Grain Germination Changes the Profile of Phenolic Compounds and Benzoxazinoids in Wheat: A Study on Hard and Soft Cultivars.

Pre-harvest sprouting is a frequent problem for wheat culture that can be simulated by laboratory-based germination. Despite reducing baking properties, wheat sprouting has been shown to increase the bioavailability of some nutrients. It was investigated whether wheat cultivars bearing distinct grain texture characteristics (BRS Guaraim, soft vs. BRS Marcante, hard texture) would have different behavior in terms of the changes in phytochemical compounds during germination. Using LC-Q-TOF-MS, higher contents of benzoxazinoids and flavonoids were found in the hard cultivar than in the soft one. Free phytochemicals, mainly benzoxazinoids, increased during germination in both cultivars. Before germination, soft and hard cultivars had a similar profile of matrix-bound phytochemicals, but during germination, these compounds have been shown to decrease only in the hard-texture cultivar, due to decreased levels of phenolic acids (trans-ferulic acid) and flavonoids (apigenin) that were bound to the cell wall through ester-type bonds. These findings confirm the hypothesis that hard and soft wheat cultivars have distinct behavior during germination concerning the changes in phytochemical compounds, namely the matrix-bound compounds. In addition, germination has been shown to remarkably increase the content of benzoxazinoids and the antioxidant capacity, which could bring a health-beneficial appeal for pre-harvested sprouted grains.

Feasibility of Applying Untargeted Metabolomics with GC-Orbitrap-HRMS and Chemometrics for Authentication of Black Pepper (Piper nigrum L.) and Identification of Geographical and Processing Markers.

Black pepper is one of the most consumed spices all over the world. Due to its high demand and nutritional value, a metabolomics approach based on GC-Orbitrap-HRMS fingerprinting and chemometrics was applied to assess its geographical traceability and processing authenticity. GC-HRMS-based fingerprints were obtained using a simple ultrasound-assisted extraction method, which may be easily implemented in routine activities of quality control. Unsupervised methods, such as principal component analysis (PCA), were performed for sample overview according to the investigated origins (Brazil, Vietnam, and Sri Lanka) and processing (sterilized vs nonsterilized samples). Further orthogonal partial least squares discriminant analysis (OPLS-DA) models were validated by cross- and external validation, providing satisfactory performance for geographical and processing authentication, as well as excellent predictive ability for further samples. Furthermore, reliable putative identification of 12 key metabolites (markers) was performed, highlighting the feasibility of combining untargeted GC-HRMS analysis with chemometrics for quality control of black pepper.

Comparison of several extraction procedures for the determination of biopesticides in soil samples by ultrahigh pressure LC-MS/MS.

A new procedure has been proposed for the determination of biopesticides (nicotine, sabadine, veratridine, rotenone, azadirachtin, cevadine, deguelin, spynosad D, and pyrethrins) and piperonyl butoxide in agricultural soils. Several extraction procedures such as solid-liquid extraction using mechanical shaking, sonication, pressurized liquid extraction, and modified QuEChERS (quick, easy, cheap, effective, rugged, and safe) have been tested, obtaining better results when QuEChERS procedure without further cleanup steps was applied. The determination of the compounds was carried out by ultra high pressure liquid chromatography coupled to tandem mass spectrometry, using methanol and aqueous solution of ammonium formate 5 mM as mobile phase. The method was validated for all compounds at concentrations ranging from 10 to 100 µg/kg and recoveries ranged from 68 to 116%, except for nicotine and sabadine, with recoveries lower than 50%. Precision was estimated through intra- and inter-day studies, obtaining intra-day precision lower than 20% for most of the compounds, and inter-day precision was lower than 25%. Limits of detection and quantification were also estimated, obtaining limits of quantification equal or lower than 10 µg/kg. Finally, the method was applied to the analysis of 20 real agricultural soil samples and no biopesticide residues were found over the limit of quantification.