Use of carbon black based electrode as sensor for solid-state electrochemical studies and voltammetric determination of solid residues of lead.

For the first time carbon black based electrode modified with paraffin was applied as a sensor on voltammetry of immobilized microparticles (VIMP) approach for determination of lead solid residues in hair dye samples. The solid microparticles of Pb(II) (Pb(CH3COO)2(s)) immobilized into the carbon paste sensor containing carbon black and paraffin were firstly reduced at initial potentials and further reoxidized at around -0.60 V during anodic scan. Electroanalytical parameters as well as supporting electrolyte composition, and pH were also evaluated. An analytical curve in 0.2 mol L-1 phosphate buffer solution (pH 5.0) from 0.04 to 3.2 µg (R2 = 0.999) with detection and quantification limits of 4 and 13 ng, respectively, were achieved. The method was applied to quantify lead solid residues in hair dye samples without previous mineralization or complex sample pre-treatment. Besides adequate repeatability, stability and selectivity of the developed sensor based on VIMP features, the method using carbon black based sensor was considered advantageous comparing to the results recorded by a spectrometric method (relative error lower than 8%) from several analytical viewpoints.

Ready-to-use 3D-printed electrochemical cell for in situ voltammetry of immobilized microparticles and Raman spectroscopy.

We report in this communication a ready-to-use fused deposition modeling (FDM) based 3D-printed spectroelectrochemical cell to perform for the first time voltammetry of immobilized microparticles (VIMP) and Raman spectroscopy in situ using acrylonitrile butadiene styrene (ABS) as the filament material for printing. The 3D-printed cell was applied to evaluate solid state electrochemical behavior of tadalafil as a proof-of-concept. Several advantages were achieved in the use of the developed device, such as less manipulation of the working electrode, monitoring the same region of the solid microparticles before and after electrochemical measurements, better control of the laser incidence, low-cost and low-time production. Furthermore, the device was printed in a single-step, without handling to assembly and it has an estimated material cost of approximately 2 $. The use of 3D-printing technology was significantly important to integrate Raman spectroscopic method with VIMP measurements and to support mechanism elucidation and characterization of the compounds with less manipulation of the working electrode, avoiding loss of solid products formed from electrochemical reactions.

A new approach to ion exchange chromatography with conductivity detection for adulterants investigation in dietary supplements.

The extent of adulteration of dietary supplements has significantly increased in recent years. This situation worries health authorities and requires auxiliary analytical tools for the investigation of illegal substances purposely added. Ion exchange chromatography with conductivity detection is a consolidated analytical technique for the determination of inorganic compounds in various matrices. This technique has been applied to the pharmaceutical characterization of mainly impurities and degradation products. This work presents a new approach to ion exchange chromatography as a screening method to investigate the presence of amfepramone, femproporex, sibutramine, bisacodyl and amiloride in dietary supplements advertised for weight loss. The method was optimized and validated using a Metrosep C4 100/4.0 cation exchange column. The mobile phase consisted of 1.8 mm HNO3 containing 2% acetonitrile (v/v), with a flow rate of 0.9 ml min-1 , and nonsuppressed conductivity detection was applied. The limits of detection and quantification varied from 1.01 to 3.62 mg L-1 and from 1.48 to 8.72 mg L-1 , respectively. The proposed method was successful applied to 78 solid dietary supplement samples, in two of which adulterations were found. Moreover, ion exchange chromatography with conductivity detection could be easily used for quality control without prior complex sample pre-treatment.

A liquid chromatography-atmospheric pressure photoionization tandem mass spectrometric method for the determination of organosulfur compounds in petroleum asphalt cements.

We present a sensitive liquid chromatography-atmospheric pressure photoionization tandem mass spectrometric (UHPLC-APPI-MS/MS) method for the determination of selected organosulfur compounds in Brazilian asphalt cements. It was possible to detect 14 organosulfur compounds of different classes where sulfoxides and sulfones presented higher sensibility in ionization than thiophenes and aromatic sulfides. A dopant-assisted APPI method was also tested, however, when chromatographic flow rate was optimized a decrease in signal was observed for all compounds. PAHs were tested and ruled out as possible interfering compounds and the matrix effect of asphalt cements was within an acceptable range for the quantification of organosulfur compounds. The proposed method was found to have satisfactory linearity and accuracy with recoveries between 83.85 and 110.28% for thianaphthene and 3-methylbenzothiophene, respectively. Therefore, the method allowed the characterization of organosulfur compounds in Brazilian asphalt cements and demonstrated changes in the amount quantified in asphaltenic and maltenic fractions after the RTFOT+SUNTEST aging process.

Supercritical CO2 extraction, chemical characterisation and antioxidant potential of Brassica oleracea var capitata against HO·, O2(·-) and ROO·.

In this work were extracted bioactive compounds from Brassica oleracea var capitata using supercritical CO2 and evaluated the antioxidant potential of the extracts. Five extractions were accomplished to investigate the influence of pressure (10-25 MPa) and temperature (20-60 °C) in the extraction yield, chemical composition and antioxidant potential towards peroxyl, superoxide and hydroxyl radicals. The highest extraction yield was obtained at 60 °C and 25 MPa, which was 0.47 wt% (run 2). In the characterisation of the extracts obtained was possible the identification of sulforaphane and iberin nitrile that present known biological properties. The extracts of all runs presented antioxidant activities towards the three radicals, but the highest activities for all radicals were using the extracts obtained in the run 2. The use of supercritical CO2 extraction to obtain bioactive compounds of B. oleracea var capitata showed to be a promising alternative to conventional extraction methods, since allowed the extraction of compounds with scientific and industrial interest.