Honeybee Pollen From Southern Chile: Phenolic Profile, Antioxidant Capacity, Bioaccessibility, and Inhibition of DNA Damage.

Honeybee pollen (HBP) chemical composition is highly variable conforming to the floral and geographical origin of the pollen grains. The beneficial effects and functional properties of the HBP are well-known and have been mainly attributed to their high content of antioxidant polyphenols. In this work, twelve HBPs samples from the Southern region of Chile (X Región de Los Lagos) were characterized for the first time according to their botanical origin, phenolic composition, and antioxidant activity. The in vitro gastrointestinal digestion assay was done to simulate the human upper digestive tract. Selected honeybee pollen extracts (HBPEs) were assessed as bioaccessible fractions during an in vitro gastrointestinal digestion. Contents of phenolic compounds, antioxidant capacity, and recovery index of quercetin, myricetin, and cinnamic acid were monitored in different steps of gastrointestinal digestion. Furthermore, the protective effect of in vitro digested HBP towards DNA damage induced by peroxyl radicals was evaluated. The introduced species Brassica rapa L. (Brassicaceae), Lotus pedunculatus Cav. (Fabaceae), and Ulex europaeus L. (Fabaceae) predominated in all the HBPs analyzed, while the native species Buddleja globosa Hope (Scrophulariaceae), Luma apiculata (DC.) Burret (Myrtaceae), Embothrium coccineum J.R. Forst. & G. Forst. (Proteaceae) and Eucryphia cordifolia Cav. (Cunoniaceae) appeared less frequently. The content of polyphenols and antioxidant capacity in HBPEs achieved full bioaccessibility at the end of the intestinal digestion step. However, results obtained by a state-of-the-art technique (i.e. HPLC-DAD) demonstrated relatively low values of bioaccessible quercetin and cinnamic acid after the digestion process. In contrast, myricetin showed a high bioaccessibility in the intestinal digestion steps. The protective effect of in vitro digested HBP towards DNA damage induced by peroxyl radicals showed promising results (up to 91.2% protection). In conclusion, HBPs from the X Region de Los Lagos are rich sources of phenolic antioxidants that protect DNA from strand breakage. Therefore, the potential of HBPEs in preventing gastric and/or intestinal cancer should be further considered.

Chickpeas from a Chilean Region Affected by a Climate-Related Catastrophe: Effects of Water Stress on Grain Yield and Flavonoid Composition.

The Valparaiso region in Chile was decreed a zone affected by catastrophe in 2019 as a consequence of one of the driest seasons of the last 50 years. In this study, three varieties ('Alfa-INIA', 'California-INIA', and one landrace, 'Local Navidad') of kabuli-type chickpea seeds produced in 2018 (control) and 2019 (climate-related catastrophe, hereafter named water stress) were evaluated for their grain yield. Furthermore, the flavonoid profile of both free and esterified phenolic extracts was determined using liquid chromatography-mass spectrometry, and the concentration of the main flavonoid, biochanin A, was determined using liquid chromatography with diode array detection. The grain yield was decreased by up to 25 times in 2019. The concentration of biochanin A was up to 3.2 times higher in samples from the second season (water stress). This study demonstrates that water stress induces biosynthesis of biochanin A. However, positive changes in the biochanin A concentration are overshadowed by negative changes in the grain yield. Therefore, water stress, which may be worsened by climate change in the upcoming years, may jeopardize both the production of chickpeas and the supply of biochanin A, a bioactive compound that can be used to produce dietary supplements and/or nutraceuticals.

LC-MS/MS analysis of neonicotinoid insecticides: Residue findings in chilean honeys / LC-MS/MS análises de inseticidas neonicotinoides: Resíduos encontrados em méis chilenos

ABSTRACT Neonicotinoids are a relatively new generation of insecticides that have been used for control of pests such as aphids, leafhoppers and whiteflies. This paper presents for the first time a determination of residues of four neonicotinoid insecticides (acetamiprid, thiamethoxam, thiacloprid and imidacloprid) in Chilean honey using QuEChERS extraction and UHPLC-MS/MS analysis. The limits of detection and quantification found for all analytes ranging from 0.34 to 1.43 μg kg-1 and from 0.30 to 4.76 μg kg-1, respectively. The extraction using QuEChERS method provided recoveries over 79% and the precision showed coefficient of variation lower than 20%. These data are in agreement with the international criteria that recommend general recovery limits of 70 - 120%. Of the 16 samples analyzed, in three honey samples neonicotinoids pesticides were detected. These three samples were collected from the same geographical area (Rengo). Fruit and grain production characterize the province of Rengo. The analysis of the botanical origin of these honeys showed the absence of pollen grains of crops and the majority presence of pollen grains of weeds such as Medicago sativa, Galega officinalis and Brassica rapa, which could be associated with crops. Although the residue levels found were low, the results also confirm the actual occurrence of a transfer of neonicotinoid insecticides from exposed honeybees into honey.

RESUMO Os neonicotinóides são uma geração relativamente nova de inseticidas que tem sido utilizado para o controle de pragas, como pulgões, cigarrinhas e moscas brancas. Este artigo apresenta pela primeira vez a determinação de resíduos de quatro inseticidas neonicotinóides (acetamiprida, tiametoxam, tiaclopride e imidaclopride) em méis chilenos empregando para extração o método QuEChERS seguido de UHPLC-MS/MS. Foram encontrados limites de detecção e quantificação aceitáveis para todos os analitos variando de 0,34 a 1,43 μg kg-1 e de 0,30 a 4,76 μg kg-1, respectivamente. A extração usando o método QuEChERS proporcionou uma recuperação maior que 79% e a precisão do método não excedeu um coeficiente de variação de 20%. Esses dados estão de acordo com os critérios internacionais que recomendam limites gerais de recuperação de 70 - 120%. Das 16 amostras de mel analisadas foram detectados pesticidas neonicotinoides em três delas. Essas três amostras foram coletadas na mesma área geográfica (Rengo), a qual se caracteriza pela produção de grãos e frutas. A análise da origem botânica desses méis mostrou a ausência de grãos de pólen de espécies cultivadas nesta zona, porém mostrou uma presença majoritária de grãos de pólen de ervas daninhas, como Medicago sativa, Galega officinalis e Brassica rapa, as quais podem estar associadas a estes cultivos. Embora os níveis de resíduos neonicotinoides encontrados neste estudo são baixos, os resultados confirmam a ocorrência atual de uma transferência destes inseticidas ao mel das de abelhas expostas.