Influence of the ascorbic acid isoform on the sol–gel synthesis kinetics and properties of silicon–chitosan-containing glycerohydrogel plates

  • Anna B. ShipovskayaEmail author
  • Yulia Yu. Zhuravleva
  • Tat’yana G. Khonina
  • Olga N. Malinkina
  • Natalia O. Gegel
Original Paper: Sol-gel and hybrid materials for biological and health (medical) applications


Glycerohydrogel thin-film plates based on chitosan l-(d-)ascorbate and poly(vinyl alcohol) were obtained by means of template sol–gel synthesis with silicon tetraglycerolate as a biocompatible precursor. The rheokinetics of the sol–gel process is considered, the deformation and strength characteristics of the material were evaluated. The gelation time during plate formation has been established to decrease with increasing the template concentration and temperature. Chitosan d-ascorbate has been found to retard gelation. Stress–strain curves characteristic of soft elastic materials were recorded for our samples of silicon-containing glycerohydrogel plates. At rupture, the material shows some characteristic signs of macroscopic plasticity. The maximum achievable values of the physicomechanical parameters depend on the template/precursor ratio. With an increase in this ratio, the tensile strength increases, whereas the concentration dependences of the relative elongation at break and Young’s modulus show an extreme character. The plates based on chitosan D-ascorbate had higher mechanical strength and elasticity under uniaxial tension and a lower value of Young’s modulus as compared to those based on chitosan l-ascorbate. The regularities obtained are discussed from the standpoint of the influence of the ascorbic acid isoform on the conformational features of chitosan macromolecules and their supramolecular ordering in the glycerohydrogel system.


  • Glycerohydrogel plates based on chitosan l/d-ascorbates were obtained using silicon tetraglycerolate.

  • Gelation time during plate formation decreases with increasing template concentration and temperature.

  • Our sol–gel-made glycerohydrogel plates have properties of soft materials.

  • Chitosan l- and d-ascorbates differ in conformation and supramolecular ordering of macromolecules.

  • Chitosan d-ascorbate retards gelation and raises strength-elastic properties of our sol–gel material.


Chitosan Ascorbic acid isoform Sol–gel synthesis Rheokinetic Glycerohydrogel plates Physicomechanical properties 



The results of the work were obtained with the financial support of the Russian Science Foundation grant No 17-73-10076 “Chiral polymeric matrices: preparation, physicochemical properties, interaction with bioobjects”.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    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
  2. 2.
    Kumar D, Wu X, Fu Q, Ho JWC, Kanhere PD, Li L, Chen Z (2015) Development of durable self-cleaning coatings using organic-inorganic hybrid sol-gel method. Appl Surf Sci 344:205–212CrossRefGoogle Scholar
  3. 3.
    Shimizu T, Kanamori K, Nakanishi K (2017) Silicone‐based organic-inorganic hybrid aerogels and xerogels. Chemistry 23:5176–5187CrossRefGoogle Scholar
  4. 4.
    Shavandi A, AEDA Bekhit, Sun Z, Ali MA (2016) Injectable gel from squid pen chitosan for bone tissue engineering applications. J Sol-Gel Sci Technol 77:675–687CrossRefGoogle Scholar
  5. 5.
    Owens GJ, Singh RK, Foroutan F, Alqaysi M, Han CM, Mahapatra C, Knowles JC (2016) Sol-gel based materials for biomedical applications. Prog Mater Sci 77:1–79CrossRefGoogle 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.
    Shchipunov YA, Karpenko TYY (2004) Hybrid polysaccharide-silica nanocomposites prepared by the sol-gel technique. Langmuir 20:3882–3887CrossRefGoogle Scholar
  8. 8.
    Shchipunov YA, Karpenko TYY, Krekoten AV (2005) Hybrid organic-inorganic nanocomposites fabricated with a novel biocompatible precursor using sol-gel processing. Compos Interfaces 11:587–607CrossRefGoogle Scholar
  9. 9.
    Khonina TG, Chupakhin ON, Larionov LP, Boyakovskaya TG, Suvorov AL, Shadrina EV (2008) Synthesis, toxicity, and percutaneous activity of silicon glycerolates and related hydrogels. Pharm Chem J 42:609–613CrossRefGoogle Scholar
  10. 10.
    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
  11. 11.
    Spinde K, Kammer M, Freyer K, Ehrlich H, Vournakis JN, Brunner E (2011) Biomimetic silicification of fibrous chitin from diatoms. Chem Mater 23:2973–2978CrossRefGoogle Scholar
  12. 12.
    Hamedi H, Moradi S, Hudson SM, Tonelli AE (2018) Chitosan based hydrogels and their applications for drug delivery in wound dressings: a review. Carbohyd Polym 199:445–460CrossRefGoogle Scholar
  13. 13.
    Khonina T. G., Shipovskaya A. B., Shadrina E. V., Malinkina O. N., Zudina I. V., Larchenko EYu (2017) In: Taylor J. C. (ed) Formation features, properties and biomedical application of silicon-chitosan-containing glycerohydrogels, Advances in Chemistry Research. Nova Science Publ. New YorkGoogle Scholar
  14. 14.
    Gegel NO, YuYu Zhuravleva, Shipovskaya AB, Malinkina ON, Zudina IV (2018) Influence of chitosan ascorbate chirality on the gelation kinetics and properties of silicon-chitosan-containing glycerohydrogels. Polym 10:259CrossRefGoogle Scholar
  15. 15.
    Perchacz M, Beneš H, Kobera L, Walterová Z (2015) Influence of sol-gel conditions on the final structure of silica-based precursors. J Sol-Gel Sci Technol 75:649–663CrossRefGoogle Scholar
  16. 16.
    Silva GS, Oliveira PC, Giordani DS, Castro HFD (2011) Chitosan/siloxane hybrid polymer: synthesis, characterization and performance as a support for immobilizing enzyme. J Braz Chem Soc 22:1407–1417CrossRefGoogle Scholar
  17. 17.
    Wysokowki 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
  18. 18.
    Larchenko EYu, Shadrina EV, Khonina TG, Chupakhin ON (2014) New hybrid chitosan-silicone containing glycerohydrogels. Mendeleev Commun 24:201–202CrossRefGoogle Scholar
  19. 19.
    Malinkina ON, Sobolev AM, Shipovskaya AB (2016) Hybrid nanogels based on chitosan hydrochloride-ascorbate derived by sol-gel biomimetic synthesis. BioNanoSci 6(2):157–161CrossRefGoogle Scholar
  20. 20.
    Shipovskaya AB, Malinkina ON, Zhuravleva YuYu, Rogacheva SM (2016) Synthesis of silicon-containing chitosan hydrogels in a glycolic acid medium. Adv Mater Sci Eng 2016: 8Google Scholar
  21. 21.
    Ogawa K, Nakata K, Yamamoto A, Nitta Y, Yui T (1996) X-ray study of chitosan L- and D-ascorbates. Chem Mater 8:2349–2351CrossRefGoogle Scholar
  22. 22.
    Baker MI, Walsh SP, Schwartz Z, Boyan BD (2012) A review of polyvinyl alcohol and its uses in cartilage and orthopedic applications. J Biomed Mater Res Part B: Appl Biomater 100:1451–1457CrossRefGoogle Scholar
  23. 23.
    Costa-Júnior ES, Barbosa-Stancioli EF, Mansur AA, Vasconcelos WL, Mansur HS (2009) Preparation and characterization of chitosan/poly(vinyl alcohol) chemically crosslinked blends for biomedical applications. Carbohydr Polym 76:472–481CrossRefGoogle Scholar
  24. 24.
    Haque MA, Kurokawa T, Gong JP (2012) Super tough double network hydrogels and their application as biomaterials. Polym 53:1805–1822CrossRefGoogle Scholar
  25. 25.
    Ziraki S, Zebarjad SM, Hadianfard MJ (2016) A study on the tensile properties of silicone rubber/polypropylene fibers/silica hybrid nanocomposites. J Mech Behav Biomed Mater 57:289–296CrossRefGoogle Scholar
  26. 26.
    Ovcharenko EA, Klyshnikov KU, Yuzhalin AE, Savrasov GV, Glushkova TV, Vasukov GU, Barbarash LS (2017) Comparison of xenopericardial patches of different origin and type of fixation implemented for TAVI. Int J Biomed Eng Technol 25:44–59CrossRefGoogle Scholar
  27. 27.
    Whelan A, Duffy J, Gaul RT, O’Reilly D, Nolan DR, Gunning P, Lally C (2019) Collagen fibre orientation and dispersion govern ultimate tensile strength, stiffness and the fatigue performance of bovine pericardium. J Mech Behav Biomed Mater 90:54–60CrossRefGoogle Scholar
  28. 28.
    Liu Y, Ballarini R, Eppell SJ (2016) Tension tests on mammalian collagen fibrils. Interface Focus 6:20150080CrossRefGoogle Scholar
  29. 29.
    Peloquin JM, Santare MH, Elliott DM (2018) Short cracks in knee meniscus tissue cause strain concentrations, but not weakness, in single-cycle uniaxial tension. Roy SOC 5:181166Google Scholar
  30. 30.
    Johnson GA, Tramaglini DM, Levine RE, Ohno K, Choi NY, L-Y Woo S (1994) Tensile and viscoelastic properties of human patellar tendon. J Orthop Res 12:796–803CrossRefGoogle Scholar
  31. 31.
    Singh J, Kumar S, Dutta PK (2009) Preparation and chiroptical properties of chitosan acid derivatives in dilute solution. J Polym Mater 26:167–176Google Scholar
  32. 32.
    Nova A, Keten S, Pugno NM (2010) Molecular and nanostructural mechanisms of deformation, strength and toughness of spider silk fibrils. Nano Lett 10:2626–2634CrossRefGoogle Scholar
  33. 33.
    Del Mercato LL, Maruccio G, Pompa PP (2008) Amyloid-like fibrils in elastin-related polypeptides: structural characterization and elastic properties. BioMacroMol 9:796–803CrossRefGoogle Scholar
  34. 34.
    Li QX, Song BZ, Yang ZQ, Fan HL (2006) Electrolytic conductivity behaviors and solution conformations of chitosan in different acid solutions. Carbohydr Polym 63:272–282CrossRefGoogle Scholar

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

Authors and Affiliations

  1. 1.Saratov State UniversitySaratovRussia
  2. 2.Institute of Biochemistry and Physiology of Plants and MicroorganismsRussian Academy of SciencesSaratovRussia
  3. 3.Institute of Organic SynthesisUral Branch of the Russian Academy of SciencesEkaterinburgRussia

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