Carbon Fiber Paper Sensor for Determination of Trimethoprim Antibiotic in Fish Samples.

The increase in anthropogenic pollution raises serious concerns regarding contamination of water bodies and aquatic species with potential implications on human health. Pharmaceutical compounds are a type of contaminants of emerging concern that are increasingly consumed and, thus, being frequently found in the aquatic environment. In this sense, an electrochemical sensor based on an unmodified and untreated carbon fiber paper (CPS-carbon paper sensor) was simply employed for the analysis of trimethoprim antibiotic in fish samples. First, the analytical conditions were thoroughly optimized in order for the CPS to achieve maximum performance in trimethoprim determination. Therefore, an electrolyte (0.1 M Britton-Robinson buffer) pH of 7 was selected and for square wave voltammetry parameters, optimum values of amplitude, frequency and step potential corresponded to 0.02 V, 50 Hz, and 0.015 V, respectively, whereas the deposition of analyte occurred at +0.7 V for 60 s. In these optimum conditions, the obtained liner range (0.05 to 2 µM), sensitivity (48.8 µA µM-1 cm-2), and LOD (0.065 µM) competes favorably with the commonly used GCE-based sensors or BDD electrodes that employ nanostructuration or are more expensive. The CPS was then applied for trimethoprim determination in fish samples after employing a solid phase extraction procedure based on QuEChERS salts, resulting in recoveries of 105.9 ± 1.8% by the standard addition method.

Mineral Content of Various Portuguese Breads: Characterization, Dietary Intake, and Discriminant Analysis.

The chemical composition and daily mineral intake (DMI) of six macro (calcium, magnesium, sodium, potassium, phosphorous, and chloride) and four microminerals (copper, iron, manganese, and zinc) were determined in four types of Portuguese breads (white wheat, maize, wheat/maize, and maize/rye breads). Samples were processed with microwave assisted digestion and mineral composition was determined with a high-resolution continuum-source atomic absorption spectrometer with flame and graphite furnace. Bread contributes to an equilibrated diet since it is rich in several minerals (0.21 mg/100 g of copper in wheat bread to 537 mg/100 g of sodium in maize/rye bread). Maize/rye bread presented the highest content of all minerals (except phosphorous and chloride), while the lowest levels were mainly found in wheat bread. Median sodium concentrations (422-537 mg/100 g) represented more than 28% of the recommended daily allowance, being in close range of the maximum Portuguese limit (550 mg/100 g). Maize/rye bread exhibited the highest DMI of manganese (181%), sodium (36%), magnesium (32%), copper (32%), zinc (24%), iron (22%), potassium (20%), and calcium (3.0%). A Principal Component Analysis (PCA) model based on the mineral content allowed the differentiation among white wheat, maize, and maize/rye bread. Zinc, magnesium, manganese, iron, phosphorus, potassium, copper, and calcium proved to be good chemical markers to differentiate bread compositions.

The simpler the better: Highly sensitive 17α-ethinylestradiol sensor based on an unmodified carbon paper transducer.

The remarkable features of a carbon fiber paper sensor (CP) were employed for detection of the estrogenic hormone 17α-ethinylestradiol (EE2), considered a contaminant of emerging concern due to its potential ecotoxicity and widespread in the aquatic ecosystems. In this work, an unpreceded CP pre-treatment study was conducted with the (Il)-hexacyanoferrate(III) ion pair, however a bare sensor without pre-treatment revealed higher efficiency on the oxidation of EE2 compared to a chemical and electrochemical pre-treated CP and a gold nanoparticles modified CP, being thus selected for EE2 determinations. The analytical conditions were thoroughly optimized in terms of electrolyte pH (pH 7), differential pulse voltammetry parameters (modulation time 0.003 s, amplitude 0.09 V, interval time 0.1 s and step potential 0.01 V), and analyte preconcentration potential (0.4 V) and time (180 s). The hormone can be determined by the CP in a wide linear range from 0.1 to 1000 nM, achieving a detection limit of 0.14 ± 0.005 nM and an outstanding sensitivity of 1636 ± 232 µA µM-1 cm-2 in the lowest linear zone (0.1-1 nM). The sensor was validated in river water and fish reaching good recoveries (91.2 ± 4.6 to 109.0 ± 7.1%), reproducibility and repeatability. Moreover, the sensor showed high selectivity to EE2 in the presence of several potential interfering compounds and frequently prescribed drugs, though it could not discriminate the similar hormone, 17ß-estradiol, being the total concentration obtained in this case. CP-based sensors emerge as efficient electroanalytical tools, suggesting that modification of the surface may not always be beneficial in terms of sensitivity.

Laccase bioconjugate and multi-walled carbon nanotubes-based biosensor for bisphenol A analysis.

Bisphenol A (BPA) is an endocrine disruptor compound that has been detected in aquatic ecosystems. In this work, the development of an electrochemical biosensor for BPA determination based on laccase from Trametes versicolor is reported. A bioconjugate was optimized to maximize the biosensor electrocatalytic activity and stability, which for the first time involved the synergistic effect of this specific enzyme (6.8 UmL-1), chitosan (5 mgmL-1) and the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate in an optimum 5:5:2 (v/v/v) proportion. This bioconjugate was deposited onto a screen-printed carbon electrode previously modified with multi-walled carbon nanotubes (MWCNTs). Nanostructuration with MWCNTs enlarged the electrocatalytic activity and surface area, thus improving the biosensor performance. The BPA electrochemical reaction follows an EC mechanism at the optimum pH value of 5.0. Linearity up to 12 µM, a sensitivity of (6.59 ± 0.04) × 10-2 µAµM-1 and a detection limit of 8.4 ± 0.3 nM were obtained coupled with high reproducibility (relative standard deviations lower than 6%) and stability (87% of the initial response after one month). The developed biosensor was employed to the analysis of BPA in river water displaying appropriate accuracy (94.6-97.9%) and repeatability (3.1 to 6% relative standard deviations) proving its high potential applicability for in situ environmental analysis.

(Bio)Sensing Strategies Based on Ionic Liquid-Functionalized Carbon Nanocomposites for Pharmaceuticals: Towards Greener Electrochemical Tools.

The interaction of carbon-based nanomaterials and ionic liquids (ILs) has been thoroughly exploited for diverse electroanalytical solutions since the first report in 2003. This combination, either through covalent or non-covalent functionalization, takes advantage of the unique characteristics inherent to each material, resulting in synergistic effects that are conferred to the electrochemical (bio)sensing system. From one side, carbon nanomaterials offer miniaturization capacity with enhanced electron transfer rates at a reduced cost, whereas from the other side, ILs contribute as ecological dispersing media for the nanostructures, improving conductivity and biocompatibility. The present review focuses on the use of this interesting type of nanocomposites for the development of (bio)sensors specifically for pharmaceutical detection, with emphasis on the analytical (bio)sensing features. The literature search displayed the conjugation of more than 20 different ILs and several carbon nanomaterials (MWCNT, SWCNT, graphene, carbon nanofibers, fullerene, and carbon quantum dots, among others) that were applied for a large set (about 60) of pharmaceutical compounds. This great variability causes a straightforward comparison between sensors to be a challenging task. Undoubtedly, electrochemical sensors based on the conjugation of carbon nanomaterials with ILs can potentially be established as sustainable analytical tools and viable alternatives to more traditional methods, especially concerning in situ environmental analysis.

Carbon paper as a promising sensing material: Characterization and electroanalysis of ketoprofen in wastewater and fish.

In the present work, the exceptional electrochemical properties of carbon paper were characterized and explored in the development of a sensor for the anti-inflammatory drug, ketoprofen. An initial electrochemical characterization of the carbon paper with a redox indicator revealed much higher voltammetric peaks in comparison with other carbon-based electrodes, namely, screen-printed carbon electrode, boron-doped diamond electrode, glassy carbon electrode, pyrolytic graphite electrode, and pencil graphite electrode, predicting a good sensing performance. Ketoprofen showed a pronounced cathodic peak around -1.1 V vs Ag/AgCl (KCl, 3 M) at pH 5 in Britton-Robinson buffer, presenting a diffusion-controlled process. An optimized differential pulse voltammetry procedure was employed for ketoprofen determination achieving a limit of detection of 0.11 ± 0.01 µM, a linearity up to 6.02 µM, and a high sensitivity of 24 ± 4 or 35 ± 3 µA µM-1 cm-2 (depending on the calibration range: 0.088-1.96 µM or 1.96-6.02 µM, respectively) with acceptable (6-15% relative standard deviation) reproducibility and repeatability considering the challenging conditions of its detection in aqueous solutions. The sensor revealed to be highly selective in the presence of common interferents and other widely consumed anti-inflammatory drugs. Moreover, the developed sensor reached good accuracy in wastewater and fish samples with recoveries varying from 82.3 ± 4.4 to 88.6 ± 4.5%.

Nanostructured pencil graphite electrodes for application as high power biocathodes in miniaturized biofuel cells and bio-batteries.

This work describes a simple method for the fabrication of an enzymatic electrode with high sensitivity to oxygen and good performance when applied as biocathode. Pencil graphite electrodes (PGE) were chosen as disposable transducers given their availability and good electrochemical response. After electrochemical characterization regarding hardness and surface pre-treatment suited modification with carbon-based nanostructures, namely with reduced graphene, MWCNT and carbon black for optimal performance was proceeded. The bioelectrode was finally assembled through immobilization of bilirubin oxidase (BOx) lashed on the modified surface of MWCNT via π-π stacking and amide bond functionalization. The high sensitivity towards dissolved oxygen of 648 ± 51 µA mM-1 cm-2, and a LOD of 1.7 µM, was achieved for the PGE with surface previously modified with reduced graphene (rGO), almost the double registered for direct anchorage on the bare PGE surface. Polarization curves resulted in an open circuit potential (OCP) of 1.68 V (vs Zn electrode) and generated a maximum current density of about 650 µA cm-2 in O2 saturated solution.

Application of Nanostructured Carbon-Based Electrochemical (Bio)Sensors for Screening of Emerging Pharmaceutical Pollutants in Waters and Aquatic Species: A Review.

Pharmaceuticals, as a contaminant of emergent concern, are being released uncontrollably into the environment potentially causing hazardous effects to aquatic ecosystems and consequently to human health. In the absence of well-established monitoring programs, one can only imagine the full extent of this problem and so there is an urgent need for the development of extremely sensitive, portable, and low-cost devices to perform analysis. Carbon-based nanomaterials are the most used nanostructures in (bio)sensors construction attributed to their facile and well-characterized production methods, commercial availability, reduced cost, high chemical stability, and low toxicity. However, most importantly, their relatively good conductivity enabling appropriate electron transfer rates-as well as their high surface area yielding attachment and extraordinary loading capacity for biomolecules-have been relevant and desirable features, justifying the key role that they have been playing, and will continue to play, in electrochemical (bio)sensor development. The present review outlines the contribution of carbon nanomaterials (carbon nanotubes, graphene, fullerene, carbon nanofibers, carbon black, carbon nanopowder, biochar nanoparticles, and graphite oxide), used alone or combined with other (nano)materials, to the field of environmental (bio)sensing, and more specifically, to pharmaceutical pollutants analysis in waters and aquatic species. The main trends of this field of research are also addressed.

Commercial octopus species from different geographical origins: Levels of polycyclic aromatic hydrocarbons and potential health risks for consumers.

Polycyclic aromatic hydrocarbons (PAHs) are persistent pollutants that have been raising global concern due to their carcinogenic and mutagenic properties. A total of 18 PAHs (16 USEPA priority compounds, benzo(j)fluoranthene and dibenzo(a,l)pyrene) were assessed in the edible tissues of raw octopus (Octopus vulgaris, Octopus maya, and Eledone cirrhosa) from six geographical origins available to Portuguese consumers. Inter- and intra-species comparison was statistically performed. The concentrations of total PAHs (∑PAHs) ranged between 8.59 and 12.8 µg/kg w.w. Octopus vulgaris caught in northwest Atlantic Ocean presented ΣPAHs significantly higher than those captured in Pacific Ocean and Mediterranean Sea, as well as than the other characterized species from western central and northeast Atlantic Ocean. PAHs with 2-3 rings were the predominant compounds (86-92% of ∑PAHs) but diagnostic ratios indicated the existence of pyrogenic sources in addition to petrogenic sources. Known and possible/probable carcinogenic compounds represented 11-21% of ΣPAHs. World and Portuguese per capita ingestion of ∑PAHs due to cephalopods consumption varied between 1.62-2.55 × 10-4 and 7.09-11.2 × 10-4 µg/kg body weight per day, respectively. Potential risks estimated for low and high consumers according to USEPA methodology suggested that a regular consumption of raw octopus does not pose public health risks.

Biosensing based on pencil graphite electrodes.

Pencil leads have been increasingly used as electrode material in electrochemical applications. Commonly denominated as pencil graphite electrodes (PGE), they represent a viable alternative to other standard electrodes due to their comparable electrical properties but mainly for their low cost and availability, enabling disposable applications. In order to achieve the best analytical performance literature evidences the type of lead (hardness level) and electrode surface pre-treatment are critical to the envisaged application. The present review describes the use of PGE in biosensing analysis, more specifically those sensors comprising immobilized enzymes but also briefly referring nucleic acids and other biological entities. It lays an emphasis in the immobilization process of the biological entities while focusing in the analytical performance of each biosensor, mainly sensitivity, linear range and limit of detection as comparative criteria. This review also addresses the main characteristics and properties of PGEs as transducer material in the electrochemical field.

Octopus lipid and vitamin E composition: interspecies, interorigin, and nutritional variability.

Octopus vulgaris, Octopus maya, and Eledone cirrhosa from distinct marine environments [Northeast Atlantic (NEA), Northwest Atlantic (NWA), Eastern Central Atlantic, Western Central Atlantic (WCA), Pacific Ocean, and Mediterranean Sea] were characterized regarding their lipid and vitamin E composition. These species are those commercially more relevant worldwide. Significant interspecies and interorigin differences were observed. Unsaturated fatty acids account for more than 65% of total fatty acids, mostly ω-3 PUFA due to docosahexaenoic (18.4-29.3%) and eicosapentanoic acid (11.4-23.9%) contributions. The highest ω-3 PUFA amounts and ω-3/ω-6 ratios were quantified in the heaviest specimens, O. vulgaris from NWA, with high market price, and simultaneously in the lowest graded samples, E. cirrhosa from NEA, of reduced dimensions. Although having the highest cholesterol contents, E. cirrhosa from NEA and O. maya from WCA have also higher protective fatty acid indexes. Chemometric discrimination allowed clustering the selected species and several origins based on lipid and vitamin E profiles.