RESUMO
Among healthy vegetables, those of the genus Allium stand out. Antioxidant and anti-inflammatory properties have been associated with these vegetables, attributed mainly to organosulfur compounds (OSCs). In turn, they are linked to a protective effect counteracting cardiovascular disease development. Now, to really ensure the bioactive efficacy of the said compounds once consumed, it is necessary to previously evaluate the ADME (absorption, distribution, metabolism, and excretion) profile. Alternatively, in vitro and in silico methods attempt to avoid or reduce experimental animals' use and provide preliminary information on drugs' ability to overcome the various biological barriers inherent in the ADME process. In this sense, in silico methods serve to provide primary information on drugs' bioavailability mechanisms. High-performance liquid chromatography (HPLC) using a stationary phase composed of phospholipids, the so-called immobilized artificial membrane (IAM), has been widely recognized as a valuable alternative method to extract and quantify information about the structure and physicochemical properties of organic compounds which are extensively used in studies of quantitative structure-activity relationships (QSARs). In the present study, the chromatographic capacity factors (log k' (IAM)) for 28 OSCs were determined by IAM-HPLC. In order to evaluate the ability of the IAM phase in assessing lipophilicity of the compounds under study, several quantitative structure-retention relationships (QSRRs) were derived from exploring fundamental intermolecular interactions that govern the retention of compounds under study on IAM phases. As expected, the hydrophobic factors are of prime importance for the IAM retention of these compounds. However, the molecular flexibility and specific polar interactions expressed by several electronic descriptors (relative negative charge, RNCG, and Mulliken electronegativity) are also involved. We also evaluated the IAM phase ability to assess several ADME parameters for the OSCs under study obtained using the SwissADME web tool integrated into the SwissDrugDesign workspace and the PreADMET web tool. The human gastrointestinal absorption (HIA), blood-brain barrier (BBB) permeation, and skin permeability were investigated through QSAR modeling, using several chemometric approaches. The ADME properties under study are strongly dependent on hydrophobic factors as expressed by log k'(IAM), which provide evidence for the great potential of the IAM phases in the development of QSAR models.
RESUMO
Amongst functional foods, garlic and its by-products stand out given their rich phytochemical profile. A comprehensive analytical approach becomes necessary to fully address garlic preparations health-promoting activities, considering the coexistence of several active ingredients from different chemical families. For this, we developed a multi-phytochemical protocol combining Ultrasound and Dispersive Liquid-Liquid Microextraction, coupled to Liquid Chromatography, for the determination of flavonols, organosulfur compounds, and inulin. Hydrophilic interaction chromatography showed an adequate resolution of flavonols and sugars in a shorter time. The protocol showed a suitable performance and acceptable quantitative yields for garlic powder, cooked garlic, black garlic, and liquid garlic flavouring samples. Additionally, the proposed methodology represented a useful tool to assess how the different garlic products related to functional properties, taking into account the various phytochemical families present in each sample. This is the first time a comprehensive and multi-phytochemical validated analysis of garlic preparations is proposed.
Assuntos
Cromatografia Líquida/métodos , Suplementos Nutricionais/análise , Alho/química , Microextração em Fase Líquida/métodos , Compostos Fitoquímicos/análise , Flavonóis/análise , Análise de Alimentos/métodos , Alimento Funcional/análise , Interações Hidrofóbicas e Hidrofílicas , Inulina/análise , Compostos de Enxofre/análise , UltrassomRESUMO
Organosulphur compounds (OSCs) present in garlic (Allium sativum L.) are responsible of several biological properties. Functional foods researches indicate the importance of quantifying these compounds in food matrices and biological fluids. For this purpose, this paper introduces a novel methodology based on dispersive liquid-liquid microextraction (DLLME) coupled to high performance liquid chromatography with ultraviolet detector (HPLC-UV) for the extraction and determination of organosulphur compounds in different matrices. The target analytes were allicin, (E)- and (Z)-ajoene, 2-vinyl-4H-1,2-dithiin (2-VD), diallyl sulphide (DAS) and diallyl disulphide (DADS). The microextraction technique was optimized using an experimental design, and the analytical performance was evaluated under optimum conditions. The desirability function presented an optimal value for 600µL of chloroform as extraction solvent using acetonitrile as dispersant. The method proved to be reliable, precise and accurate. It was successfully applied to determine OSCs in cooked garlic samples as well as blood plasma and digestive fluids.