Determination of the hydroxycinnamate profile of 12 members of the Asteraceae family

• Published in: Phytochemistry (Oxford) 2011-06, Vol.72 (8), p.781-790
• Main Authors: Jaiswal, Rakesh, Kiprotich, Joseph, Kuhnert, Nikolai
• Format: Article
• Language: English
• Subjects: Achillea millefolium; Arnica montana; Asteraceae; Asteraceae - chemistry; Caffeoylquinic acids; Caffeoyltartaric acid; Caffeoyl–feruloyltartaric acid; Centaurea benedicta; Chicoric acid; chlorogenic acid; Chlorogenic Acid - chemistry; Chlorogenic acids; Cichorium intybus; Cinnamates - analysis; Cynara cardunculus; Echinops; Feruloylquinic acids; Inula helenium; Lactuca sativa; Mass Spectrometry; Molecular Structure; p-Coumaroylquinic acids; p-Coumaroyl–caffeoylquinic acid; Petasites hybridus; Quinic Acid - analogs & derivatives; Quinic Acid - analysis; Quinic Acid - chemistry; Quinic Acid - isolation & purification; Solidago virgaurea; Stereoisomerism; Tanacetum parthenium; Tandem MS
• ISSN: 0031-9422; 1873-3700
• DOI: 10.1016/j.phytochem.2011.02.027

For the first time 1- p-coumaroyl-5-caffeoylquinic acid ( 30) and 1- p-coumaroyl-3-caffeoylquinic acid ( 33) are reported in nature and their regiochemistry is assigned by tandem mass spectrometry. [Display omitted] ► Chlorogenic acids and hydroxycinnamates based on cis and trans-cinnamic acids have identical MS n spectra. ► Chlorogenic acid regioisomers were easily distinguish by their characteristic tandem mass spectra. ► First time 1- p-coumaroyl-3-caffeoylquinic acid and 1- p-coumaroyl-3-caffeoylquinic acid were identified in nature. The hydroxycinnamates of the leaves of 12 plants of the Astreraceae family, Achillea millefolium, Arnica montana, Artemesia dracunculus, Cichorium intybus, Cnicus benedictus, Cynara scolymus, Echinops humilis, Inula helenium, Lactuca sativa, Petasites hybridus, Solidago virgaurea, and Tanacetum parthenium were investigated qualitatively by LC–MS n . Thirty-nine chlorogenic acids were detected and all characterized to regioisomeric level on the basis of their fragmentation pattern in the tandem MS spectra, most of them for the first time from these sources with two of them previously not reported in nature. Both chlorogenic acids based on trans and cis-cinnamic acid substituents were identified. Assignment to the level of individual regioisomers was possible for seven caffeoylquinic acids ( 1–7), 11 dicaffeoylquinic acids ( 17–27), six feruloylquinic acids ( 9–14), two p-coumaroylquinic acids ( 15–16), two caffeoyl–feruloylquinic acids ( 28 and 29), four caffeoyl- p-coumaroylquinic acids ( 30– 33), three dicaffeoyl–succinoylquinic acids ( 34– 36), two dicaffeoyl–methoxyoxaloylquinic acids ( 37 and 38), and one tricaffeoylquinic acid ( 39). Furthermore, one caffeoylshikimic acid ( 40), one caffeoyltartaric acid ( 41), three dicaffeoyltartaric acids ( 42– 44), and three caffeoyl–feruloyltartaric acids ( 45– 47) were detected and shown to possess characteristic tandem MS spectra and were tentatively assigned on the basis of their retention time and previously developed hierarchical keys.