Greener production of a starch-based nanohybrid material (core-shell) for the simultaneous extraction of persistent organic pollutants in shrimp samples.

Here, a novel nanohybrid material (Ag@CD@ANS) based on oat starch was produced, characterized, and applied to extract persistent organic pollutants in a shrimp sample. By the characterization experiments, Ag@CD@ANS was successfully synthesized. The functionalization of the material by 1,2-naphthoquinone-4-sulphonic acid (ANS) was confirmed using the infrared technique and CHN elemental analysis. The isotherm study showed that the material has a high adsorption capacity for the pesticides of interest (flutriafol, atrazine, heptachlor, DDT and bifenthrin) allowing their extraction from shrimp samples. The optimal condition for extraction was obtained using multivariate analysis. The nature of the elution solvent (hexane, methanol, acetonitrile) and the mass ratio between sample:adsorbent (1:1; 1:5 and 1:10) were the evaluated factors for extraction using Ag@CD@ANS and commercial adsorbents (neutral alumina, octadecyl, silica gel). From the multivariate analysis, it was observed that the optimal condition for pesticide extraction using Ag@CD@ANS was reached, using a 1:5 ratio (sample:adsorbent) and acetonitrile (10 mL) as elution solvent. For the commercial adsorbents, the optimal condition for pesticide extraction was reached, using a 1:3 ratio (sample:adsorbent), acetonitrile (10 mL) and neutral alumina as commercial adsorbent. Ag@CD@ANS efficiency was compared with an optimal commercial adsorbent (neutral alumina). No significant difference (p < 0.05) between neutral alumina and Ag@CD@ANS was observed. Recoveries ranging from 75 to 105 % with coefficients of variation ≤ 15 % (n = 3) were obtained using neutral alumina while using Ag@CD@ANS, recoveries ranging from 73 to 102 %, with coefficient of variation ≤ 13 % (n = 3) were obtained for the target pesticides. Limits of detection ranging from 0.5 to 1.0 µg Kg-1 and limits of quantification ranging from 1.6 to 3.3 µg Kg-1 were reached. The results demonstrated that Ag@CD@ANS can alternatively be used as a support for the extraction of persistent organic pollutants, having the advantage of being reusable for up to three cycles.

Eugenol diffusion coefficient and its potential to control Sitophilus zeamais in rice.

Given the insecticidal potential of eugenol as a fumigant, this work aimed to determine the diffusion coefficient of eugenol emanating from a pure standard solution (99%), as well as from clove essential oil (Eugenia caryophillata Thunb. (Myrtaceae)) through rice grain; to chemically analyse the volatile composition of commercially available eugenol and clove essential oil; and to evaluate the mortality of Sitophilus zeamais Motschulsky (Coleoptera: curculionidae) after exposure to eugenol inside a test chamber filled with rice. The solid phase microextraction method of extracting and quantifying eugenol by gas chromatography presented a good analytical response for the quantification of the analyte. There was no significant difference between the diffusion coefficient of eugenol diffusing from pure eugenol or from clove essential oil. The diffusion coefficient of eugenol through rice with the conditions herein adopted is 1.09 × 10-3 cm2 s-1. The characterization of clove essential oil confirmed the presence of eugenol as its major component (74.25%). A difference was observed in the composition of the distinct phases evaluated. The exposure of adult S. zeamais to diffused eugenol from pure eugenol over seven days resulted in significantly higher mortality rates (~37%) than eugenol diffused from clove essential oil (~11%). No differences in mortality rates were observed in individuals placed at different positions inside the test chamber during eugenol fumigation.