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Glycerol as a green solvent for enhancing the formulation of dextran methacrylate and gellan-based semi-interpenetrating polymer networks

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Abstract

Recently, glycerol has been exploited in a number of industrial applications, thanks to its high availability, its low cost and, overall, its peculiar properties which fit well with the green chemistry principles. In this work, the ability of glycerol to solubilize high molecular weight polymers and to allow the formation of glycerol-based semi-interpenetrating polymer networks, called “gly-semi-IPNs”, has been investigated. Compared to water, glycerol deeply affects the structural properties of the biopolymers, especially with reference to their chain flexibility. Among the polysaccharides, dextran methacrylate (DexMA) and gellan gum (Ge) were selected. Glycerol solutions of both polysaccharides and their mixtures, as well as a DexMA network (obtained by cross-linking in glycerol and in the presence of a photoinitiator), were rheologically characterized to assess the role of the solvent on the chain conformation and on the mechanical properties of the networks. Interestingly, glycerol was found to deeply influence the mechanical, morphological and optical properties of the formed hydrogels, as well as to improve the cross-linking kinetic of DexMA. Furthermore, glycerol leads to more homogeneous mixtures of the two polysaccharides than those observed in aqueous buffers. As such, novel gly-semi-IPNs, with enhanced formulation and mechanical properties, were prepared and characterized.

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References

  1. The Soap and Detergent Association (1990). Glycerine an overview. 475 Park Avenue South, New York

  2. Farrán A, Cai C, Sandoval M, Xu Y, Liu J, Hernáiz MJ, Linhardt RJ (2015) Green solvents in carbohydrate chemistry: from raw materials to fine chemicals. Chem Rev 115:6811–6853

    Article  Google Scholar 

  3. Gu Y, Barrault J, Jérôme F (2008) Glycerol as an efficient promoting medium for organic reactions. Adv Synth Catal 350:2007–2012

    Article  CAS  Google Scholar 

  4. Díaz-Álvarez AE, Francos J, Croche P, Cadierno V (2014) Recent advances in the use of glycerol as green solvent for synthetic organic chemistry. Curr Green Chem 1:51–65

    Article  Google Scholar 

  5. Garcia JI, Garcia-Marin H, Pires E (2014) Glycerol based solvents: synthesis, properties and applications. Green Chem 16:1007–1033

    Article  CAS  Google Scholar 

  6. Fernandes BS, Carlos Pinto J, Cabral-Albuquerque EC, Fialho RL (2015) Free-radical polymerization of urea, acrylic acid, and glycerol in aqueous solutions. Polym Eng Sci 55:1219–1229

    Article  CAS  Google Scholar 

  7. Osmanov TO, Kozlova NV, Markov VY (1990) Polymerization of acrylamide in water–glycerol mixtures. Polym Sci USSR 32:650–654

    Article  Google Scholar 

  8. Chun BC, Chong MH, Chung YC (2007) Effect of glycerol cross-linking and hard segment content on the shape memory property of polyurethane block copolymer. J Mater Sci 42:6524–6531. https://doi.org/10.1007/s10853-007-1568-z

    Article  CAS  Google Scholar 

  9. Cerqueira MA, Souza BW, Teixeira JA, Vicente AA (2012) Effect of glycerol and corn oil on physicochemical properties of polysaccharide films—a comparative study. Food Hydrocoll 27:175–184

    Article  CAS  Google Scholar 

  10. Vieira MGA, Da Silva MA, Dos Santos LO, Beppu MM (2011) Natural-based plasticizers and biopolymer films: a review. Eur Polym J 47:254–263

    Article  CAS  Google Scholar 

  11. Paolicelli P, Petralito S, Varani G, Nardoni M, Pacelli S, Di Muzio L, Tirillò J, Bartuli C, Cesa S, Casadei MA, Adrover A (2018) Effect of glycerol on the physical and mechanical properties of thin gellan gum films for oral drug delivery. Int J Pharm 547:226–234

    Article  CAS  Google Scholar 

  12. Stout EI, McKessor A (2012) Glycerin-based hydrogel for infection control. Adv Wound Care 1:48–51

    Article  Google Scholar 

  13. Björklund S, Engblom J, Thuresson K, Sparr E (2013) Glycerol and urea can be used to increase skin permeability in reduced hydration conditions. Eur J Pharm Sci 50:638–645

    Article  Google Scholar 

  14. Cassanelli M, Norton I, Mills T (2017) Effect of alcohols on gellan gum gel structure: bridging the molecular level and the three-dimensional network. Food Struct 14:112–120

    Article  Google Scholar 

  15. Liu ZQ, Yi XS, Feng Y (2001) Effects of glycerin and glycerol monostearate on performance of thermoplastic starch. J Mater Sci 36:1809–1815. https://doi.org/10.1023/A:1017589028611

    Article  CAS  Google Scholar 

  16. Guo MQ, Hu X, Wang C, Ai L (2017) Polysaccharides: structure and solubility. In: Zhenbo Xu (ed) Solubility of polysaccharides, InTech, Croatia, p 7–21. https://doi.org/10.5772/66033

  17. Häkkinen R, Abbott A (2019) Solvation of carbohydrates in five choline chloride-based deep eutectic solvents and the implication for cellulose solubility. Green Chem 21:4673–4682

    Article  Google Scholar 

  18. Jenkins AD, Kratochvíl P, Stepto RFT, Suter UW (1996) Glossary of basic terms in polymer science (IUPAC recommendations 1996). Pure Appl Chem 68:2287–2311

    Article  CAS  Google Scholar 

  19. Qi X, Wei W, Li J, Liu Y, Hu X, Zhang J, Lirong B, Dong W (2015) Fabrication and characterization of a novel anticancer drug delivery system: salecan/poly (methacrylic acid) semi-interpenetrating polymer network hydrogel. ACS Biomater Sci Eng 1:1287–1299

    Article  CAS  Google Scholar 

  20. Qi X, Wei W, Li J, Su T, Pan X, Zuo G, Zhang J, Dong W (2017) Design of Salecan-containing semi-IPN hydrogel for amoxicillin delivery. Mater Sci Eng C 75:487–494

    Article  CAS  Google Scholar 

  21. Qi X, Yuan Y, Zhang J, Bulte JW, Dong W (2018) Oral administration of salecan-based hydrogels for controlled insulin delivery. J Agric Food Chem 66:10479–10489

    Article  CAS  Google Scholar 

  22. Matricardi P, Pontoriero M, Coviello T, Casadei MA, Alhaique F (2008) In situ cross-linkable novel alginate-dextran methacrylate IPN hydrogels for biomedical applications: mechanical characterization and drug delivery properties. Biomacromolecules 9:2014–2020

    Article  CAS  Google Scholar 

  23. Pescosolido L, Schuurman W, Malda J, Matricardi P, Alhaique F, Coviello T, Van Weeren PR, Dhert WJA, Hennink WE, Vermonden T (2011) Hyaluronic acid and dextran-based semi-IPN hydrogels as biomaterials for bioprinting. Biomacromolecules 12:1831–1838

    Article  CAS  Google Scholar 

  24. Bellini D, Cencetti C, Meraner J, Stoppoloni D, Scotto D’Abusco A, Matricardi P (2015) An in situ gelling system for bone regeneration of osteochondral defects. Eur Polym J 72:642–650

    Article  CAS  Google Scholar 

  25. Pescosolido L, Vermonden T, Malda J, Censi R, Dhert WJ, Alhaique F, Hennink WE, Matricardi P (2011) In situ forming IPN hydrogels of calcium alginate and dextran-HEMA for biomedical applications. Acta Biomater 7:1627–1633

    Article  CAS  Google Scholar 

  26. Van Dijk-Wolthuis WNE, Franssen O, Talsma H, van Steenbergen MJ, Kettenes-van den Bosh JJ, Hennink WE (1995) Synthesis, characterization, and polymerization of glycidyl methacrylate derivatized dextran. Macromolecules 28:6317–6322

    Article  Google Scholar 

  27. De Smedt SC, Lauwers A, Demeester J, Van Steenberg MJ, Hennink WE, Roefs SPFM (1995) Characterization of the network structure of dextran glycidyl methacrylate hydrogels by studying the rheological and swelling behaviour. Macromolecules 28:5082–5088

    Article  Google Scholar 

  28. Amici A, Caracciolo G, Digiacomo L, Gambini V, Marchini C, Tilio M, Capriotti AL, Colapicchioni V, Matassa R, Familiari G, Palchetti S, Pozzi D, Mahmoudi M, Lagan A (2017) In vivo protein corona patterns of lipid nanoparticles. RSC Adv 7:1137–1145

    Article  CAS  Google Scholar 

  29. Antoniou E, Tsianou M, Alexandridis P (2018) Solvent modulation of polysacharide conformation. In: AIChE annual meeting, conference proceedings

  30. Miyoshi E, Nishinari K (1999) Non-Newtonian flow behaviour of gellan gum aqueous solutions. Colloid Polym Sci 277:727–734

    Article  CAS  Google Scholar 

  31. Dentini M, Coviello T, Burchard W, Crescenzi V (1998) Solution properties of exocellular microbial polysaccharides. 3. Light scattering from gellan and from the exocellular polysaccharide of Rhizobium trifolii (strain TA-1) in the ordered state. Macromolecules 21:3312–3320

    Article  Google Scholar 

  32. Yang L, Paulson AT (2000) Mechanical and water vapour barrier properties of edible gellan films. Food Res Int 33:563–570

    Article  CAS  Google Scholar 

  33. Zhao S, Shen Z, Wang J, Li X, Zeng Y, Wang B, He Y, Du Y (2014) Glycerol-mediated nanostructure modification leading to improved transparency of porous polymeric scaffolds for high performance 3D cell imaging. Biomacromolecules 15:2521–2531

    Article  CAS  Google Scholar 

  34. Matassa R, Orlanducci S, Guglielmotti V, Sordi D, Tamburri E, Terranova ML, Passeri M, Rossi D (2014) Characterization of carbon structures produced by graphene self-assembling. J Appl Crystallogr 47:222–227

    Article  CAS  Google Scholar 

  35. Matassa R, Familiari G, Battaglione E, Sibilia C, Leahu G, Belardini A, Venditti I, Fontana L, Fratoddi I (2016) Electron microscopy reveals layered architecture of individual gold nanoparticles self-anchored by fluorescence monomers. Nanoscale 8:18161–18169

    Article  CAS  Google Scholar 

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Acknowledgments

The authors thank Ezio Battaglione (Section of Human Anatomy, Electron Microscopy Laboratory “Pietro M Motta”, University of Rome “Sapienza”) for his support in electron microscopy experiments.

Funding

The authors acknowledge financial support from Sapienza University of Rome (“Finanziamenti di Ateneo per la Ricerca Scientifica – RP116154C2EF9AC8 and RM11715C1743EE89”).

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Authors and Affiliations

  1. Department of Drug Chemistry and Technologies, Sapienza University of Rome, P.le A. Moro 5, 00185, Rome, Italy

    Nicole Zoratto, Elita Montanari, Stefania Petralito, Tommasina Coviello, Chiara Di Meo & Pietro Matricardi

  2. Section of Human Anatomy, Department of Anatomical, Histological, Forensic and Orthopaedic Sciences, Sapienza University of Rome, Via A. Borelli 50, 00161, Rome, Italy

    Roberto Matassa & Giuseppe Familiari

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  1. Nicole Zoratto
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  2. Roberto Matassa
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  6. Tommasina Coviello
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  8. Pietro Matricardi
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Contributions

Data curation was carried out by Tommasina Coviello and Stefania Petralito; funding was acquired by Pietro Matricardi and Giuseppe Familiari; investigation was performed by Nicole Zoratto and Roberto Matassa; methodology was designed by Nicole Zoratto and Elita Montanari; project administration was conducted by Chiara Di Meo and Pietro Matricardi; original draft was written by Nicole Zoratto; review was written and edited by Tommasina Coviello and Elita Montanari.

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Correspondence to Pietro Matricardi.

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Zoratto, N., Matassa, R., Montanari, E. et al. Glycerol as a green solvent for enhancing the formulation of dextran methacrylate and gellan-based semi-interpenetrating polymer networks. J Mater Sci 55, 9562–9577 (2020). https://doi.org/10.1007/s10853-020-04732-1

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