Este trabalho apresenta a primeira investigação sobre a estrutura química dos flavonóis presentes em cascas das três variedades de maçãs mais cultivadas no Brasil: Gala, Golden e Fuji. As análises foram feitas por CL/UV/EM (cromatografia líquida de alta eficiência com detector UV com arranjo de diodos acoplada à espectrometria de massas), usando adição pós-coluna de reagentes de deslocamento de UV e também espectrometria de massas de múltiplos estágios (EM n ) com ionização "electrospray" no modo negativo. A identificação "on-line" com base nos dados de CL/UV/EM demonstrou a presença de rutina, hiperosídeo, isoquercitrina, quercitrina e outros três derivados de quercetina-3-O-pentosídeo. As análises por CL/UV/EM também demonstraram que as três variedades de maçã têm perfis cromatográficos semelhantes.This work describes the first detailed investigation into the chemical structures of flavonols present in the three apple varieties most commonly cultivated in Brazil: Gala, Golden and Fuji. The analyses were carried out by LC/UV/MS (high-performance liquid chromatography coupled to diode array UV detection and mass spectrometry), using post-column addition of UV shift reagents, as well as multiple stage mass spectrometry (MS n ) with electrospray ionization in the negative ion mode. Rutin, hyperoside, isoquercitrin, quercitrin, quercetin and three other quercetin-3-pentoside derivatives were identified through the characterization of on-line-based LC/UV/MS data. LC/UV/MS analysis also revealed that the three apple cultivars have similar chromatographic profiles.
Keywords: apple, flavonols, LC/UV/MS, UV shift reagents
IntroductionApple (Malus domestica Borkh., Rosaceae) cultivation stands out as an important and rapidly growing market segment in Brazil. While a few traditional apple varieties have been locally grown, such as Rainha, Soberana and Brazil varieties, other varieties such as Gala, Golden and Fuji have proved superior in terms of growth and productivity, particularly in Brazil's southern and central regions. 1,2 Previous papers have reported on the chemical composition of apple varieties from the USA and from Europe, identifying the main components as esters of caffeic and coumaric acids, procyanidines and flavonols (quercetin glycosylated derivatives). [3][4][5][6][7][8][9][10] In recent years, an increasing number of publications have reported the chemistry of flavonols, especially in view of their biological (antibacterial, antiviral, anti-inflammatory, anti-allergic, anti-trombotic, vasodilatory, anti-mutagenic and neoplastic) properties and their ability to protect against or inhibit the development of cancer when consumed on a regular basis. 11 Notwithstanding the data available from apple samples cultivated in the Northern hemisphere, it must be pointed out that the production of flavonols may vary in response to different environmental conditions. 11 Therefore, the possibility of differences in the chemical composition of flavonols from samples cultivated in the Southern hemisphere cannot be e...