Abstract
The rheological properties of hydrogels of a natural polysaccharide sodium alginate and small amount of clay nanotubes of halloysite were investigated. Changes of rheological properties during the transition from a semidiluted polymer solution to a hydrogel upon cross-linking by calcium ions were shown. In the gel state, the samples have a yield stress, and their viscosity decreases with the shear rate, but the properties are quickly recovered after the load removal. It was discovered that the addition of up to 0.3 vol % nanotubes of natural clay halloysite leads to an increase by several times of a storage modulus and a yield stress of the hydrogels. At the same time, the practically important properties of shear thinning and the rapid recovery of properties after the load removing make the nanocomposite hydrogels of alginate and halloysite nanotubes promising for use as ink for extrusion 3D printing.
REFERENCES
Liu, J., Sun, L., Xu, W., Wang, Q., Yu, S., and Sun, J., Current advances and future perspectives of 3D printing natural-derived biopolymers, Carbohydr. Polym., 2019, vol. 207, pp. 297–316. https://doi.org/10.1016/j.carbpol.2018.11.077
Mobaraki, M., Ghaffari, M., Yazdanpanah, A., Luo, Ya., and Mills, D.K., Bioinks and bioprinting: A focused review, Bioprinting, 2020, vol. 18, p. e00080. https://doi.org/10.1016/j.bprint.2020.e00080
Valentine, A.D., Busbee, T.A., Boley, J.W., Raney, J.R., Chortos, A., Kotikian, A., Berrigan, J.D., Durstock, M.F., and Lewis, J.A., Hybrid 3D printing of soft electronics, Adv. Mater., 2017, vol. 29, no. 40, p. 1703817. https://doi.org/10.1002/adma.201703817
Arzhakova, O.V., Arzhakov, M.S., Badamshina, E.R., Bryuzgina, E.B., Bryuzgin, E.V., Bystrova, A.V., Vaganov, G.V., Vasilevskaya, V.V., Vdovichenko, A.Yu., Gallyamov, M.O., Gumerov, R.A., Didenko, A.L., Zefirov, V.V., Karpov, S.V., Komarov, P.V., Kulichi-khin, V.G., Kurochkin, S.A., Larin, S.V., Malkin, A.Ya., Milenin, S.A., Muzafarov, A.M., Molchanov, V.S., Navrotskiy, A.V., Novakov, I.A., Panarin, E.F., Panova, I.G., Potemkin, I.I., Svetlichny, V.M., Sedush, N.G., Serenko, O.A., Uspenskii, S.A., Philippova, O.E., Khokhlov, A.R., Chvalun, S.N., Sheiko, S.S., Shibaev, A.V., Elmanovich, I.V., Yudin, V.E., Yakimansky, A.V., and Yaroslavov, A.A., Polymers for the future, Russ. Chem. Rev., 2022, vol. 91, no. 12, p. RCR5062. https://doi.org/10.57634/rcr5062
Li, H., Tan, C., and Li, L., Review of 3D printable hydrogels and constructs, Mater. Des., 2018, vol. 159, pp. 20–38. https://doi.org/10.1016/j.matdes.2018.08.023
Truby, R.L. and Lewis, J.A., Printing soft matter in three dimensions, Nature, 2016, vol. 540, no. 7633, pp. 371–378. https://doi.org/10.1038/nature21003
Heinrich, M.A., Liu, W., Jimenez, A., Yang, J., Akpek, A., Liu, X., Pi, Q., Mu, X., Hu, N., Schiffelers, R.M., Prakash, J., Xie, J., and Zhang, Yu.S., 3D bioprinting: From benches to translational applications, Small, 2019, vol. 15, no. 23, p. 1805510. https://doi.org/10.1002/smll.201970126
Stanton, M.M., Samitier, J., and Sánchez, S., Bioprinting of 3D hydrogels, Lab a Chip, 2015, vol. 15, no. 15, pp. 3111–3115. https://doi.org/10.1039/c5lc90069g
Rastogi, P. and Kandasubramanian, B., Review of alginate-based hydrogel bioprinting for application in tissue engineering, Biofabrication, 2019, vol. 11, no. 4, p. 042001. https://doi.org/10.1088/1758-5090/ab331e
Diañez, I., Gallegos, C., Brito-De La Fuente, E., Martínez, I., Valencia, C., Sánchez, M.C., Diaz, M.J., and Franco, J.M., 3D printing in situ gelification of κ‑carrageenan solutions: Effect of printing variables on the rheological response, Food Hydrocolloids, 2019, vol. 87, pp. 321–330. https://doi.org/10.1016/j.foodhyd.2018.08.010
Hu, C., Du, Z., Tai, X., Mao, X., and Liu, X., The property study of sodium dodecyl benzenesulfonate and polyvinylpyrrolidone complexes, Colloid Polym. Sci., 2018, vol. 296, no. 2, pp. 335–340. https://doi.org/10.1007/s00396-017-4248-9
Axpe, E. and Oyen, M., Applications of alginate-based bioinks in 3D bioprinting, Int. J. Mol. Sci., 2016, vol. 17, no. 12, p. 1976. https://doi.org/10.3390/ijms17121976
Murphy, S.V. and Atala, A., 3D bioprinting of tissues and organs, Nat. Biotechnol., 2014, vol. 32, no. 8, pp. 773–785. https://doi.org/10.1038/nbt.2958
Dávila, J.L. and D’ávila, M.A., Rheological evaluation of Laponite/alginate inks for 3D extrusion-based printing, Int. J. Adv. Manuf. Technol., 2019, vol. 101, nos. 1–4, pp. 675–686. https://doi.org/10.1007/s00170-018-2876-y
Peak, C.W., Stein, J., Gold, K.A., and Gaharwar, A.K., Nanoengineered colloidal inks for 3D bioprinting, Langmuir, 2018, vol. 34, no. 3, pp. 917–925. https://doi.org/10.1021/acs.langmuir.7b02540
Liu, L., Wan, Ya., Xie, Yi., Zhai, R., Zhang, B., and Liu, J., The removal of dye from aqueous solution using alginate-halloysite nanotube beads, Chem. Eng. J., 2012, vol. 187, pp. 210–216. https://doi.org/10.1016/j.cej.2012.01.136
Del Buffa, S., Rinaldi, E., Carretti, E., Ridi, F., Bonini, M., and Baglioni, P., Injectable composites via functionalization of 1D nanoclays and biodegradable coupling with a polysaccharide hydrogel, Colloids Surf. B: Biointerfaces, 2016, vol. 145, pp. 562–566. https://doi.org/10.1016/j.colsurfb.2016.05.056
Li, H., Liu, S., and Lin, L., Rheological study on 3D printability of alginate hydrogel and effect of graphene oxide, Int. J. Bioprinting, 2016, vol. 2, no. 2, pp. 58–66. https://doi.org/10.18063/ijb.2016.02.007
Glukhova, S., Molchanov, V., Lokshin, B., Rogachev, A., Tsarenko, A., Patsaev, T., Kamyshinsky, R., and Philippova, O., Printable alginate hydrogels with embedded network of halloysite nanotubes: Effect of polymer cross-linking on rheological properties and microstructure, Polymers, 2021, vol. 13, no. 23, p. 4130. https://doi.org/10.3390/polym13234130
Glukhova, S.A., Molchanov, V.S., Chesnokov, Yu.M., Lokshin, B.V., Kharitonova, E.P., and Philippova, O.E., Green nanocomposite gels based on binary network of sodium alginate and percolating halloysite clay nanotubes for 3D printing, Carbohydr. Polym., 2022, vol. 282, p. 119106. https://doi.org/10.1016/j.carbpol.2022.119106
Stokke, B.T., Draget, K.I., Smidsrød, O., Yuguchi, Yo., Urakawa, H., and Kajiwara, K., Small-angle X-ray scattering and rheological characterization of alginate gels. 1. Ca−alginate gels, Macromolecules, 2000, vol. 33, no. 5, pp. 1853–1863. https://doi.org/10.1021/ma991559q
Lvov Y., Abdullayev E. Functional polymer-clay nanotube composites with sustained release of chemical agents. Prog Polym Sci. 2013; 38: 1690–1719. https://doi.org/10.1016/j.progpolymsci. 2013.05.009
Cavallaro, G., Chiappisi, L., Pasbakhsh, P., Gradzielski, M., and Lazzara, G., A structural comparison of halloysite nanotubes of different origin by small-angle neutron scattering (SANS) and electric birefringence, Appl. Clay Sci., 2018, vol. 160, pp. 71–80. https://doi.org/10.1016/j.clay.2017.12.044
Hernández, R., Sacristán, J., and Mijangos, C., Sol/Gel transition of aqueous alginate solutions induced by Fe2+ cations, Macromol. Chem. Phys., 2010, vol. 211, no. 11, pp. 1254–1260. https://doi.org/10.1002/macp.200900691
Li, H., Liu, S., and Lin, L., Rheological study on 3D printability of alginate hydrogel and effect of graphene oxide, Int. J. Bioprinting, 2016, vol. 2, no. 2, pp. 54–66. https://doi.org/10.18063/ijb.2016.02.007
Hashemnejad, S.M. and Kundu, S., Rheological properties and failure of alginate hydrogels with ionic and covalent crosslinks, Soft Matter, 2019, vol. 15, no. 39, pp. 7852–7862. https://doi.org/10.1039/c9sm01039d
Molchanov, V.S., Efremova, M.A., Kiseleva, T.Yu., and Philippova, O.E., Injectable ultra-soft hydrogel with natural nanoclay, Nanosystems: Phys., Chem., Math., 2019, vol. 10, no. 1, pp. 76–85. https://doi.org/10.17586/2220-8054-2019-10-1-76-85
Shishkhanova, K.B., Molchanov, V.S., Baranov, A.N., Kharitonova, E.P., Orekhov, A.S., Arkharova, N.A., and Philippova, O.E., A pH-triggered reinforcement of transient network of wormlike micelles by halloysite nanotubes of different charge, J. Mol. Liq., 2023, vol. 370, p. 121032. https://doi.org/10.1016/j.molliq.2022.121032
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The work was carried out with financial support from the Russian Science Foundation (project no. 23-13-00177).
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Molchanov, V.S., Glukhova, S.A. & Philippova, O.E. Rheological Behavior of Polysaccharide Hydrogels of Alginate Reinforced by a Small Amount of Halloysite Nanotubes for Extrusion 3D Printing. Moscow Univ. Biol.Sci. Bull. 78 (Suppl 1), S72–S77 (2023). https://doi.org/10.3103/S0096392523700268
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DOI: https://doi.org/10.3103/S0096392523700268