High resolution LC-MS/MS screening for secondary metabolites in bulgarian species of genus <i>Astragalus L</i>

Shkondrov, Aleksandar M.; Krasteva, Ilina N.

doi:10.21577/0100-4042.20170730

Acessibilidade / Reportar erro

Brasil

Español English

sumário « anterior atual seguinte »

Sumário

Artigo • Quím. Nova 44 (6) • June 2021 • https://doi.org/10.21577/0100-4042.20170730 copy

High resolution LC-MS/MS screening for secondary metabolites in bulgarian species of genus Astragalus L

Authorship SCIMAGO INSTITUTIONS RANKINGS

The phytochemical content of some Astragalus species distributed in Bulgarian flora has been previously studied. Among other compounds, flavoalkaloids, acylated flavonoids, flavonoid triglycosides and cycloartane saponins have been isolated so far. The composition of the rest of the representatives of this genus in Bulgaria is not explored yet. The aim of this study was to perform a screening for the presence of selected rare secondary metabolites (flavoalkaloids, acylated flavonoids, flavonoid triglycosides and cycloartane saponins) in selected Astragalus species. Samples were collected in different phenological stages and from different locations in the country. A novel and rapid ultra-high performance liquid chromatography – high resolution electrospray ionisation mass spectrometry (UHPLC-HRESIMS) method was developed and applied. For the first time a flavoalkaloid glycoside was determined from extracts of A. onobrychis var. chlorocarpus and A. glycyphylloides. From A. depressus an acylated derivative of kaempferol was newly identified. The flavonol triglycosides camelliaside A, alcesefoliside and mauritianin were proved in samples of A. glycyphylloides, A. onobrychis var. chlorocarpus and A. cicer for the first time as well.

Keywords:
Astragalus species; flavoalkaloids; flavonoids; saponins; qualitative analysis; UHPLC-HRESIMS

Sample No.	Overground parts of	Year	Locality; coordinates	Voucher specimen	Phenological stage
1	A. cicer	2013	Sofia; 42º41'52''N, 23º19'19''E	SO 102681	flowering
2	A. cicer	2016	Sofia; 42º41'52''N, 23º19'19''E	SOM 1394	fructification
3	A. depressus	2015	Erma; 42º48'45''N, 22º34'52''E	SOM 1402	flowering
4	A. glycyphylloides	2018	Vitosha; 42º33'36''N, 23º16'48''E	SO 093817	flowering
5	A. glycyphyllos	2019	Rila; 42º7'40''N, 23º7'56''E	SO 107612	flowering
6	A. glycyphyllos	2012	Vitosha; 42º33'36''N, 23º16'48''E	SO 107613	flowering
7	A. monspessulanus subsp. monspessulanus	2016	Devin; 41º43'41''N, 24º26'59''E	SOM 1391	fructification
8	A. monspessulanus subsp. monspessulanus	2016	Slavianka; 41º33'57''N, 24º44'41''E	SOM 1392	flowering
9	A. monspessulanus subsp. illyricus	2015	Erma; 42º48'45''N, 22º34'52''E	SO 107532	flowering
10	A. onobrychis var. chlorocarpus	2013	Stara Zagora; 42º23'37''N, 25º38'46''E	SO 107538	flowering
11	A. onobrychis var. chlorocarpus	2016	Golo Bardo; 42º35' 17''N, 23º3'2''E	SOM 1393	flowering
12	A. onobrychis var. chlorocarpus	2016	Vitosha; 42º33'36''N, 23º16'48''E	SOM 1390	flowering
13	A. ponticus	2013	Pleven; 43º24'32''N, 24º37'4''E	SO 107539	flowering

Standard substance (abbreviation)	Rt ± SD, min	Exact mass; molecular formula	ESI (+) Precursor ion; MS² (relative abundance in %)*	ESI (-) Precursor ion; MS² (relative abundance in %)*	LOD ± SD, ng/mL
N-(8-methylquercetin-3-O-[α-L-rhamnopyranosyl-(1→2)-[α-L-rhamnopyranosyl-(1→6)]-β-D-galactopyranosyl])-3-hydroxypiperidin-2-one (QueFA)	2.47 ± 0.015	883.2695; C₃₉H₄₉NO₂₂	884.2809 C₃₉H₅₀NO₂₂⁺; 771.2345 C₃₄H₄₃O₂₀⁺ (28), 625.1763 C₂₈H₃₃O₁₆⁺ (3), 479.1189 C₂₂H₂₃O₁₂⁺ (12), 317.0728 C₁₆H₁₃O₇⁺ (100)	882.2692 C₃₉H₄₈NO₂₂^-; 769.2191 C₃₄H₄₁O₂₀^- (21), 623.1612 C₂₈H₃₁O₁₆^- (8), 477.1033 C₂₂H₂₁O₁₂^- (10), 315.0505 C₁₆H₁₁O₇^- (100)	0.18 ± 0.01
N-(8-methylkaempferol-3-O-[α-L-rhamnopyranosyl-(1→2)-[α-L-rhamnopyranosyl-(1→6)]-β-D-galactopyranosyl])-3-hydroxypiperidin-2-one (KaeFA)	3.00 ± 0.010	867.2747; C₃₉H₄₉NO₂₁	868.2857 C₃₉H₅₀NO₂₁⁺; 755.2399 C₃₄H₄₃O₁₉⁺ (11), 609.1820 C₂₈H₃₃O₁₅⁺ (6), 463.1075 C₂₂H₂₃O₁₁⁺ (44), 301.0711 C₁₆H₁₃O₆⁺ (100)	901.2642 C₃₉H₄₈NO₂₁Cl^-; 866.2718 C₃₉H₄₈NO₂₁^- (100), 753.2240 C₃₄H₄₁O₁₉^- (45), 607.1660 C₂₈H₃₁O₁₅^- (2), 461.1080 C₂₂H₂₁O₁₁^- (16), 299.4627 C₁₆H₁₁O₆^- (10)	0.17 ± 0.02
Quercetin-3-O-α-L-rhamnopyranosyl-(1→2)-[6-O-(3-hydroxy-3-methylglutaryl)-β-D-galactopyranoside (QueHMG)	5.79 ± 0.010	754.1956; C₃₃H₃₈O₂₀	755.2020 C₃₃H₃₉O₂₀ ⁺; 611.1593 C₂₇H₃₁O₁₆⁺ (49), 465.1027 C₂₁H₂₁O₁₂⁺ (2), 303.0494 C₁₅H₁₁O₇⁺ (100), 153.0181 C₇H₅O₄⁺ (3)	753.1893 C₃₃H₃₇O₂₀ ^-; 609.1462 C₂₇H₂₈O₁₆^- (15), 463.0910 C₂₁H₁₉O₁₂^- (1), 301.0347 C₁₅H₉O₇^- (22), 300.0277 C₁₅H₈O₇^-• (100), 151.0024 C₇H₃O₄^- (4)	0.18 ± 0.02
Kaempferol-3-O-α-L-rhamnopyranosyl-(1→2)-[6-O-(3-hydroxy-3-methylglutaryl)-β-D-galactopyranoside (KaeHMG)	6.21 ± 0.010	738.2007; C₃₃H₃₈O₁₉	739.2072 C₃₃H₃₉O₁₉⁺; 595.1538 C₂₇H₃₁O₁₅⁺ (8), 449.1078 C₂₁H₂₁O₁₁⁺ (1), 287.0545 C₁₅H₁₁O₆⁺ (100), 153.0180 C₇H₅O₄⁺ (6)	737.1942 C₃₃H₃₇O₁₉^-; 593.1515 C₂₇H₂₉O₁₅^- (12), 447.0917 C₂₁H₁₉O₁₁^- (1), 284.0327 C₁₅H₈O₆^-• (100), 285.0398 C₁₅H₉O₆^- (29), 151.0031 C₇H₃O₄^- (3)	0.17 ± 0.02
Kaempferol-3-O-[2-O-β-D-galactopyranosyl-6-O-α-L-rhamnopyranosyl]-β-D-glucopyranoside (camelliaside A, CamA)	4.99 ± 0.010	756.2112; C₃₃H₄₀O₂₀	757.2191 C₃₃H₄₁O₂₀⁺; 611.1625 C₂₇H₃₁O₁₆⁺ (3), 449.1091 C₂₁H₂₁O₁₁⁺ (5), 287.0551 C₁₅H₁₁O₆⁺ (100), 153.0184 C₇H₅O₄⁺ (2)	755.2035 C₃₃H₃₉O₂₀^-; 609.1450 C₂₇H₂₉O₁₆^- (4), 447.0919 C₂₁H₁₉O₁₁^- (3), 284.0328 C₁₅H₈O₆^-• (100), 285.0399 C₁₅H₉O₆^- (47), 151.0026 C₇H₃O₄^- (1)	0.19 ± 0.01
Quercetin-3-O-α-L-rhamnopyranosyl-(1→2)-[α-L-rhamnopyranosyl-(1→6)]-β-D-galactopyranoside (alcesefoliside, Alce)	4.94 ± 0.010	756.2114; C₃₃H₄₀O₂₀	757.2191 C₃₃H₄₁O₂₀⁺; 611.1604 C₂₇H₃₁O₁₆⁺ (27), 465.1023 C₂₁H₂₁O₁₂⁺ (13), 303.0499 C₁₅H₁₁O₇⁺ (100), 153.0179 C₇H₅O₄⁺ (1)	755.2045 C₃₃H₃₉O₂₀^-; 609.1480 C₂₇H₂₉O₁₆^- (2), 463.0880 C₂₁H₁₉O₁₂^- (1) 300.0279 C₁₅H₈O₇^-• (100), 301.0328 C₁₅H₉O₇^- (13), 151.0030 C₇H₃O₄^- (6)	0.16 ± 0.03
Kaempferol-3-O-α-L-rhamnopyranosyl-(1→2)-[α-L-rhamnopyranosyl-(1→6)]-β-D-galactopyranoside (mauritianin, Maur)	5.37 ± 0.020	740.2164; C₃₃H₄₀O₁₉	741.2245 C₃₃H₄₁O₁₉⁺; 595.1655 C₂₇H₃₁O₁₅⁺ (30), 449.1073 C₂₁H₂₁O₁₁⁺ (15), 287.0549 C₁₅H₁₁O₆⁺ (100), 153.0182 C₇H₅O₄⁺ (2)	739.2100 C₃₃H₃₉O₁₉^-; 593.1489 C₂₇H₂₉O₁₅^- (2), 447.0929 C₂₁H₁₉O₁₁^- (1), 284.0329 C₁₅H₈O₆^-• (100), 285.0393 C₁₅H₉O₆^- (26), 151.0025 C₇H₃O₄^- (4)	0.17 ± 0.03
Quercetin-3-O-α-L-rhamnopyranosyl-(1→6)-β-D-glucopyranoside (Rutin)	5.69 ± 0.010	610.1533; C₂₇H₃₀O₁₆	611.1605 C₂₇H₃₁O₁₆⁺; 465.1026 C₂₁H₂₁O₁₂⁺ (24), 303.0496 C₁₅H₁₁O₇⁺ (100), 153.0180 C₇H₅O₄⁺ (5)	609.1470 C₂₇H₂₉O₁₆^-; 463.0922 C₂₁H₁₉O₁₂^- (1), 300.0280 C₁₅H₈O₇^-• (100), 301.0349 C₁₅H₉O₇^- (48), 151.0028 C₇H₃O₄^- (14),	0.14 ± 0.01
17(R),20(R)-3β,6α,16β-trihydroxycycloartanyl-23-carboxilic acid 16-lactone 3-O-β-D-glucopyranoside (ECAS)	10.27 ± 0.010	578.3526; C₃₂H₅₀O₉	579.3531 C₃₂H₅₁O₉⁺; 417.3015 C₂₆H₄₁O₄⁺ (100)	623.3438 C₃₃H₅₁O₁₁^-; 577.3381 C₃₂H₄₉O₉^- (100), 415.3015 C₂₆H₃₉O₄^- (56)	0.19 ± 0.01

Sample No.	Species	QueFA	KaeFA	QueHMG	KaeHMG	CamA	Alce	Maur	Rutin	ECAS
1	A. cicer	-	-	-	-	-	+	+	+	-
2	A. cicer	-	-	-	-	-	+	+	+	-
3	A. depressus	-	-	-	+	-	-	-	-	-
4	A. glycyphylloides	-	+	-	-	+	+	+	-	-
5	A. glycyphyllos	-	-	-	-	+	-	+	+	+
6	A. glycyphyllos	-	-	-	-	+	-	+	+	+
7	A. monspessulanus subsp. monspessulanus	+	+	-	-	-	+	+	+	-
8	A. monspessulanus subsp. monspessulanus	+	+	-	-	-	+	+	+	-
9	A. monspessulanus subsp. illyricus	-	-	+	+	-	+	+	+	-
10	A. onobrychis var. chlorocarpus	-	+	-	-	+	+	+	+	+
11	A. onobrychis var. chlorocarpus	-	+	-	-	+	+	+	+	+
12	A. onobrychis var. chlorocarpus	-	+	-	-	+	+	+	+	+
13	A. ponticus	-	-	-	-	-		+	+	-

Sociedade Brasileira de Química Secretaria Executiva, Av. Prof. Lineu Prestes, 748 - bloco 3 - Superior, 05508-000 São Paulo SP - Brazil, C.P. 26.037 - 05599-970, Tel.: +55 11 3032.2299, Fax: +55 11 3814.3602 - São Paulo - SP - Brazil
E-mail: quimicanova@sbq.org.br

Acompanhe os números deste periódico no seu leitor de RSS

[1] *e-mail: krasteva.ilina@abv.bg