Novel bioanalytical strategy using isotope pattern deconvolution and ICP-QMS for the study of iron incorporation in erythrocytes: An insight to better assessment.

Iron is an essential element for human life and its nutritional status in the human body is directly linked to human health. More than 1015 atoms of iron per second are necessary for the maintenance of haemoglobin formation. To predict iron bioavailability three approaches are normally employed: (a) faecal recovery; (b) plasma appearance; and (c) erythrocyte incorporation (the most used). Isotope Pattern Deconvolution (IPD) is a mathematical tool that allows the isolation of distinct isotope signatures from mixtures of natural abundance and enriched tracers. In this work we propose a novel strategy to assess erythrocyte iron incorporation, based on the use of an iron stable isotope (57Fe) and the IPD concept. This strategy allows direct calculation of the exogenous concentration of 57Fe incorporated into RBCs after supplementation. In this way, to determine the mass of iron incorporated into erythrocytes, the unique prediction that must be made is the blood volume, estimate to reproduce the natural dilution of the tracer (57Fe) in the blood. This novel bioanalytical approach was applied for the measurements of iron incorporation and further iron absorption studies in humans, using a group of twelve healthy participants, that should be further evaluated for the assessment of other chemical elements that could be of health concerns and directly impact society.

Development of an electrochemical sensor based on ternary oxide SiO2/Al2O3/SnO2 modified with carbon black for direct determination of clothianidin in environmental and food samples.

This study presents the development of an electrochemical sensor, denoted as GCE/CB/SiAlSn, based on the modification of a glassy carbon electrode surface with the ternary oxide SiO2/Al2O3/SnO2 associated with carbon black, for direct determination of the neonicotinoid pesticide clothianidin in different matrices, such as environmental and food samples. Morphological characterization by the scanning electron microscopy technique, electroanalytical analyses using the cyclic voltammetry technique and differential pulse voltammetry are presented which demonstrated that the developed electrochemical platform presents high sensitivity in the electroanalytical clothianidin determination. The linear range studied was from 2.99 × 10-7 to 6.04 × 10-5 mol L-1, with an LOD of 2.47 nmol L-1. This high sensitivity was explained using the synergistic relationship between carbon black and ternary oxide that maximized the electroactive surface area of the GCE/CB/SiAlSn sensor. Interferent studies were performed that showed high selectivity of the sensor to the pesticide in the presence of Ca2+, K+, Na+, and Mg2+ and carbendazim, glyphosate, imidacloprid and thiamethoxam pesticides. The sensor was applied to real samples of tap water and apple juice obtaining recoveries from 91.0% to 103.0%.

Evaluation of microplastic contamination by metals in a controlled environment: A risk to be considered.

The metal contamination and the degradation of polyethylene terephthalate (PET) due to human activities have contributed to the worsening of environmental problems in aquatic systems. Therefore, the study aimed to evaluate PET microplastic adsorption levels when exposed to high amounts of Ni, Cu and Co. The PET microplastic was characterized by scanning electron microscopy, Brunner-Emmet-Teller, porosimetry system, Barrett-Joyner-Halenda and Fourier transform infrared spectroscopy with attenuated total reflectance for evaluation of surface morphology, surface area, porosity, pore size and functional groups, respectively. The results showed that the surface area, the presence of macro and mesopores, and the functional groups influence the adsorption of metals on the surface of PET microplastic. The adsorption isotherms confirmed the presence of mesoporosity and macroporosity on the PET microplastic surface. The Freundlich and Langmuir models were used to study the adsorption capacity. The kinetics of adsorptions were interpreted using pseudo-first order and pseudo-second order models. The results indicated that the Langmuir isotherm and the pseudo-second order adequately described the adsorption of metals by the PET microplastic. The removal rates by the PET microplastic varied from 8 to 34% for Ni, 5 to 40% for Cu and 7 to 27% for Co after a period of 5 days. Furthermore, the adsorption was predominantly chemical and extremely fast, indicating that the presence of microplastics in the environment can lead to a rapid metal accumulation which elevates the hazards potential of microplastic in living beings.

An electrochemical sensor-based carbon black associated with a modified mixed oxide (SiO2/TiO2/Sb2O5) for direct determination of thiamethoxam in raw honey and water samples.

The study aimed to develop an electrochemical sensor based on glassy carbon, mixed oxide (SiO2/TiO2/Sb2O5), and carbon black. The material was synthesized, characterized, and used to determine thiamethoxam in raw honey and water. The morphologic structure and electrochemical performance of the sensor was characterized by scanning electron microscopy and cyclic voltammetry. Differential pulse voltammetry with a concentration of 0.1 mol L-1 of Britton-Robinson buffer at pH 7.0 allowed the generation of a method to determine thiamethoxam in a linear range of 0.25 to 100.5 µmol L-1 and with a limit of detection of 0.012 µmol L-1. The system efficiently quantified traces of thiamethoxam in raw honey and tap water samples. The modified sensor did not present interferences of K+, Na+, Ca2+, Mg2+, glyphosate, imidacloprid, and carbendazim. In addition, the device showed good recovery values for thiamethoxam when applied directly to honey and water samples without any treatment, presenting an electrochemical sensor to monitor real-time hazardous substances in environmental and food matrices.

Non-enzymatic electrochemical determination of creatinine using a novel screen-printed microcell.

A low-cost and disposable microcell was constructed with a screen-printed electrode for the non-enzymatic electrochemical determination of creatinine. The working electrode was modified with carbon black and maintained in contact with paper-adsorbed iron (III) ions. A small sample volume of 3 µL was required for the device operation. Then, iron (III) ions were complexed in the presence of creatinine in a chemical step, followed by an electrochemical reduction of non-complexed metallic ions in excess. Cyclic voltammetry and differential-pulse voltammetry experiments were employed for the electrochemical characterizations and analytical performance evaluation of the microcell. The working electrode modification with carbon black provided a significant increase of analytical signal. The sensor presented a linear response for creatinine concentrations ranging from 0.10 to 6.5 mmol L-1, with a limit of detection of 0.043 mmol L-1. Experiments for creatinine determination in real samples were successful performed through of standard recovery in urine.

Square-wave adsorptive anodic stripping voltammetric determination of norfloxacin using a glassy carbon electrode modified with carbon black and CdTe quantum dots in a chitosan film.

A glassy carbon electrode was modified with carbon black and CdTe quantum dots in a chitosan film to obtained a sensor for norfloxacin (NOR) in the presence of dopamine, caffeine, and uric acid. The morphological, structural and electrochemical characteristics of the nanostructured material were evaluated using spectrophotometry, X-ray diffraction, transmission electronic microscopy and voltammetry. The high electrochemical activity, fast electron transfer rate and high surface area enhanced the oxidation peak currents and shifted the peak potentials of NOR for more negative values (typically at 0.95 V vs. Ag/AgCl). Electrochemical determination of NOR was carried out using square-wave adsorptive anodic stripping voltammetry (SWAdASV). Response is linear in the 0.2 to 7.4 µmol L-1 NOR concentration range, and the detection limit is as low as 6.6 nmol L-1. The method was successfully applied to the determination of norfloxacin in pharmaceutical formulation, synthetic urine and spiked serum. Graphical abstract Schematic presentation of a voltammetric method using a glassy carbon electrode modified with carbon black and CdTe quantum dots in a chitosan film for the determination of norfloxacin in serum and urine samples.

Graphene nanosheets and quantum dots: a smart material for electrochemical applications.

A novel material for the electrochemical determination of endocrine disruptors using a composite based on graphene oxide modified with cadmium telluride quantum dots has been evaluated. The morphology, structure and electrochemical performance of the composite electrodes were characterised by transmission electron microscopy, dynamic light scattering, UV-visible absorption spectra, fluorescence spectra, Raman spectra and cyclic voltammetry. The dynamic light scattering, transmission electronic microscopy and spectrophotometric measurements all showed good distribution of the quantum dots with a small particle size. The electrochemical measurements demonstrated the high performance of the composite response in the presence of a light source. Differential pulse voltammetry allowed the development of a method to determine 17ß-estradiol levels in the range from 0.2 to 4.0 µmol L(-1) with a detection limit of 2.8 nmol L(-1) (0.76 µg L(-1)).