Polyelectrolyte Complexes between Hyperbranched and Linear Polysaccharides: Fucoidan/Chitosan

Ekaterina R. Gasilova; Daria N. Poshina; Aleksandra O. Sitnikova; Natalia N. Saprykina; Yury A. Skorik

doi:10.1007/s10118-024-3069-9

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Polyelectrolyte Complexes between Hyperbranched and Linear Polysaccharides: Fucoidan/Chitosan

RESEARCH ARTICLE | Updated：2024-03-14

- Polyelectrolyte Complexes between Hyperbranched and Linear Polysaccharides: Fucoidan/Chitosan
- Polyelectrolyte Complexes between Hyperbranched and Linear Polysaccharides: Fucoidan/Chitosan
- 高分子科学（英文版） 2024年42卷第4期页码：468-479
- Affiliations：
  
  Institute of Macromolecular Compounds of the Russian Academy of Sciences, Bolshoi VO 31, St. Petersburg 199004, Russian Federation
- Author bio：
  
  katja.gasilova@gmail.com
- Funds：
  
  This work was jointly funded by the Russian Science Foundation and the St.-Petersburg Science Foundation (No. 23-23-10005). The authors thank Dr. A.A. Kulminskaya for providing the fucoidan sample.;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-024-3069-9.
- DOI：10.1007/s10118-024-3069-9
  中图分类号：
- 收稿：2023-10-03，
  
  修回：2023-11-1，
  
  录用：2023-11-15，
  
  网络首发：2023-12-12，
  
  纸质出版：2024-04-01
- Accepted：
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Gasilova, E. R.; Poshina, D. N.; Sitnikova, A. O.; Saprykina, N. N.; Skorik, Y. A. Polyelectrolyte complexes between hyperbranched and linear polysaccharides: fucoidan/chitosan. Chinese J. Polym. Sci. 2024, 42, 468–479

Ekaterina R. Gasilova, Daria N. Poshina, Aleksandra O. Sitnikova, et al. Polyelectrolyte Complexes between Hyperbranched and Linear Polysaccharides: Fucoidan/Chitosan[J]. Chinese Journal of Polymer Science, 2024, 42(4): 468-479.
Gasilova, E. R.; Poshina, D. N.; Sitnikova, A. O.; Saprykina, N. N.; Skorik, Y. A. Polyelectrolyte complexes between hyperbranched and linear polysaccharides: fucoidan/chitosan. Chinese J. Polym. Sci. 2024, 42, 468–479 DOI： 10.1007/s10118-024-3069-9.

Ekaterina R. Gasilova, Daria N. Poshina, Aleksandra O. Sitnikova, et al. Polyelectrolyte Complexes between Hyperbranched and Linear Polysaccharides: Fucoidan/Chitosan[J]. Chinese Journal of Polymer Science, 2024, 42(4): 468-479. DOI： 10.1007/s10118-024-3069-9.

摘要

Internal structure

size

and mobility of nanoparticles formed by polyelectrolyte complexation between large macromolecules of hyperbranched anionic polysaccharide fucoidan and several chitosans (smaller linear cationic polysaccharides) were studied in dilute solutions by light scattering methods (SLS

DLS

and EDS) and by SEM and AFM in a dry state.

Abstract

Polyelectrolyte complexes (PECs) of hyperbranched (HB) and linear polysaccharides are promising as more effective encapsulation agents compared to PECs formed by linear polysaccharides. We investigated the PECs between the HB anionic polysaccharide fucoidan (FUC) and the cationic linear polysaccharide chitosan (CS). The FUC had a molecular weight (MW) of 30×10

. The PECs were prepared in three solvents (water

0.01 and 0.1 mol/L acetic acid) with CS of MW of 15

110 and 170 kDa

and deacetylation degrees (DDA) of 70% and 97%. The structures of the PECs and the initial FUC were investigated by multi-angle static and dynamic light scattering. As the FUC contained 18 wt% of ―OSO

groups and 5 wt% of uronic acid units

it was a "strong-weak" copolyanion

so the HB macromolecules of the FUC formed nanogel particles in 0.1 mol/L AcOH and open branched structures in water

as confirmed by the Kratky plots. After mixing the solutions of original components

the PEC structures underwent an equilibration period

the duration of which increased with the MW of CS. As the charge stoichiometry was approached

the PECs shrank; the fractal dimension approached unity

indicating the side-by-side packing of adjacent FUC branches with the help of CS. Secondary aggregation in the vicinity of the charge compensation was hardly observed

as it occurred in a very narrow region. The PEC content at the

-potential inversion depended on solvents’ pH and the DDA of CS. In the extreme case of core-shell PECs in 0.1 mol/L AcOH

obtained by mixing FUC nanogels with the solutions of high MW CS of 97% DDA

the protruding tails of CS formed a positively charged shell in the whole range of FUC content (10 wt%

FUC

90 wt%). Scanning electron microscopy and atomic force microscopy images of dried samples were discussed in relation to the light scattering results.

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