The prevention of chronic and degenerative diseases, is a health concern deeply associated with oxidative stress. Such progressive phenomena can be avoided through exogenous antioxidant intake, which set up a reductant cascade, mopping up damaging free radicals. Medicinal herbs are commonly associated with high antioxidant potential, and hence their health benefits. The commerce of dried herbal extracts movements a big portion of developing countries economy. The determination of medicinal herbs the antioxidant activity capacity is of utmost importance. The assessment of antioxidant activity in phytotherapics is mostly achieved by spectrophotometric assays, however colored substances can produce interferences that do not occur in electroanalytical methods. Therefore, the aim of this paper is to compare spectrophotometric and voltammetric techniques to evaluate antioxidant activity in herbal drugs such as: Ginkgo biloba L., Camellia sinensis (L.) Kuntze, Theaceae; Hypericum perforatum L., Hypericaceae; Aesculus hippocastanum L., Sapindaceae; Rosmarinus officinalis L., Lamiaceae; Morinda citrifolia L., Rubiaceae; Centella asiatica (L.) Urb., Apiaceae; Trifolium pratense L., Fabaceae; Crataegus oxyacantha L., Rosaceae; and Vaccinium macrocarpon Aiton, Ericaceae. The spectrophotometric methods employed were DPPH (2,2-diphenyl-1-picrylhydrazyl), ABTS (2,2′-azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) and the Folin-Ciocalteu assays. The electroanalytical method used was voltammetry and it was developed a phenoloxidase based biosensor. The redox behavior observed for each herbal sample resulted in distinguishable voltammetric profiles. The highest electrochemical indexes were found to G. biloba and H. perforatum, corroborating to traditional spectrophotometric methods. Thus, the electroanalysis of herbal drugs, may be a promising tool for antioxidant potential assessment.
Paper Spray Ionization (PSI) and Leaf Spray (LS) are two new sources of ambient ionization mass spectrometry. In PSI, the sample is deposited on a triangular paper and ions are generated by applying a high voltage on a moistened paper with an organic protic solvent. The LS technique is a variant of PSI, where the paper is now substituted by the matrix itself to be studied, a triangular leaf. Both methods allow rapid and inexpensive analyses compared to traditional API techniques. In this work, both sources were applied to identify and quantify agrochemicals which are widely used in fruits and vegetables. The analytical performance of PS and LS techniques was evaluated from the construction of calibration curves in the positive ionization mode (PSI(+) and LS(+)) using atrazine, diuron and methomyl agrochemicals in arugula, basil, cabbage, lettuce and kale vegetable samples. The concentration ranged from 10 to 1000 ppb. Atrazine and diuron were used as internal standards, not requiring the use of deuterated standards. Both analytical methods demonstrated similar performance for the three agrochemicals with R2 > 0.99, and values of LOD and LOQ ranging from 1.23 to 25.00 and 4.12 to 83.33 ppb for PSI(+)-MS and from 0.03 to 36.00 and 0.11–120.00 ppb for LS(+)-MS. In almost all cases, these values were lower than the established MRLs (Maximum Residue Limits), which are 250 ppb for atrazine and 100 ppb for diuron and methomyl.
Microcystin-leucine arginine (MC-LR) is the most abundant and toxic secondary metabolite produced by freshwater cyanobacteria. This toxin has a high potential hazard health due to potential interactions with liver, kidney and the nervous system. The aim of this work was the design of a simple and environmentally friendly electrochemical system based on highly efficient nanostructured electrodes for the removal of MC-LR in tap water. Titania nanoparticles were deposited on carbon (graphite) under a simple and efficient microwave assisted approach for the design of the electrode, further utilized in the electrochemical remediation assays. Parameters including the applied voltage, time of removal and pH (natural tap water or alkaline condition) were investigated in the process, with results pointing to a high removal efficiency for MC-LR (60% in tap water and 90% in alkaline media experiments, under optimized conditions).