Gao L et al. (2022), Structure Elucidation of Fucan Sulfate from Sea...

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Int J Mol Sci 2022 Apr 19;239:. doi: 10.3390/ijms23094488.

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Structure Elucidation of Fucan Sulfate from Sea Cucumber Holothuria fuscopunctata through a Bottom-Up Strategy and the Antioxidant Activity Analysis.

Gao L , Xu C , Tao X , Zuo Z , Ning Z , Wang L , Gao N , Zhao J .

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Fucan sulfate I (FSI) from the sea cucumber Holothuria fuscopunctata was purified and its structure was clarified based on a bottom-up strategy. The unambiguous structures of a series of oligosaccharides including disaccharides, trisaccharides, and tetrasaccharides, which were released from mild acid hydrolysis of FSI, were identified by one-dimensional (1D)/two-dimensional (2D) nuclear magnetic resonance (NMR) and mass spectrometry (MS) analysis. All the glycosidic bonds in these oligosaccharides were presented as α1,3 linkages confirmed by correlated signals from their 1H-1H ROESY and 1H-13C HMBC spectra. The structural sequence of these oligosaccharides formed by Fuc2S4S, Fuc2S, and non-sulfated ones (Fuc0S), along with the general structural information of FSI, indicated that the structure of FSI could be elucidated as: [-L-Fuc2S4S-α1,3-L-Fuc(2S)-α1,3-L-Fuc2S-α1,3-L-Fuc0S-α1,3-1-]n. Moreover, the L-Fuc0S-α1,3-L-Fuc2S4S linkage in FSI was susceptible to be cleaved by mild acid hydrolysis. The antioxidant activity assays in vitro showed that FSI and the depolymerized product (dFSI') had potent activities for superoxide radical scavenging activity with IC50 of 65.71 and 83.72 μg/mL, respectively, while there was no scavenging effect on DPPH, hydroxyl and ABTS radicals.

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	Figure 1. High-performance gel permeation chromatography (HPGPC) profiles of the products released from mild acid hydrolysis of fucan sulfate I (FSI). (A) HPGPC of the hydrolyzed products at different times at 80 °C determined on a Shodex OHpak SB-804 HQ column (8.0 mm × 300 mm) eluted with 0.1 M NaCl solution at a flow rate of 0.5 mL/min detected by refractive index detector (RID), respectively. (B) HPGPC profiles of mild acid hydrolyzed product (dFSI) and its oligosaccharides analyzed on a Superdex peptide 10/300 GL column eluted with 0.2 M NaCl solution at a flow rate of 0.4 mL/min detected by RID.
	Figure 2. The 1H (A,B) and 13C (C,D) spectra of FI and FII, correlation spectroscopy(1H-1H COSY) (E) and heteronuclear multiple bond correlation (1H-13C HMBC) (F) of FI; the overlapped spectra (G) of 1H-1H COSY (gray), total correlation spectroscopy (1H-1H TOCSY)(red) and rotating frame Overhauser effect spectroscopy (1H-1H ROESY) (blue) of FII; and the overlapped spectra (H) of heteronuclear single quantum coherence (1H- 13C HSQC) (gray) and 1H- 13C HMBC (red).
	Figure 3. The 1H (A,B) and 13C (C,D) spectra of FIII and FIV, 1H–1H COSY (E) and ROESY (F) of FIII; the overlapped 1H–1H COSY (gray), TOCSY (red) and ROESY (blue) spectra (G) of FIV; and the overlapped 1H-13C HSQC (gray) and 1H-13C HMBC (red) spectra (H).
	Figure 4. The 1H (A,B) and 13C (C,D) spectra of FVI and FV; the overlapped 1H-13C HSQC (gray) and 1H-13C HMBC (red) spectra (E) of FV, partial 1H-1H COSY (gray), 1H-1H TOCSY (red) and 1H-1H ROESY (green in (F) and blue in (G)); and the overlapped spectra of FV (F) and FVI (G).
	Figure 5. The mass spectrometry (MS) spectra of oligosaccharides FIII (A), FIV (B), FV (C) and FVI (D).
	Scheme 1. The basic structure of FSI was confirmed with bottom-up strategy. The letters below the structure of each oligosaccharide are used as labels for assignments in the NMR spectra, respectively.
	Figure 6. Partial overlapped spectra (A) of 1H-1H COSY (gray), ROESY (blue) and TOCSY (red) of depolymerized product (dFSI′) and possible cross-peaks from H-1 in ROESY marked by blue arrows (B). The capital letters A, B, C and D represent Fuc2S4S, Fuc(2S), Fuc2S and Fuc, respectively.
	Figure 7. Scavenging effect of FSI and dFSI′ on hydroxyl radicals (A), ABTS radicals (B), DPPH radicals (C) and superoxide radicals (D), respectively. (n = 3).