RESUMO
This study reports a combined approach to assess the antioxidant activity of Zuccagnia-type propolis. Fractions exhibiting the highest antioxidant activities evidenced by DPPH, a ß-carotene bleaching and superoxide radical scavenging activity-non-enzymatic assays, were processed by LC-HRMS/MS to characterize the relevant chemical compounds. A computational protocol based on the DFT calculations was used to rationalize the main outcomes. Among the 28 identified flavonoids, caffeic acids derivatives were in the fraction exhibiting the highest antioxidant activity, with 1-methyl-3-(4'-hydroxyphenyl)-propyl caffeic acid ester and 1-methyl-3-(3',4'-dihydroxyphenyl)-propyl caffeic acid ester as major components. Results clearly showed roles of specific chemical motifs, which can be supported by the computational analysis. This is the first report ascribing the antioxidant ability of Zuccagnia-type propolis to its content in specific caffeic acid derivatives, a potential source of radical scavenging phytochemicals. The proposed protocol can be extended to the study of other plant-products to address the most interesting bioactive compounds.
Assuntos
Antioxidantes , Própole , Espectrometria de Massas em Tandem , Própole/química , Antioxidantes/química , Ácidos Cafeicos/química , Ácidos Cafeicos/análise , Flavonoides/química , Flavonoides/análise , Estrutura Molecular , Cromatografia Líquida/métodos , Cromatografia Líquida de Alta PressãoRESUMO
Noncommunicable diseases (NCDs) are the leading cause of mortality worldwide. Dietary intake of polyphenols may protect against the development of NCDs. Coffee is a rich source of phenolic acids in the Western diet that may prevent or treat hyperlipidemia, type 2 diabetes, chronic liver diseases, and obesity. These health effects are attributed, at least partially, to the antioxidant properties and inhibitory activity of phenolic acids on lipases. However, the effect of milk on these properties is not clear. Thus, we aimed to evaluate the antiradical properties and inhibitory activity on pancreatic lipase in vitro of phenolic acids from coffee. We obtained commercial traditional and decaffeinated espresso coffee capsules and prepared the beverages according to the manufacturer's instructions using a domestic coffee maker. Espresso prepared with traditional and decaffeinated coffee capsules were evaluated with and without the addition of milk following in vitro digestion.The total phenolic content ranged from 168.21 to 397.38 mg equivalent to chlorogenic acid/mL. All coffee-based beverages showed antioxidant activity, with emphasis on decaffeinated and milk-added beverages, respectively. Caffeic acid was the most abundant phenolic compound followed by 5-caffeoylquinic acid before digestion. In contrast after in vitro digestion, only caffeic acid was bioaccessible. The addition of milk improved the bioaccessibility of caffeic acid and caffeine. Overall, the half-maximal inhibitory concentration of the samples for pancreatic lipase varied between 222 and 3035.8 µg/mL. Decaffeinated coffee had a greater inhibitory effect than regular coffee regardless of milk addition. In conclusion, decaffeinated and milk-added coffee beverages have a greater effect on lipase inhibition. This may be related to the greater bioaccessibility of phenolic compounds in these samples. Further studies are needed to elucidate the mechanisms of enzymatic inhibition by phenolic acids.
Assuntos
Café , Diabetes Mellitus Tipo 2 , Animais , Antioxidantes/análise , Antioxidantes/farmacologia , Ácidos Cafeicos/análise , Humanos , Lipase , Leite/química , Fenóis/análiseRESUMO
Abstract Caffeic acid is a phenolic compound widely distributed in plants and beverages such as coffee. Although its mechanism of action is poorly understood, caffeic acid reportedly induces antidepressant-like and neuroprotective effects. This study aimed to investigate the involvement of cellular signaling pathways in acute antidepressant-like effect induced by caffeic acid in mice. All procedures were approved by the Institutional Animal Ethics Committee of the UNIVALI n. 021/2013. Female Swiss mice were administered with vehicle, caffeic acid (5 mg/ kg, p.o.), inhibitor (H-89, U0126, chelerythrine, or PD9859, i.c.v.) or caffeic acid plus inhibitor. The behavioral effects were evaluated 1h after the administration of compounds to mice using tail suspension test (TST) and open field test (OFT). The results showed that the antidepressant- like effect of caffeic acid in mice was possibly mediated by the activation of PKA, MEK 1/2, PKC and MAPK (as assessed using TST), without compromising their locomotor activity (as assessed using OFT). Our results demonstrated, at least in part, the pathways involved in the neuroprotective and behavioral effects of caffeic acid.
Assuntos
Animais , Feminino , Camundongos , Ácidos Cafeicos/análise , Café/efeitos adversos , Fármacos Neuroprotetores/administração & dosagem , Antidepressivos/efeitos adversos , Plantas , Transdução de Sinais , Quinases de Proteína Quinase Ativadas por Mitógeno , Comitês de Cuidado Animal/classificação , Teste de Campo AbertoRESUMO
Coffee beans contain different volatile and non-volatile compounds that are responsible for their flavor and aroma. Herein, principal component analysis (PCA) was employed to correlate the non-volatile composition of specialty and traditional coffees with drink quality. The quantified non-volatile compounds included caffeine, chlorogenic acid, caffeic acid, and nicotinic acid in both types of coffee samples, while 5-hydroxymethylfurfural was only quantified in the specialty coffee samples. The most abundant compounds present in specialty coffees were associated with the aroma and flavor, affording a high drink quality. In traditional coffees, the most abundant compounds included nicotinic acid and caffeine, indicating a stronger roasting process, loss of sensory characteristics, and blended formulations. PCA showed a distinction between the traditional and specialty coffees such that a relationship between the contents of the compounds in each type of coffee, quality, and classification could be established.
Assuntos
Coffea/química , Café/química , Brasil , Ácidos Cafeicos/análise , Cafeína/análise , Cromatografia Líquida de Alta Pressão , Coffea/metabolismo , Niacina/análise , Análise de Componente PrincipalRESUMO
Echinacea purpurea is a traditional medicinal plant widely used as adjuvant for the treatment of respiratory and urinary infections. Caffeic acid derivatives are considered the main active markers, such as chicoric acid, caftaric acid and chlorogenic acid. An analytical method using ultra performance liquid chromatography (UPLC) and diode array detector was developed and validated, to quantify caffeic acid derivatives in commercial dried extracts of EP. UPLC method was developed using a C18 column (50 × 2.1 mm, 1.8 µm), at 30°C. Mobile phase was composed of acetonitrile and 0.05% (v/v) formic acid aqueous solution (10:90), flow rate 0.2 mL/min. Injection volume was 10 µL and detection was performed at 300 and 330 nm. The developed method complied with all required validation parameters, and showed to be linear, precise, accurate, selective and robust for all caffeic acid derivatives. Using the validated method, the levels of caftaric acid (0.110-0.507%w/w), chicoric acid (0.040-0.179%w/w) and chlorogenic acid (0.013-0.084%w/w) were determined in five commercial dried extracts of E. purpurea, with significant variation in the contents between different samples, indicating the need of standardization and control of individual caffeic acid derivatives in commercial extracts.
Assuntos
Ácidos Cafeicos/análise , Cromatografia Líquida de Alta Pressão/métodos , Echinacea/química , Extratos Vegetais/química , Limite de Detecção , Modelos Lineares , Reprodutibilidade dos TestesRESUMO
The effect of micronization of granulometrically fractionated olive pomace (OP) on the bioaccessibility of polyphenols and the antioxidant capacity was investigated during sequential in vitro static digestion. Crude OP was fractionated in a 2-mm sieve (F1: > 2 mm; F2: < 2 mm) and then micronized (300 r min-1, 5 h) generating F1AG (17.8 µm) and F2AG (15.6 µm). Micronization increased the release of hydroxytyrosol, oleuropein, caffeic acid, and decarboxymethyl oleuropein aglycone (3,4-DHPEA-EDA) in the salivary and gastric phase, beyond luteolin in the gastric phase. Micronization also increased the intestinal bioaccessibility of hydroxytyrosol, 3,4-DHPEA-EDA, oleuropein, luteolin, and apigenin; it was more effective for F2AG than F1AG. Micronized samples increased antioxidant capacity in the gastric phase. F2AG exhibited the highest antioxidant capacity in the insoluble intestinal fraction. Thus, micronization can be further exploited to improve the nutraceutical properties of OP by increasing the bioaccessibility and antioxidant capacity of phenolic compounds.
Assuntos
Manipulação de Alimentos/métodos , Olea/química , Polifenóis/análise , Antioxidantes/química , Ácidos Cafeicos/análise , Cromatografia Líquida de Alta Pressão , Suplementos Nutricionais/análise , Digestão , Glucosídeos Iridoides , Iridoides/análise , Olea/metabolismo , Azeite de Oliva/química , Extratos Vegetais/química , Análise de Componente Principal , Espectrometria de Massas em TandemRESUMO
A factorial design with a duplicate in the central point was used to investigate the effect of treating arabica coffee beans with asparaginase. The investigated factors were enzymatic load (1000 and 5000 ASNU/Kg), water percentage (30 and 90%), and hydrolysis time (1 and 3 h). The acrylamide content was determined by UPLC-MS/MS, and the caffeic acid, chlorogenic acid and caffeine concentrations were determined by HPLC-DAD. The statistical analysis was carried out in the R platform using RStudio graphical interface. The results indicated the importance of coffee bean pretreatment with steam, and that the enzyme load reduced the acrylamide content to 65 mg/kg in coffee beans. The predicted reduction was obtained with hydrolysis time of 2 h, water content of 90%, and asparaginase load of 5000 ASNU/kg. The asparaginase treatment did not influence the major bioactive compounds in coffee.
Assuntos
Acrilamida/análise , Asparaginase/metabolismo , Ácidos Cafeicos/análise , Cafeína/análise , Ácido Clorogênico/análise , Café/metabolismo , Ácidos Cafeicos/isolamento & purificação , Cafeína/isolamento & purificação , Ácido Clorogênico/isolamento & purificação , Cromatografia Líquida de Alta Pressão , Café/química , Hidrólise , Extração em Fase Sólida , Espectrometria de Massas em TandemRESUMO
The Commelina erecta L. (C. erecta) also known as erva-de-santa-luzia is reported by local population to have medical properties against some pathological conditions. In this study, two extracts of C. erecta leaves (aqueous and ethanolic) were phytochemically analysed and evaluated for their in-vitro antioxidant activities by DPPH, TBARS, NO assays and cell viability assays. The ultra-high performance liquid chromatography followed by tandem mass spectrometry analysis showed the presence of rutin and caffeic acid in aqueous and ethanolic extract. The total polyphenols in aqueous and ethanolic extracts found were 142.7 ± 3.0 and 123.1 ± 5.8 µg/mL of GAE, respectively. The ethanolic extract (5 mg/mL) inhibits TBARS by 33.8%, and the aqueous extract (5 mg/mL) exhibited scavenger property against nitric oxide derivatives to an extent of 77.8%. In cell culture, both extracts improved cell survivability under H2O2 induced oxidative stress. Thus, C. erecta extract is a good candidate to become a phytotherapic medicine.
Assuntos
Antioxidantes/farmacologia , Ácidos Cafeicos/análise , Cromatografia Líquida de Alta Pressão/métodos , Commelina/química , Extratos Vegetais/farmacologia , Rutina/análise , Animais , Técnicas de Cultura de Células , Humanos , Peróxido de Hidrogênio/farmacocinética , Estresse Oxidativo/efeitos dos fármacos , Fenóis/análise , Compostos Fitoquímicos/análise , Folhas de Planta/química , Polifenóis/análise , Espectrometria de Massas em Tandem/métodosRESUMO
In this work, different chemometric tools were compared to classify n = 26 conventional (CONV) and n = 19 organic (ORG) coffees from the main Brazilian producing regions based on the chemical composition, physicochemical properties, and antioxidant activity. Principal component analysis separated ORG and CONV coffees but the distinction among the producing regions of Brazilian coffee was not possible. Partial least squares discriminant analysis classified all ORG and CONV coffees in the external validation. Similarly, linear discriminant analysis was able to discriminate 100% and 81% of ORG and CONV coffees in the external validation, respectively, in which total phenolic content (TPC), ferric reducing antioxidant activity, and caffeic acid were the main discriminant variables. Overall 100% of samples from Paraná, Minas Gerais, and blended samples were correctly classified, where TPC, flavonoids, inhibition of lipid peroxidation, caffeic acid, pH, and soluble solids were the main discriminant variables. Support vector machines classified 95% ORG and 88% CONV, 100% Coffea arabica, and 88% and 78% coffees produced in São Paulo and Minas Gerais. k-Nearest neighbors was effective in distinguishing 100% CONV, 89% ORG, 100% coffees from São Paulo, and 100% C. arabica coffees. Overall, HPLC data and simple physicochemical parameters allied to chemometrics were effective in authenticating the cultivation system and the botanical origin of Brazilian coffees. PRACTICAL APPLICATION: Coffee adulteration is a serious problem in the food chain as some fraudsters replace coffee powder by other cheaper products. In the case of organic coffee, this scenario is even worse as still there is not a universal method to differentiate conventionally grown coffee from its organic counterpart. In addition, Brazilian coffee is produced in different regions and the commercial value varies. Therefore, we analyzed some physicochemical, chemical, and antioxidant properties of Brazilian coffees from distinct origins and classified the samples using chemometrics. Our approach seems to be interesting for quality control purposes.
Assuntos
Coffea/química , Café/química , Contaminação de Alimentos/análise , Antioxidantes/análise , Antioxidantes/farmacologia , Brasil , Ácidos Cafeicos/análise , Fenômenos Químicos , Análise Discriminante , Flavonoides/análise , Concentração de Íons de Hidrogênio , Análise dos Mínimos Quadrados , Fenóis/análise , Análise de Componente Principal , Sementes/químicaRESUMO
The phenolic-profiling of seven different wheat (Triticum aestivum) genotypes was investigated for the first time during different stages of grain development (milky, softy, physiological maturity and mature). Free and bound phenolic compounds were extracted separately and analyzed by UPLC-QTOF-MSE. Total phenolic content significantly decreased, up to 50% depending on the genotype, towards the maturation of grain. The highest content (free and bound) was observed in the most immature grains, while the lowest level was found in mature grains (408.0 and 165.0 GAE mg/100â¯g, respectively). Globally, 237 phenolic compounds were identified, divided into 5 classes: flavonoids (85), phenolic acids (77), other polyphenols (51), lignans (16) and stilbenes (8). UPLC-MS results showed a progressively decrease of the number of phenolic identification (ID) all along grain development, milky (213), softy (192), physiological maturity (169) and mature (144). The proportion bound to free phenolic progressively increased, reaching the maximum at physiological maturity, indicating a possible enzymatic reactions and complexation during grain growth. Ferulic acid, diphyllin, 4-hydroxybenzoic acid, ferulic acid isomer, apigenin 7-O-apiosyl-glucoside isomer and myricetin isomer were the most abundant compounds. Chemometric tools showed a clear separation between immature and mature grain for all genotypes. Phenolic profile varied significantly among genotypes, this result can help the selection of varieties towards a higher retention of bioactive compounds. Noteworthy, immature wheat grains can be considered a rich source of phenolic compounds and as an attractive ingredient to incorporate to functional foods.