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. 2023 Mar 24;21(4):205.
doi: 10.3390/md21040205.

Glycosaminoglycans from the Starfish Lethasterias fusca: Structures and Influence on Hematopoiesis

Maria I Bilan  1 , Natalia Yu Anisimova  2 , Alexandra I Tokatly  1 , Sofya P Nikogosova  1 , Dmitriy Z Vinnitskiy  1 , Nadezhda E Ustyuzhanina  1 , Andrey S Dmitrenok  1 , Evgenia A Tsvetkova  1 , Mikhail V Kiselevskiy  2 , Nikolay E Nifantiev  1 , Anatolii I Usov  1
Affiliations

Glycosaminoglycans from the Starfish Lethasterias fusca: Structures and Influence on Hematopoiesis

Maria I Bilan et al. Mar Drugs. .

Abstract

Crude anionic polysaccharides extracted from the Pacific starfish Lethasterias fusca were purified by anion-exchange chromatography. The main fraction LF, having MW 14.5 kDa and dispersity 1.28 (data of gel-permeation chromatography), was solvolytically desulfated and giving rise to preparation LF-deS with a structure of dermatan core [→3)-β-d-GalNAc-(1→4)-α-l-IdoA-(1→]n, which was identified according to NMR spectroscopy data. Analysis of the NMR spectra of the parent fraction LF led to identification of the main component as dermatan sulfate LF-Derm →3)-β-d-GalNAc4R-(1→4)-α-l-IdoA2R3S-(1→ (where R was SO3 or H), bearing sulfate groups at O-3 or both at O-2 and O-3 of α-l-iduronic acid, as well as at O-4 of some N-acetyl-d-galactosamine residues. The minor signals in NMR spectra of LF were assigned as resonances of heparinoid LF-Hep composed of the fragments →4)-α-d-GlcNS3S6S-(1→4)-α-l-IdoA2S3S-(1→. The 3-O-sulfated and 2,3-di-O-sulfated iduronic acid residues are very unusual for natural glycosaminoglycans, and further studies are needed to elucidate their possible specific influence on the biological activity of the corresponding polysaccharides. To confirm the presence of these units in LF-Derm and LF-Hep, a series of variously sulfated model 3-aminopropyl iduronosides were synthesized and their NMR spectra were compared with those of the polysaccharides. Preparations LF and LF-deS were studied as stimulators of hematopoiesis in vitro. Surprisingly, it was found that both preparations were active in these tests, and hence, the high level of sulfation is not necessary for hematopoiesis stimulation in this particular case.

Keywords: Lethasterias fusca; dermatan sulfate; hematopoiesis; heparinoid; starfish; synthetic sulfated iduronosides.

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Conflict of interest statement

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

Figures

Figure 1
Figure 1
The 1H NMR (A) and 13C NMR (B) spectra of preparations LF and LF-deS.
Figure 2
Figure 2
The structures of polysaccharides LF-deS, LF-Derm and LF-Hep.
Figure 3
Figure 3
The COSY (A) and HSQC (B) NMR spectra of preparation LF.
Scheme 1
Scheme 1
Synthesis of uronic acid derivatives 7-11. Reagents and conditions: (a) i: MeONa, MeOH, ii: p-Anisaldehyde, CH(OMe)3, CSA, CH3CN, iii: Bu2SnO, MeOH, reflux, iv: 2-bromomethyl naphthalene, CsF, DMF, v: TFA (90% aq.); (b) i: BAIB, TEMPO, DCM/H2O, 0 °C, ii: MeI, K2CO3, DMF; (c) MeONa, MeOH; (d) i: Bu2SnO, Tol., reflux, ii: BzCl, iii: TBSOTf, NEt3, DCM; (e) i: 3-chloroperbenzoic acid, DCM, −30 °C, ii: N3(CH2)3OH, Tf2O, DTBMP, AW300, DCM, rt. (f) i: TBAF, THF, 50 °C, ii: LiOH 2 M(aq.), H2O, iii: NaOH 1 M(aq.), iv: H2, Pd(OH)2/C, THF/H2O; (g) i: K2CO3, MeOH, ii: Py·SO3, DMF, iii: TBAF, THF, 50 °C, iv: LiOH 2 M(aq.), H2O, v: H2, Pd(OH)2/C, THF/H2O; (h) i: DDQ, DCM/H2O, ii: TBAF, THF, 50 °C; iii: LiOH 2 M(aq.), H2O; iv: NaOH 1 M(aq.), v: H2, Pd(OH)2/C, THF/H2O; (i) i: TBAF, THF, 50 °C, ii: DDQ, DCM/H2O, iii: Py·SO3, DMF, iv: LiOH 2 M(aq.), H2O, v: NaOH 1 M(aq.), vi: H2, Pd(OH)2/C, THF/H2O; (j) i: TBAF, THF, 50 °C, ii: DDQ, DCM/H2O, iii: K2CO3, MeOH, iv: Py·SO3, DMF, v:. LiOH 2 M(aq.), H2O, vi: H2, Pd(OH)2/C, THF/H2O.
Figure 4
Figure 4
Electrophoresis in polyacrylamide gel of Hep (heparin Sigma, MW 15 kDa), Enox (enoxaparin, Clexane®, Sanofi, MW 4.5 kDa) and LF.
Figure 5
Figure 5
Influence of preparations LF and LF-deS on bone marrow cell proliferation. rG-CSF was used as a positive control. Intact cells were considered as a control.
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