Features of formation and structure of silicon–polysaccharide-containing polyolate hydrogels obtained by the method of biomimetic mineralization

  • Maria V. Ivanenko
  • Elena Yu. Nikitina
  • Tat’yana G. KhoninaEmail author
  • Elena V. Shadrina
  • Maria E. Novoselova
  • Dmitry K. Kuznetsov
  • Maxim S. Karabanalov
Original Paper: Sol-gel and hybrid materials for biological and health (medical) applications


We have demonstrated that our patented water-soluble biocompatible polyolate precursors of silicon tetraglycerolate and silicon tetrapolyethylene glycolate can be successfully utilized in biomimetical mineralization of polysaccharides of different nature. By the example of chitosan (cationic), xanthan gum (anionic), and hydroxyethyl cellulose (uncharged) polysaccharides, an accelerating effect on the gelation process has been demonstrated, and a stabilizing effect has been revealed on the hydrogels formed as transparent monoliths showing resistance to syneresis. Structural features of silicon–polysaccharide-containing hydrogels were investigated using advanced physical methods of cryo-scanning electron microscopy and transmission electron microscopy. Thus formed silicon-containing 3D network of gels is found to be polymeric and appears to have an ordered amorphous morphostructure, which can be explained as caused by the effect of polysaccharides serving as templates. The difference in the reactivity of precursors leads to the peculiarities of the gelation process in the presence of the polysaccharides under study, as well as to the difference in the composition of the formed products. The sol-gel process utilized to obtain the silicon–polysaccharide-containing hydrogels proceeds under the mild conditions with no catalyst or any organic solvent, and thus can be regarded as belonging to the green chemistry methods that show promise for biomedical material applications.


  • Silicon tetraglycerolate and tetrapolyethylene glycolate are promising precursors in sol-gel process.

  • The precursors were successfully used for biomimetic mineralization of polysaccharides.

  • Polysaccharides accelerate the gelation, stabilize hydrogels formed, and order their morphostructure.

  • Polymeric network of gels contains polyolate bridges between silicon atoms.

  • Silicon–polysaccharide-containing polyolate hydrogels are promising for biomedical purposes.


Biomimetic mineralization of polysaccharides Sol-gel process Silicon polyolates Water-soluble biocompatible precursor 3D polymeric network Chemism of hydrogels formation 



We are grateful to Natasha Pomortseva for help in translating the paper. The equipment of the Ural Center for Shared Use “Modern Nanotechnology” and Laboratory of Structural Methods of Analysis and Properties of Materials and Nanomaterials of the Ural Federal University was used. This work was carried out in the framework of the state assignment of Russia (theme no. АААА-А19-119011790134-1).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Wysokowski M, Jesionowski T, Ehrlich H (2018) Biosilica as a source for inspiration in biological materials science. Am Mineral 103:665–691CrossRefGoogle Scholar
  2. 2.
    Sigel A, Sigel H, Roland KO (2008) Biomineralization: from nature to application. Wiley, ChichesterGoogle Scholar
  3. 3.
    Spinde K, Kammer M, Freyer K, Ehrlich H, Vournakis JN, Brunner E (2011) Biomimetic silicification of fibrous chitin from diatoms. Chem Mater 23(11):2973–2978CrossRefGoogle Scholar
  4. 4.
    Wysokowski M, Behm T, Born R, Bazhenov VV, Meißner H, Richter G, Szwarc-Rzepka K, Makarova A, Vyalikh D, Schupp P, Jesionowski T, Ehrlich H (2013) Preparation of chitin–silica composites by in vitro silicification of two-dimensional Ianthella basta demosponge chitinous scaffolds under modified Stöber conditions. Mater Sci Eng C 33:3935–3941CrossRefGoogle Scholar
  5. 5.
    Singh V, Srivastava P, Singh A, Singh D, Malviya T (2016) Polysaccharide-silica hybrids: design and applications. Polym Rev 56:113–136CrossRefGoogle Scholar
  6. 6.
    Salama A (2016) Polysaccharides/silica hybrid materials: new perspectives for sustainable raw materials. J Carbohydr Chem 35:131–149CrossRefGoogle Scholar
  7. 7.
    Owens GJ, Singh RK, Foroutan F, Alqaysi M, Han CM, Mahapatra C, Kim HW, Knowles JC (2016) Sol-gel based materials for biomedical applications. Progr Mater Sci 77:1–79CrossRefGoogle Scholar
  8. 8.
    Pipattanawarothai A, Suksai C, Srisook K, Trakulsujaritchok T (2017) Non-cytotoxic hybrid bioscaffolds of chitosan-silica: sol-gel synthesis, characterization and proposed application. Carbohyd Polym 178:190–199CrossRefGoogle Scholar
  9. 9.
    Ehrlich H, Janussen D, Simon P, Bazhenov V, Shapkin N, Erler C, Mertig M, Born R, Heinemann S, Hanke T, Worch H, Vournakis J (2008) Nanostructural organization of naturally occurring composites—part II: silica-chitin-based biocomposites. J Nanomater
  10. 10.
    Pandey S, Mishra SB (2011) Sol-gel derived organic–inorganic hybrid materials: synthesis, characterizations and applications. J Sol-Gel Sci Technol 59:73–94CrossRefGoogle Scholar
  11. 11.
    Wang D, Liu W, Feng Q, Dong C, Liu Q, Duan L, Huang J, Zhu W, Li Z, Xiong J, Liang Y, Chen J, Sune R, Bian L, Wang D (2017) Effect of inorganic/organic ratio and chemical coupling on the performance of porous silica/chitosan hybrid scaffolds. Mater Sci Eng C 70:969–975CrossRefGoogle Scholar
  12. 12.
    Ates B, Koytepe S, Balcioglu S, Ulu A, Gurses C (2017) In: Thakur VK, Thakur MK, Pappu A (eds) Hybrid polymer composite materials: applications. Elsevier, CambridgeGoogle Scholar
  13. 13.
    Shchipunov YA, Karpenko TYu (2004) Hybrid polysaccharide-silica nanocomposites prepared by the sol-gel technique. Langmuir 20:3882–3887CrossRefGoogle Scholar
  14. 14.
    Shchipunov YA, Karpenko TYu, Krekoten AV, Postnova IV (2005) Gelling of otherwise nongelable polysaccharides. J Colloid Interface Sci 287:373–378CrossRefGoogle Scholar
  15. 15.
    Wang G, Zhang L (2007) Manipulating formation and drug-release behavior of new sol-gel silicamatrix by hydroxypropyl guar gum. J Phys Chem B 30:10665–10670CrossRefGoogle Scholar
  16. 16.
    Shchipunov YA, Postnova IV (2018) Cellulose mineralization as a route for novel functional materials. Adv Funct Mater 28:1705042. CrossRefGoogle Scholar
  17. 17.
    Larchenko EY, Shadrina EV, Khonina TG, Chupakhin ON (2014) New hybrid chitosan–silicone-containing glycerohydrogels. Mendeleev Commun 24:201–202CrossRefGoogle Scholar
  18. 18.
    Larchenko EYu, Khonina TG, Shadrina EV, Pestov AV, Chupakhin ON, Men’shutina NV, Lebedev AE, Lovskaya DD, Larionov LP, Chigvintsev SA (2014) Formation and pharmacological activity of silicon–chitosan-containing glycerohydrogels obtained by biomimetic mineralization. Russ Chem Bull 63:1225–1231CrossRefGoogle Scholar
  19. 19.
    Shadrina EV, Malinkina ON, Khonina TG, Shipovskaya AB, Fomina VI, Larchenko EYu, Popova NA, Zyryanova IG, Larionov LP (2015) Study of formation and pharmacological activity of silicon,chitosan–glycerohydrogel obtained by biomimetic mineralization. Russ Chem Bull 7:1633–1639CrossRefGoogle Scholar
  20. 20.
    Zhovtyak PB, Grigoryev SS, Khonina TG, Shadrina EV, Chupakhin ON, Larionov LP, Ron GI, Chernysheva ND, Popova NA (2016) Agent for local treatment of lichen acuminatus of oral mucosa and method of treating lichen acuminatus of oral mucosa. RU Patent 2583945Google Scholar
  21. 21.
    Khonina TG, Safronov AP, Ivanenko MV, Shadrina EV, Chupakhin ON (2015) Features of silicon– and titanium–polyethylene glycol precursors in sol-gel processing. J Mater Chem B 3:5490–5500CrossRefGoogle Scholar
  22. 22.
    Khonina TG, Shadrina EV, Boyko AA, Chupakhin ON, Larionov LP, Volkov AA, Burda VD (2010) Synthesis of hydrogels based on silicon polyolates. Russ Chem Bull 59(1):75–80CrossRefGoogle Scholar
  23. 23.
    Gill I, Ballesteros A (1998) Encapsulation of biologicals within silicate, siloxane, and hybrid sol-gel polymers: an efficient and generic approach. J Am Chem Soc 120:8587–8598CrossRefGoogle Scholar
  24. 24.
    Brook MA, Chen Y, Guo K, Zhang Z, Brennan JD (2004) Sugar-modified silanes: precursors for silica monoliths J Mater Chem 14:1469–1479CrossRefGoogle Scholar
  25. 25.
    Brandhuber D, Torma V, Raab C, Peterlik H, Kulak A, Hüsing N (2005) Glycol-modified silanes in the synthesis of mesoscopically organized silica monoliths with hierarchical porosity. Mater Chem 17:4262–4271CrossRefGoogle Scholar
  26. 26.
    Khonina TG, Safronov AP, Shadrina EV, Ivanenko MV, Suvorova AI, Chupakhin ON (2012) Mechanism of structural networking in hydrogels based on silicon and titanium glycerolates. J Colloid Interface Sci 365:81–89CrossRefGoogle Scholar
  27. 27.
    Larchenko ЕYu, Permikin VV, Safronov AP, Khonina ТG (2017) Structural features of polymeric silicon glycerolates hydrogels. Russ Chem Bull 66(8):1478–1482CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  • Maria V. Ivanenko
    • 1
  • Elena Yu. Nikitina
    • 1
  • Tat’yana G. Khonina
    • 1
    Email author
  • Elena V. Shadrina
    • 1
  • Maria E. Novoselova
    • 2
  • Dmitry K. Kuznetsov
    • 2
  • Maxim S. Karabanalov
    • 2
  1. 1.Postovsky Institute of Organic Synthesis, Russian Academy of Sciences (Ural Branch)EkaterinburgRussian Federation
  2. 2.Ural Federal UniversityEkaterinburgRussian Federation

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