Caffeoylquinic Acids and Flavonoids of Fringed Sagewort (Artemisia frigida Willd.): HPLC-DAD-ESI-QQQ-MS Profile, HPLC-DAD Quantification, in Vitro Digestion Stability, and Antioxidant Capacity
Abstract
:1. Introduction
2. Materials and Methods
2.1. Plant Materials and Chemicals
2.2. Total Extract and Herbal Tea Preparation
2.3. High-Performance Liquid Chromatography with Diode Array Detection and Electrospray Ionization Triple Quadrupole Mass Spectrometric Detection (HPLC-DAD-ESI-QQQ-MS) Profiling Condition
2.4. HPLC-DAD Quantification Condition
2.5. Validation Analysis
2.6. Organoleptic Analysis and Crude Composition Analysis
2.7. General Phytochemical Analysis
2.8. Antioxidant Activity Analysis
2.8.1. DPPH• Radical Scavenging Assay
2.8.2. DPPH•-HPLC-DAD Procedure
2.8.3. Oxygen Radical Absorbance Capacity (ORAC) Assay
2.9. Simulated Gastrointestinal Digestion Assay
2.10. Statistical and Multivariative Analysis
3. Results and Discussion
3.1. Caffeoylquinic Acids and Flavonoids of Artemisia frigida Herb: HPLC-DAD-ESI-QQQ-MS Profile, Organ Distribution and Chemotaxonomy
3.1.1. Caffeoylquinic Acids
3.1.2. Flavonoid Glycosides
3.1.3. Flavonoid Aglycones
3.1.4. Organ Distribution of Caffeoylquinic Acids and Flavonoids in A. frigida Plant
3.1.5. Chemotaxonomic Significance of Flavonoids and Caffeoylquinic Acids in the Subsection Frigidae of Artemisia Genus
3.2. Variation of Phenolics in A. frigida Herb: HPLC Quantification and Principal Component Analysis Data of Twenty One Siberian Populations
3.3. A. frigida Herbal Tea Phenolics: General Characteristics, HPLC Profile, in vitro Digestion Stability and Antioxidant Capacity
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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No | Collection Place | Collection Date | Coordinates | Height (m a.s.l.) | Voucher Specimens No |
---|---|---|---|---|---|
A-01 | Altaiskii Krai, Smolenskii District, Belokurikha | 20.VII.2017 | 51°58′12.5′′N, 84°57′23.5′′E | 448 | BU/AK-As-ar/h-0717-027 |
A-02 | Altaiskii Krai, Novichikhinskii District, Mel’nikovo | 27.VII.2017 | 52°10′47.0′′N, 81°12′34.1′′E | 230 | BU/AK-As-ar/h-0717-032 |
A-03 | Buryatia Republic, Mukhorshibirskii District, Mukhorshibir’ | 21.VII.2018 | 51°01′45.3′′N, 107°47′49.9′′E | 765 | BU/BR-As-ar/h-0718-094 |
A-04 | Buryatia Republic, Zakamenskii District, Tsakir | 19.VII.2016 | 50°24′59.2′′N, 103°34′02.6′′E | 1078 | BU/BR-As-ar/h-0716-041 |
A-05 | Buryatia Republic, Okinskii District, Orlik | 22.VII.2017 | 52°29′35.3′′N, 99°47′08.2′′E | 1857 | BU/BR-As-ar/h-0717-026 |
A-06 | Buryatia Republic, Bauntovskii District, Malovskii | 29.VII.2015 | 54°22′45.1′′N, 113°32′16.3′′E | 950 | BU/BR-As-ar/h-0715-116 |
A-07 | Buryatia Republic, Severobaikal’skii District, Kumora | 31.VII.2017 | 55°52′02.7′′N, 111°10′58.4′′E | 578 | BU/BR-As-ar/h-0717-094 |
A-08 | Chita Oblast, Akshinskii District, Ureisk | 21.VII.2017 | 50°16′59.0′′N, 113°10′42.5′′E | 902 | BU/CO-As-ar/h-0717-012 |
A-09 | Chita Oblast, Alexandrovo Zavodskii District, Klichka | 24.VII.2017 | 50°28′07.9′′N, 118°06′30.0′′E | 1085 | BU/CO-As-ar/h-0717-029 |
A-10 | Irkutsk Oblast, Shelokhovskii District, Olkha | 18.VII.2017 | 52°09′10.4′′N, 104°06′46.2′′E | 490 | BU/IO-As-ar/h-0717-006 |
A-11 | Irkutsk Oblast, Bratskii District, Vikhorevka | 24.VII.2016 | 56°08′32.7′′N, 101°12′32.3′′E | 381 | BU/IO-As-ar/h-0716-011 |
A-12 | Irkutsk Oblast, Katangskii District, Erbogachen | 28.VII.2016 | 61°15′50.3′′N 108°00′50.5′′E | 301 | BU/IO-As-ar/h-0716-027 |
A-13 | Krasnoyarskii Krai, Berezovskii District, Lopatino | 17.VII.2015 | 55°56′39.1′′N, 93°17′33.1′′E | 375 | BU/KK-As-ar/h-0715-006 |
A-14 | Krasnoyarskii Krai, Turukhanskii District, Kellog | 22.VII.2015 | 62°26′38.5′′N, 86°18′16.1′′E | 77 | BU/KK-As-ar/h-0715-014 |
A-15 | Tyva Republic, Kaa-Khemskii District, Saryg-Sep | 25.VII.2018 | 51°28′48.5′′N, 95°29′26.5′′E | 778 | BU/TR-As-ar/h-0718-012 |
A-16 | Tyva Republic, Barun-Khemchikskii District, Ak-Dovurak | 27.VII.2018 | 51°08′28.0′′N, 90°37′38.1′′E | 853 | BU/TR-As-ar/h-0718-018 |
A-17 | Yakutia (Sakha) Republic, Mirninskii Ulus, Almaznyi | 25.VII.2017 | 62°28′01.9′′N, 113°50′58.1′′E | 388 | BU/YR-As-ar/h-0717-063 |
A-18 | Yakutia (Sakha) Republic, Oimyakonskii Ulus, Ust’-Nera | 30.VII.2017 | 64°31′50.4′′N, 142°59′42.1′′E | 506 | BU/YR-As-ar/h-0717-085 |
A-19 | Yakutia (Sakha) Republic, Verkhekolymskii Ulus, Ugol’noye | 1.VIII.2017 | 65°43′40.7′′N, 149°45′19.4′′E | 134 | BU/YR-As-ar/h-0817-106 |
A-20 | Yakutia (Sakha) Republic, Srednekolymskii Ulus, Sylgy-Ytar | 21.VII.2018 | 67°50′00.4′′N, 154°48′01.6′′E | 31 | BU/YR-As-ar/h-0718-064 |
A-21 | Yakutia (Sakha) Republic, Nizhnekolymskii Ulus, Tymkino | 27.VII.2018 | 68°28′46.8′′N, 160°07′56.7′′E | 9 | BU/YR-As-ar/h-0718-072 |
No | tR, min | Compound | UV, λmax, nm | CE, eV | ESI-MS/MS, m/z | Ref. | |
---|---|---|---|---|---|---|---|
(M–H) − | MS/MS Fragment Ions | ||||||
1 | 1.285 | 1-O-Caffeoylquinic acid a | 327 | 30 | 353 | (353): 191, 179, 135 | [42] |
2 | 1.376 | 4-O-Caffeoylquinic acid a | 327 | 30 | 353 | (353): 191, 179, 135 | [42] |
3 | 1.485 | Friginoside B (Tent.) b | 270, 352 | 15 | 695 | (695): 519, 343; [343]: 329, 301 | [15] |
4 | 1.614 | 5-O-Caffeoylquinic acid a | 327 | 30 | 353 | (353): 191, 179, 135 | [42] |
5 | 1.627 | 3-O-Caffeoylquinic acid a | 327 | 30 | 353 | (353): 191, 179, 135 | [42] |
6 | 1.687 | 1,3-Di-O-caffeoylquinic acid a | 328 | 35 | 515 | (515): 353, 335, 191, 179 | [42] |
7 | 1.742 | Vicenin-2 (Api-6,8-di-C-Glc) a | 255, 329 | 30 | 593 | (593): 503, 473, 413; (473): 383, 353 | [43] |
8 | 1.871 | Isoorientin (Lut-6-C-Glc) a | 255, 267, 348 | 25 | 447 | (447): 357, 327 | [44] |
9 | 1.886 | Isoschaftoside (Api-6-C-Ara-8-C-Glc) a | 273, 329 | 30 | 563 | (563): 503, 473, 443, 413, 383, 353; (353): 325, 297 | [44] |
10 | 1.897 | Orientin (Lut-8-C-Glc) a | 255, 267, 348 | 25 | 447 | (447): 357, 327 | [44] |
11 | 1.938 | Schaftoside (Api-6-C-Glc-8-C-Ara) a | 273, 329 | 30 | 563 | (563): 503, 473, 443, 413, 383, 353; (353): 325, 297 | [44] |
12 | 1.942 | Chrysoeriol-O-Ac-Hex b | 269, 336 | 15 | 503 | (503): 461, 299 | [43] |
13 | 2.043 | Vitexin (Api-8-C-Glc) a | 272, 330 | 25 | 431 | (431): 341, 311 | [44] |
14 | 2.063 | Apigenin-C-Hex-O-Hex b | 273, 329 | 30 | 593 | (593): 431, 341, 311 | [44] |
15 | 1.121 | Isovitexin (Api-6-C-Glc) a | 272, 330 | 20 | 431 | (431): 341, 311 | [44] |
16 | 1.124 | 6-Hydroxyluteolin-7-O-Glc a | 251, 280, 345 | 10 | 463 | (463): 301 | [22] |
17 | 1.129 | Cynaroside (Lut-7-O-Glc) a | 256, 265, 347 | 10 | 447 | (447): 285 | [44] |
18 | 1.132 | Nepitrin (Nep-7-O-Glc) a | 271, 345 | 20 | 477 | (477): 315, 301 | [22] |
19 | 2.188 | 3,4-Di-O-caffeoylquinic acid a | 328 | 40 | 515 | (515): 353, 335, 191 | [42] |
20 | 2.210 | Diosmetin-7-O-Glc a | 251, 268, 345 | 15 | 461 | (461): 299, 285 | [22] |
21 | 2.251 | 3,5-Di-O-caffeoylquinic acid a | 327 | 40 | 515 | (515): 353, 191, 179, 135 | [42] |
22 | 2.312 | Thermopsoside (Chr-7-O-Glc) a | 253, 267, 346 | 15 | 461 | (461): 299, 285 | [44] |
23 | 3.316 | Rhaunoside F (Nep-3′-O-Glc) a | 268, 339 | 10 | 477 | (477): 315, 301 | [22] |
24 | 2.372 | 4,5-Di-O-caffeoylquinic acid a | 328 | 40 | 515 | (515): 353, 179 | [42] |
25 | 2.378 | 6-Hydroxyluteolin-dimethyl ether-O-Hex b | 253, 267, 343 | 25 | 491 | (491): 329, 301 | [22] |
26 | 2.380 | 1,5-Di-O-caffeoylquinic acid a | 328 | 35 | 515 | (515): 353, 191, 179, 135 | [42] |
27 | 2.437 | Luteolin-4′-O-Glc a | 267, 337 | 10 | 447 | (447): 285 | [44] |
28 | 2.497 | Chrysoeriol-O-Ac-Hex b | 269, 336 | 15 | 503 | (503): 461, 299 | [43] |
29 | 2.504 | Apigenin-7-O-glucoside (cosmosiin) a | 265, 334 | 10 | 431 | (431): 269 | [44] |
30 | 2.562 | 6-Hydroxyluteolin-3′-O-Glc (Tent.) b | 275, 339 | 10 | 463 | (463): 301 | [22] |
31 | 2.626 | 1,3,5-Tri-O-caffeoylquinic acid a | 326 | 45 | 677 | (677): 515, 353; (515): 353, 191, 179, 135 | [42] |
32 | 2.688 | 1,4,5-Tri-O-caffeoylquinic acid a | 326 | 45 | 677 | (677): 515, 353; (515): 353, 191, 179 | [42] |
33 | 2.714 | Chrysoeriol-4′-O-Glc a | 268, 337 | 15 | 461 | (461): 299, 285 | [44] |
34 | 2.718 | Nepetin-4′-O-Glc a | 268, 341 | 25 | 477 | (477): 315, 301 | [22] |
35 | 2.722 | 6-Hydroxyluteolin-dimethyl ether-O-Hex b | 253, 267, 344 | 25 | 491 | (491): 329, 301 | [22] |
36 | 2.756 | 3,4,5-Tri-O-caffeoylquinic acid a | 326 | 48 | 677 | (677): 515; (515): 353, 179 | [42] |
37 | 2.810 | Chrysoeriol-O-Ac-Hex b | 269, 336 | 15 | 503 | (503): 461, 299 | [43] |
38 | 2.819 | Rhaunoside C (6-hydroxyluteolin-4′-O-Glc) a | 286, 335 | 10 | 463 | (463): 301 | [22] |
39 | 2.875 | Chrysoeriol-5-O-Glc (Tent.) b | 261, 343 | 15 | 461 | (461): 299, 285 | [45] |
40 | 2.934 | 6-Hydroxyluteolin-dimethyl ether-O-Hex b | 252, 267, 342 | 25 | 491 | (491): 329, 301 | [22] |
41 | 3.120 | Tricin a | 270, 345 | 35 | 329 | (329): 315, 301 | [44] |
42 | 3.236 | Apigenin a | 267, 334 | 10 | 269 | [44] | |
43 | 3.251 | Hispidulin a | 273, 333 | 10 | 299 | (299): 285 | [44] |
44 | 3.259 | 5,7,3′-Trihydroxy-6,4′,5′-trimethoxyflavone b | 273, 331 | 35 | 359 | (359): 345, 331, 317 | [12] |
45 | 3.312 | Jaceosidine a | 273, 343 | 35 | 329 | (329): 315, 301 | [44] |
46 | 3.375 | 5,7,3′,4′,5′-Pentahydroxy-6,8-dimethoxyflavone b | 269, 370 | 40 | 361 | (361): 347, 333 | [17] |
47 | 3.482 | Chrysoeriol a | 252, 272, 345 | 35 | 299 | (299): 285 | [44] |
48 | 3.562 | 5,7,4′-Trihydroxy-6,3′,5′-trimethoxyflavone b | 272, 347 | 35 | 359 | (359): 345, 331, 317 | [12] |
49 | 3.621 | Desmethylcentaureidin b | 252, 273, 346 | 35 | 329 | (329): 315, 301 | [44] |
50 | 3.638 | Luteolin-3′,4′-dimethyl ether a | 251, 271, 342 | 40 | 313 | (313): 299, 285 | [44] |
51 | 3.752 | Eupatorin a | 252, 275, 343 | 40 | 343 | (343): 329, 315, 301 | [44] |
52 | 3.812 | 5,7,3′,4′-Tetrahydroxy-6,5′-dimethoxyflavone b | 272, 350 | 40 | 345 | (345): 331, 317 | [13] |
53 | 3.879 | Quercetagetin-3,6,3′,4′-tetramethyl ether b | 256, 272, 344 | 40 | 373 | (373): 359, 345, 331 | [44] |
54 | 3.894 | Acacetin a | 270, 327 | 20 | 283 | (283): 269 | [44] |
55 | 4.062 | Cirsimaritin a | 274, 332 | 35 | 313 | (313): 299, 285 | [44] |
56 | 4.124 | Cirsilineol a | 273, 345 | 35 | 343 | (343): 329, 315, 301 | [44] |
57 | 4.187 | Velutin a | 251, 344 | 35 | 313 | (313): 299, 285 | [44] |
58 | 4.251 | Pilloin b | 251, 275, 340 | 35 | 313 | (313): 299, 285 | [44] |
59 | 4.782 | Genkwanin a | 268, 335 | 20 | 283 | (283): 269 | [44] |
Compounds | A. frigida Herbal Tea, mg/100 mL | ||
---|---|---|---|
Non-Treated | After Gastric Phase | After Intestinal Phase | |
Caffeoylquinic acids | |||
4-O-Caffeoylquinic acid | 0.45 ± 0.01 | 0.44 ± 0.01 | 0.39 ± 0.01 |
5-O-Caffeoylquinic acid | 16.09 ± 0.45 | 15.12 ± 0.42 | 12.98 ± 0.33 |
3,4-Di-O-caffeoylquinic acid | 0.82 ± 0.02 | 0.76 ± 0.02 | 0.57 ± 0.02 |
3,5-Di-O-caffeoylquinic acid | 16.35 ± 0.43 | 14.02 ± 0.35 | 8.46 ± 0.22 |
4,5-Di-O-caffeoylquinic acid | 2.87 ± 0.08 | 2.33 ± 0.06 | 1.29 ± 0.03 |
3,4,5-Tri-O-caffeoylquinic acid | tr. | tr. | tr. |
Subtotal caffeoylquinic acids | 36.58 | 32.67 | 23.69 |
Flavonoid glycosides | |||
Vicenin-2 | 1.34 ± 0.04 | 1.32 ± 0.04 | 1.31 ± 0.03 |
Isoorientin | 2.41 ± 0.06 | 2.37 ± 0.06 | 2.04 ± 0.06 |
Cynaroside | tr. | tr. | tr. |
Subtotal flavonoid glycosides | 3.75 | 3.69 | 3.35 |
Flavonoid aglycones | |||
Apigenin | n.d. | n.d. | n.d. |
Hispidulin | n.d. | n.d. | n.d. |
Jaceosidine | tr. | tr. | tr. |
Luteolin-3′,4′-dimethyl ether | n.d. | n.d. | n.d. |
Eupatorin | n.d. | n.d. | n.d. |
Acacetin | n.d. | n.d. | n.d. |
Cirsimaritin | tr. | tr. | tr. |
Subtotal flavonoid aglycones | tr. | tr. | tr. |
Total flavonoids | 3.75 | 3.69 | 3.35 |
Total phenolics | 40.33 | 36.36 | 27.04 |
© 2019 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).
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Olennikov, D.N.; Kashchenko, N.I.; Chirikova, N.K.; Vasil’eva, A.G.; Gadimli, A.I.; Isaev, J.I.; Vennos, C. Caffeoylquinic Acids and Flavonoids of Fringed Sagewort (Artemisia frigida Willd.): HPLC-DAD-ESI-QQQ-MS Profile, HPLC-DAD Quantification, in Vitro Digestion Stability, and Antioxidant Capacity. Antioxidants 2019, 8, 307. https://doi.org/10.3390/antiox8080307
Olennikov DN, Kashchenko NI, Chirikova NK, Vasil’eva AG, Gadimli AI, Isaev JI, Vennos C. Caffeoylquinic Acids and Flavonoids of Fringed Sagewort (Artemisia frigida Willd.): HPLC-DAD-ESI-QQQ-MS Profile, HPLC-DAD Quantification, in Vitro Digestion Stability, and Antioxidant Capacity. Antioxidants. 2019; 8(8):307. https://doi.org/10.3390/antiox8080307
Chicago/Turabian StyleOlennikov, Daniil N., Nina I. Kashchenko, Nadezhda K. Chirikova, Aina G. Vasil’eva, Aydan I. Gadimli, Javanshir I. Isaev, and Cecile Vennos. 2019. "Caffeoylquinic Acids and Flavonoids of Fringed Sagewort (Artemisia frigida Willd.): HPLC-DAD-ESI-QQQ-MS Profile, HPLC-DAD Quantification, in Vitro Digestion Stability, and Antioxidant Capacity" Antioxidants 8, no. 8: 307. https://doi.org/10.3390/antiox8080307