/PC supporting electrolyte. In particular, poly[1] exhibited a very good electrochemical stability, changing color between yellow and green (λ = 750 nm) during 9000 redox cycles, with a charge loss of 34.3%, an optical contrast of ΔT = 26.2%, and an optical density of ΔOD = 0.49, with a coloration efficiency of η = 75.55 cm(2) C(-1). On the other hand, poly[2] showed good optical contrast for the color change from green to russet (ΔT = 58.5%), although with moderate electrochemical stability. Finally, poly[1] was used to fabricate a solid-state electrochromic device using lateral configuration with two figures of merit: a simple shape (typology 1) and a butterfly shape (typology 2); typology 1 showed the best performance with optical contrast ΔT = 88.7% (at λ = 750 nm), coloration efficiency η = 130.4 cm(2) C(-1), and charge loss of 37.0% upon 3000 redox cycles.

Effect of Bactrocera oleae on phenolic compounds and antioxidant and antibacterial activities of two Algerian olive cultivars

Bactrocera oleae, an olive fruit fly, is a major olive pest in Algeria. In this study, olives of two Algerian cultivars (Limli and Rougette de Métidja) with different degrees of infestation by the Bactrocera oleae fly (0%, not attacked; 100%, all attacked; and real %) were analysed. The influence of this pest on individual phenolic compounds (HPLC-DAD-FLD) and antioxidant profiles was ascertained. The antibacterial activity against 8 human enteropathogenic bacteria was also assessed. The results show that Rougette de Métidja, the cultivar with higher drupe size, was attacked to a greater degree than Limli, and the B. oleae attack caused a significant decrease in the total phenolic contents (>50%), including oleuropein, verbascoside, luteolin-7-O-glucoside, tyrosol and hydroxytyrosol. The antioxidant and antibacterial activities were highly correlated with the phenolic levels. Extracts from healthy olives were more effective against bacteria than those obtained from attacked olives. Globally, olive fly affected significantly the phenolic compounds of olives and their biological properties.