Chemical Transformation of Protopanaxadiol Type Ginsenoside Rb1, Rb2 and Rc Analyzed by RRLC-Q-TOF-MS†

doi:10.7503/cjcu20170459

Abstract

Abstract:

The developed rapid resolution liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry(RRLC-Q-TOF-MS) method was applied for analyzing the chemical transformation of protopanaxadiol(PPD) type ginsenoside Rb₁, Rb₂ and Rc under acidic condition. And Rb₁, Rb₂, Rc and conversion products were analyzed in the ginseng processing. The experimental results demonstrated that chemical transformation mechanisms of protopanaxadiol type ginsenoside in acidic condition included saccharide hydrolysis, Δ20(21)- or Δ20(22)-dehydration, and hydration addition reactions at C24 and C25. The RRLC-Q-TOF-MS/MS analysis included the specific product ions of aglycone PPD(m/z 459), Δ20(21)- or Δ20(22)-dehydration-PPD(m/z 441), and C24, C25 hydrated-PPD(m/z 477). The tandem mass spectrometry(MS/MS) was discussed to provide a basis for structural characterization. The chemical trans-formation pathway for protopanaxadiol type ginsenoside was summarized. The established method was applied for analyzing PPD ginsenosides changes in raw white ginseng and processed red ginseng(100 and 120 ℃).

Key words: Protopanaxadiol type ginsenoside, Rapid resolution liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry(RRLC-Q-TOF-MS), Chemical transformation

CLC Number:

O657

TrendMD:

ZHAO Lefeng, JIAO Chuanxin, LI Hui, JIAO Lili, MA Yue, WU Wei, LIU Shuying. Chemical Transformation of Protopanaxadiol Type Ginsenoside Rb₁, Rb₂ and Rc Analyzed by RRLC-Q-TOF-MS^†[J]. Chem. J. Chinese Universities, 2018, 39(4): 667.

Figures/Tables 6

References 22

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Peak No.	Ginsenoside	Molecular formula	M_w	[M-H]^-, m/z (Measured value)	MS/MS fragment ions of [M+HCOO]^-
1	Rb₁	C₅₄H₉₂O₂₃	1108.6729	1107.5966	1153.6011[M+HCOO]^-; 1107.5976[M-H]^-; 945.5402[M-H-Glc]^-; 783.4833[M-H-GlcGlc]^-; 621.4280[M-H-GlcGlcGlc]^-; 459.3754[M-H-GlcGlcGlcGlc]^-; 179.0490[Glc-H]^-
2	Rb₂	C₅₃H₉₀O₂₂	1078.5924	1077.5842	1123.5906[M+HCOO]^-; 1077.5842[M-H]^-; 945.5380[M-H-Ara(p)]^-; 783.4863[M-H-AraGlc]^-; 621.4276[M-H-AraGlcGlc]^-; 459.3734[M-H-AraGlcGlcGlc]^-; 293.0797[AraGlc-H]^-; 149.0328[Ara-H]^-
Peak No.	Ginsenoside	Molecular formula	M_w	[M-H]^-, m/z (Measured value)	MS/MS fragment ions of [M+HCOO]^-
3	Rc	C₅₃H₉₀O₂₂	1078.5924	1077.5833	1123.5906[M+HCOO]^-; 1077.5833[M-H]^-; 945.5384[M-H-Ara(f)]^-; 783.4847[M-H-AraGlc]^-; 621.4295[M-H-AraGlcGlc]^-; 459.3741[M-H-AraGlcGlcGlc]^-; 293.0812[AraGlc-H]^-; 149.0385[Ara-H]^-
4	C-Y₁/C-Y₂	C₄₂H₇₄O₁₄	802.5079	801.5006	847.5060[M+HCOO]^-; 801.4973[M-H]^-; 639.4443[M-H-Glc]^-; 477.3875[M-H-GlcGlc]^-; 161.0370[Glc-H₂O-H]^-
5	C-Y₁/C-Y₂	C₄₂H₇₄O₁₄	802.5079	801.5006	847.5040[M+HCOO]^-; 801.4973[M-H]^-; 639.4393[M-H-Glc]^-; 477.3865[M-H-GlcGlc]^-; 161.0370[Glc-H₂O-H]^-
6	Rd	C₄₈H₈₂O₁₈	946.5501	945.5423	991.5483[M+HCOO]^-; 945.5023[M-H]^-; 783.4622[M-H-Glc]^-; 621.4124[M-H-GlcGlc]^-; 459.3643[M-H-GlcGlcGlc]^-; 161.0368[Glc-H₂O-H]^-
7	F₂	C₄₂H₇₂O₁₃	784.4973	783.49	829.4981[M+HCOO]^-; 783.4868[M-H]^-; 621.4230[M-H-Glc]^-; 161.0376[Glc-H₂O-H]^-
8	20(S)-Rg₃	C₄₂H₇₂O₁₃	784.4973	783.49	829.4960[M+HCOO]^-; 783.4879[M-H]^-; 621.4311[M-H-Glc]^-; 459.3763[M-H-GlcGlc]^-; 161.0384[Glc-H₂O-H]^-
9	20(R)-Rg₃	C₄₂H₇₂O₁₃	784.4973	783.49	829.4950[M+HCOO]^-; 783.4861[M-H]^-; 621.4310[M-H-Glc]^-; 459.3763[M-H-GlcGlc]^-; 221.0583[Glc+HCOO]^-; 161.0374[Glc-H₂O-H]^-
10	Rk₁	C₄₂H₇₀O₁₂	766.4867	765.4795	811.4848[M+HCOO]^-; 765.4749[M-H]^-; 603.4205[M-H-Glc]^-; 161.0380[Glc-H₂O-H]^-
11	Rg₅	C₄₂H₇₀O₁₂	766.4867	765.4795	811.4864[M+HCOO]^-; 765.4749[M-H]^-; 603.4215[M-H-Glc]^-; 161.0380[Glc-H₂O-H]^-

Peak No.	Ginsenoside	Molecular formula	M_w	[M-H]^-, m/z (Measured value)	MS/MS fragment ions of [M+HCOO]^-
1	Rb₁	C₅₄H₉₂O₂₃	1108.6729	1107.5966	1153.6011[M+HCOO]^-; 1107.5976[M-H]^-; 945.5402[M-H-Glc]^-; 783.4833[M-H-GlcGlc]^-; 621.4280[M-H-GlcGlcGlc]^-; 459.3754[M-H-GlcGlcGlcGlc]^-; 179.0490[Glc-H]^-
2	Rb₂	C₅₃H₉₀O₂₂	1078.5924	1077.5842	1123.5906[M+HCOO]^-; 1077.5842[M-H]^-; 945.5380[M-H-Ara(p)]^-; 783.4863[M-H-AraGlc]^-; 621.4276[M-H-AraGlcGlc]^-; 459.3734[M-H-AraGlcGlcGlc]^-; 293.0797[AraGlc-H]^-; 149.0328[Ara-H]^-
Peak No.	Ginsenoside	Molecular formula	M_w	[M-H]^-, m/z (Measured value)	MS/MS fragment ions of [M+HCOO]^-
3	Rc	C₅₃H₉₀O₂₂	1078.5924	1077.5833	1123.5906[M+HCOO]^-; 1077.5833[M-H]^-; 945.5384[M-H-Ara(f)]^-; 783.4847[M-H-AraGlc]^-; 621.4295[M-H-AraGlcGlc]^-; 459.3741[M-H-AraGlcGlcGlc]^-; 293.0812[AraGlc-H]^-; 149.0385[Ara-H]^-
4	C-Y₁/C-Y₂	C₄₂H₇₄O₁₄	802.5079	801.5006	847.5060[M+HCOO]^-; 801.4973[M-H]^-; 639.4443[M-H-Glc]^-; 477.3875[M-H-GlcGlc]^-; 161.0370[Glc-H₂O-H]^-
5	C-Y₁/C-Y₂	C₄₂H₇₄O₁₄	802.5079	801.5006	847.5040[M+HCOO]^-; 801.4973[M-H]^-; 639.4393[M-H-Glc]^-; 477.3865[M-H-GlcGlc]^-; 161.0370[Glc-H₂O-H]^-
6	Rd	C₄₈H₈₂O₁₈	946.5501	945.5423	991.5483[M+HCOO]^-; 945.5023[M-H]^-; 783.4622[M-H-Glc]^-; 621.4124[M-H-GlcGlc]^-; 459.3643[M-H-GlcGlcGlc]^-; 161.0368[Glc-H₂O-H]^-
7	F₂	C₄₂H₇₂O₁₃	784.4973	783.49	829.4981[M+HCOO]^-; 783.4868[M-H]^-; 621.4230[M-H-Glc]^-; 161.0376[Glc-H₂O-H]^-
8	20(S)-Rg₃	C₄₂H₇₂O₁₃	784.4973	783.49	829.4960[M+HCOO]^-; 783.4879[M-H]^-; 621.4311[M-H-Glc]^-; 459.3763[M-H-GlcGlc]^-; 161.0384[Glc-H₂O-H]^-
9	20(R)-Rg₃	C₄₂H₇₂O₁₃	784.4973	783.49	829.4950[M+HCOO]^-; 783.4861[M-H]^-; 621.4310[M-H-Glc]^-; 459.3763[M-H-GlcGlc]^-; 221.0583[Glc+HCOO]^-; 161.0374[Glc-H₂O-H]^-
10	Rk₁	C₄₂H₇₀O₁₂	766.4867	765.4795	811.4848[M+HCOO]^-; 765.4749[M-H]^-; 603.4205[M-H-Glc]^-; 161.0380[Glc-H₂O-H]^-
11	Rg₅	C₄₂H₇₀O₁₂	766.4867	765.4795	811.4864[M+HCOO]^-; 765.4749[M-H]^-; 603.4215[M-H-Glc]^-; 161.0380[Glc-H₂O-H]^-

Ginseng product	Content of ginsenoside/(mg·g^-1)^*
Ginseng product	Rb₁	Rb₂	Rc	Rd
White ginseng	25.27±0.57	5.29±0.08	16.36±0.53	8.58±0.15
Red ginseng(100 ℃)	27.75±0.45	7.11±0.11	13.46±0.09	9.65±0.82
Red ginseng(120 ℃)	1.64±0.16		0.8512±0.02	0.99±0.07

Ginseng product	Content of ginsenoside/(mg·g^-1)^*
Ginseng product	Rb₁	Rb₂	Rc	Rd
White ginseng	25.27±0.57	5.29±0.08	16.36±0.53	8.58±0.15
Red ginseng(100 ℃)	27.75±0.45	7.11±0.11	13.46±0.09	9.65±0.82
Red ginseng(120 ℃)	1.64±0.16		0.8512±0.02	0.99±0.07

Chemical Transformation of Protopanaxadiol Type Ginsenoside Rb₁, Rb₂ and Rc Analyzed by RRLC-Q-TOF-MS^†

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