Profile and Characterization of the Chlorogenic Acids in Green Robusta Coffee Beans by LC-MSⁿ: Identification of Seven New Classes of Compounds

Abstract

LC-MS(n) (n = 2-4) has been used to detect and characterize in green Robusta coffee beans 15 quantitatively minor sinapic acid and trimethoxycinnamoylquinic acid-containing chlorogenic acids, all reported for the first time from this source, with 13 of them not previously reported in nature. These comprise 3-sinapoylquinic acid, 4-sinapoylquinic acid, and 5-sinapoylquinic acid (M(r) 398); 3-sinapoyl-5-caffeoylquinic acid, 3-sinapoyl-4-caffeoylquinic acid, and 4-sinapoyl-3-caffeoylquinic acid (M(r) 560); 3-(3,5-dihydroxy-4-methoxy)cinnamoyl-4-feruloylquinic acid (M(r) 560); 3-sinapoyl-5-feruloylquinic acid, 3-feruloyl-4-sinapoylquinic acid, and 4-sinapoyl-5-feruloylquinic acid (M(r) 574); 4-trimethoxycinnamoyl-5-caffeoylquinic acid, 3-trimethoxycinnamoyl-5-caffeoylquinic acid (M(r) 574); and 5-feruloyl-3-trimethoxycinnamoylquinic acid, 3-trimethoxycinnamoyl-4-feruloylquinic acid, and 4-trimethoxycinnamoyl-5-feruloylquinic acid (M(r) 588). Furthermore, a series of structures including nine new triacyl quinic acids have been assigned on the basis of LC-MS(n) patterns of fragmentation, relative hydrophobicity, and analogy of fragmentation patterns if compared to feruloyl, caffeoyl, and dimethoxycinnamoyl quinic acids. Sixty-nine chlorogenic acids have now been characterized in green Robusta coffee beans.

How to identify and discriminate between the methyl quinates of chlorogenic acids by liquid chromatography–tandem mass spectrometry

“…[4,6,7,27,28] This paper reports the development and application of LC-MS n methods to the CGAs methyl esters.…”

Differential responses of Oryza sativa secondary metabolism to biotic interactions with cooperative, commensal and phytopathogenic bacteria

“…However, the relative intensities of 7 HCA derivatives (especially feruloylhexose n°7, and feruloylquinic acid n°6 0 in Nipponbare) decreased. Feruloylquinic acid is an ester of quinic and ferulic acid (Jaiswal et al 2010), and feruloyl hexose, a glycosylated form of ferulic acid. Being a precursor of lignin biosynthesis, ferulic acid confers rigidity to cell walls by cross-linking cell wall polysaccharides and lignin (Bennett and Wallsgrove 1994).…”

Impact of coffee components on inflammatory markers: A review

“…Green coffee beans contain 69 different chlorogenic acids and only a handful of them have been fully explored (Jaiswal, Patras, Eravuchira, & Kuhnert, 2010). CGAs have been shown to be readily absorbed by humans (Farah, Monteiro, Donangelo, & Lafay, 2008).…”