Abstract
The Halloysite nanotubes (HNTs) surface-modified with sodium alginate were reinforced in the PVA/PVP (Polyvinylalcohol/Polyvinylpyrrolidone) matrix employed for biomedical applications. The nanocomposite films with variable modified HNTs were fabricated using solution casting technique. The physico-chemical, thermal, and mechanical properties of the polymer blends were evaluated for their suitability for the biomedical field. The obtained mechanical and thermal properties were correlated with morphological studies by Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). The morphology results were well correlated with the Water Contact Angle (WCA), swelling behavior, and in vitro enzymatic degradation. Overall, the results show that nanocomposite films increase thermo-mechanical characteristics, uniform distribution, roughness, and enzymatic degradation, while their swelling ratio and hydrophilicity decrease. The in vitro cell proliferation and adhesion activity of blend films was carried out using NIH3T3 cells revealed their excellent proliferative and adhesive activity compared to pristine blend film. The in vitro hemocompatibility of the blend nanocomposite was determined using human RBCs. The fabricated blend films can be potentially utilized in tissue engineering applications.
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References
Abdullah ZW, Dong Y (2019) Biodegradable and water resistant poly (vinyl) alcohol (PVA)/starch (ST)/glycerol (GL)/halloysite nanotube (HNT) nanocomposite films for sustainable food packaging. Front Materials 6:1–17. https://doi.org/10.3389/fmats.2019.00058
Aloui H, Khwaldia K, Hamdi M, Fortunati E, Kenny JM, Buonocore GG, Lavorgna M (2016) Synergistic effect of halloysite and cellulose nanocrystals on the functional properties of PVA based nanocomposites. ACS Sustain Chem Eng 4:794–800. https://doi.org/10.1021/acssuschemeng.5b00806
Asghari F, Samiei M, Adibkia K, Akbarzadeh A, Davaran S (2017) Biodegradable and biocompatible polymers for tissue engineering application: a review. Artif Cells, Nanomed Biotechnol 45:185–192. https://doi.org/10.3109/21691401.2016.1146731
Balakrishnan SB, Kuppu S, Thambusamy S (2021) Biologically important alumina nanoparticles modified polyvinylpyrrolidone scaffolds in vitro characterizations and it is in vivo wound healing efficacy. J Mol Struct 1246:131195. https://doi.org/10.1016/j.molstruc.2021.131195
Barkoula NM, Alcock B, Cabrera NO, Peijs T (2008) Flame-retardancy properties of intumescent ammonium poly(phosphate) and mineral filler magnesium hydroxide in combination with graphene. Polym Polym Compos 16:101–113
Basha SS, Rao MC (2018) Spectroscopic and electrochemical properties of (1 − x) [PVA/PVP]: x [MgCl2 {6H2O}] blend polymer electrolyte films. Int J Polym Sci. https://doi.org/10.1155/2018/2926167.
Bertolino V, Cavallaro G, Milioto S, Lazzara G (2020) Polysaccharides/Halloysite nanotubes for smart bionanocomposite materials. Carbohydr Polym 245:116502. https://doi.org/10.1016/j.carbpol.2020.116502
Boonsuk P, Kaewtatip K, Chantarak S, Kelarakis A, Chaibundit C (2018) Super-tough biodegradable poly(vinyl alcohol)/poly(vinyl pyrrolidone) blends plasticized by glycerol and sorbitol. J Appl Polym Sci 135:1–8. https://doi.org/10.1002/app.46406
Cavallaro G, Lazzara G, Milioto S, Parisi F, Sparacino V (2015) Thermal and dynamic mechanical properties of beeswax-halloysite nanocomposites for consolidating waterlogged archaeological woods. Polym Degrad Stab 120:220–225. https://doi.org/10.1016/j.polymdegradstab.2015.07.007
Cavallaro G, Chiappisi L, Pasbakhsh P, Gradzielski M, Lazzara G (2018) A structural comparison of halloysite nanotubes of different origin by Small-Angle Neutron Scattering (SANS) and Electric Birefringence. Appl Clay Sci 160:71–80. https://doi.org/10.1016/j.clay.2017.12.044
Cavallaro G, Milioto S, Konnova S, Fakhrullina G, Akhatova F, Lazzara G, Fakhrullin R, Lvov Y (2020) Halloysite/Keratin nanocomposite for human hair photoprotection coating. ACS Appl Mater Interfaces 12:24348–24362. https://doi.org/10.1021/acsami.0c05252
Chen QZ, Liang SL, Wang J, Simon GP (2011) Manipulation of mechanical compliance of elastomeric PGS by incorporation of halloysite nanotubes for soft tissue engineering applications. J Mech Behav Biomed Mater 4:1805–1818. https://doi.org/10.1016/j.jmbbm.2011.05.038
Eisenbarth E (2007) Biomaterials for tissue engineering. Adv Eng Mater 9:1051–1060. https://doi.org/10.1002/adem.200700287
Fan L, Zhang J, Wang A (2013) In situ generation of sodium alginate/hydroxyapatite/halloysite nanotubes nanocomposite hydrogel beads as drug-controlled release matrices. J Mater Chem B 1:6261–6270. https://doi.org/10.1039/c3tb20971g
Gaaz TS, Kadhum AAH, Michael PKA, Al-Amiery AA, Sulong AB, Nassir MH, Jaaz AH (2017) Unique halloysite nanotubes-polyvinyl alcohol-polyvinylpyrrolidone composite complemented with physico-chemical characterization. Polymers (Basel). https://doi.org/10.3390/polym9060207
Galus S, Lenart A (2013) Development and characterization of composite edible films based on sodium alginate and pectin. J Food Eng 115:459–465. https://doi.org/10.1016/j.jfoodeng.2012.03.006
Genes NG, Rowley JA, Mooney DJ, Bonassar LJ (2004) Effect of substrate mechanics on chondrocyte adhesion to modified alginate surfaces. Arch Biochem Biophys 422:161–167. https://doi.org/10.1016/j.abb.2003.11.023
Georgieva N, Bryaskova R, Tzoneva R (2012) New Polyvinyl alcohol-based hybrid materials for biomedical application. Mater Lett 88:19–22. https://doi.org/10.1016/j.matlet.2012.07.111
Guo JL, Kim YS, Xie VY, Smith BT, Watson E, Lam J, Pearce HA, Engel PS, Mikos AG (2019) Modular, tissue-specific, and biodegradable hydrogel cross-linkers for tissue engineering. Sci Adv 5:1–12. https://doi.org/10.1126/sciadv.aaw7396
Hashmi M, Ullah S, Ullah A, Saito Y, Haider MK, Bie X, Wada K, Kim IS (2021) Carboxymethyl cellulose (Cmc) based electrospun composite nanofiber mats for food packaging. Polymers (basel) 13:1–12. https://doi.org/10.3390/polym13020302
He Y, Lu F (2016) Development of synthetic and natural materials for tissue engineering applications using adipose stem cells. Stem Cells Int. https://doi.org/10.1155/2016/5786257
Hecht H, Srebnik S (2016) Structural characterization of sodium alginate and calcium alginate. Biomacromol 17:2160–2167. https://doi.org/10.1021/acs.biomac.6b00378
Huang B, Liu M, Long Z, Shen Y, Zhou C (2017) Effects of halloysite nanotubes on physical properties and cytocompatibility of alginate composite hydrogels. Mater Sci Eng C 70:303–310. https://doi.org/10.1016/j.msec.2016.09.001
Hughes AD, King MR (2010) Use of naturally occurring halloysite nanotubes for enhanced capture of flowing cells. Langmuir 26:12155–12164. https://doi.org/10.1021/la101179y
Ionita M, Pandele MA, Iovu H (2013) Sodium alginate/graphene oxide composite films with enhanced thermal and mechanical properties. Carbohydr Polym. https://doi.org/10.1016/j.carbpol.2013.01.065
Ismail H, Khoo WS, Ariffin A (2013) Effects of halloysite nanotubes and kaolin loading on the tensile, swelling, and oxidative degradation properties of poly (vinyl alcohol)/ Chitosan Blends. J Vinyl Additive Technol. https://doi.org/10.1002/vnl
Jasinski E, Bounor-Legaré V, Taguet A, Beyou E (2021) Influence of halloysite nanotubes onto the fire properties of polymer based composites: a review. Polym Degrad Stab. https://doi.org/10.1016/j.polymdegradstab.2020.109407
Joo Y, Jeon Y, Lee SU, Sim JH, Ryu J, Lee S, Lee H, Sohn D (2012) Aggregation and stabilization of carboxylic acid functionalized halloysite nanotubes (HNT-COOH). J Phys Chem C 116:18230–18235. https://doi.org/10.1021/jp3038945
Kamoun EA, Kenawy ERS, Tamer TM, El-Meligy MA, MohyEldin MS (2015) Poly (vinyl alcohol)-alginate physically crosslinked hydrogel membranes for wound dressing applications: characterization and bio-evaluation. Arab J Chem 8:38–47. https://doi.org/10.1016/j.arabjc.2013.12.003
Kohane DS, Langer R (2008) Polymeric biomaterials in tissue engineering. Pediatr Res 63:487–491. https://doi.org/10.1203/01.pdr.0000305937.26105.e7
Koosha M, Mirzadeh H, Shokrgozar MA, Farokhi M (2015) Nanoclay-reinforced electrospun chitosan/PVA nanocomposite nanofibers for biomedical applications. RSC Adv 5:10479–10487. https://doi.org/10.1039/c4ra13972k
Kouser S, Sheik S, Prabhu A, Nagaraja GK, Prashantha K, D’souza JN, Navada MK, Manasa DJ (2021) Effects of reinforcement of sodium alginate functionalized halloysite clay nanotubes on thermo-mechanical properties and biocompatibility of poly (vinyl alcohol) nanocomposites. J Mech Behav Biomed Mater. https://doi.org/10.1016/j.jmbbm.2021.104441
Kouser S, Prabhu A, Sheik S, Prashantha K, Nagaraja GK, D’souza JN, Navada KM, Manasa DJ (2021b) Poly (caprolactone)/sodium-alginate-functionalized halloysite clay nanotube nanocomposites: potent biocompatible materials for wound healing applications. Int J Pharm 607:121048. https://doi.org/10.1016/j.ijpharm.2021.121048
Kouser S, Prabhu A, Sheik S, Prashantha K, Nagaraja GK, NeethaD’souza J, Navada KM, Manasa DJ (2021) Chitosan functionalized halloysite nanotube/poly (caprolactone) nanocomposites for wound healing application. Appl. Surf. Sci. Adv. 6:100158. https://doi.org/10.1016/j.apsadv.2021.100158
Kouser S, Prabhu A, Prashantha K, Nagaraja GK, D’souza JN, MeghanaNavada K, Qurashi A, Manasa DJ (2022) Modified halloysite nanotubes with Chitosan incorporated PVA/PVP bionanocomposite films: thermal, mechanical properties and biocompatibility for tissue engineering. Colloids Surfaces A Physicochem Eng Asp 634:127941. https://doi.org/10.1016/j.colsurfa.2021.127941
Lisuzzo L, Cavallaro G, Milioto S, Lazzara G (2020) Applied clay science effects of halloysite content on the thermo-mechanical performances of composite bioplastics. Appl Clay Sci 185:105416. https://doi.org/10.1016/j.clay.2019.105416
Liu M, Zhang Y, Wu C, Xiong S, Zhou C (2012) Chitosan/halloysite nanotubes bionanocomposites: structure, mechanical properties and biocompatibility. Int J Biol Macromol 51:566–575. https://doi.org/10.1016/j.ijbiomac.2012.06.022
Liu M, Dai L, Shi H, Xiong S, Zhou C (2015) In vitro evaluation of alginate/halloysite nanotube composite scaffolds for tissue engineering. Mater Sci Eng C 49:700–712. https://doi.org/10.1016/j.msec.2015.01.037
Lun H, Ouyang J, Yang H (2014) Natural halloysite nanotubes modified as an aspirin carrier. RSC Adv 4:44197–44202. https://doi.org/10.1039/c4ra09006c
Lutolf MP, Hubbell JA (2005) Synthetic biomaterials as instructive extracellular microenvironments for morphogenesis in tissue engineering. Nat Biotechnol 23:47–55. https://doi.org/10.1038/nbt1055
Ma PX (2008) Biomimetic materials for tissue engineering. Adv Drug Deliv Rev 60:184–198. https://doi.org/10.1016/j.addr.2007.08.041
Mohammed G, El Sayed AM, Morsi WM (2018) Spectroscopic, thermal, and electrical properties of MgO/ polyvinyl pyrrolidone/polyvinyl alcohol nanocomposites. J Phys Chem Solids 115:238–247. https://doi.org/10.1016/j.jpcs.2017.12.050
Mukai M, Ma W, Ideta K, Takahara A (2019) Preparation and characterization of boronic acid- functionalized halloysite nanotube/poly(vinyl alcohol) nanocomposites. Polymer (guildf) 178:121581. https://doi.org/10.1016/j.polymer.2019.121581
Nagarkar R, Patel J (2019) Polyvinyl alcohol: a comprehensive study. Acta Sci Pharm Sci 3:34–44
Najafiasl M, Osfouri S, Azin R, Zaeri S (2020) Alginate-based electrospun core/shell nanofibers containing dexpanthenol: a good candidate for wound dressing. J Drug Deliv Sci Technol. https://doi.org/10.1016/j.jddst.2020.101708
Naumenko E, Fakhrullin R (2019) Halloysite nanoclay/biopolymers composite materials in tissue engineering. Biotechnol J 14:1–11. https://doi.org/10.1002/biot.201900055
Nho YC, Park KR (2002) Preparation and properties of PVA/PVP hydrogels containing chitosan by radiation. J Appl Polym Sci 85:1787–1794. https://doi.org/10.1002/app.10812
Nosrati H, SarrafMamoory R, Svend Le DQ, Bünger CE (2020) Fabrication of gelatin/hydroxyapatite/3D-graphene scaffolds by a hydrogel 3D-printing method. Mater Chem Phys 239:122305. https://doi.org/10.1016/j.matchemphys.2019.122305
Nosrati H, Le DQS, Emamehc RZ, Perez MC, Bünger CE (2022) Nucleation and growth of brushite crystals on the graphene sheets applicable in bone cement. Bol La Soc Esp Ceram y Vidr 61:27–34. https://doi.org/10.1016/j.bsecv.2020.05.001
Okamoto M, John B (2013) Synthetic biopolymer nanocomposites for tissue engineering scaffolds. Prog Polym Sci 38:1487–1503. https://doi.org/10.1016/j.progpolymsci.2013.06.001
Reynaud E, Jouen T, Gauthier C, Vigier G, Varlet J (2001) Nanofillers in polymeric matrix: a study on silica reinforced PA6. Polymer (guildf) 42:8759–8768. https://doi.org/10.1016/S0032-3861(01)00446-3
Rodríguez-Rodríguez R, Espinosa-Andrews H, Velasquillo-Martínez C, García-Carvajal ZY (2020) Composite hydrogels based on gelatin, chitosan and polyvinyl alcohol to biomedical applications: a review. Int J Polym Mater Polym Biomater 69:1–20. https://doi.org/10.1080/00914037.2019.1581780
Saeed RM, Dmour I, Taha MO (2020) Stable chitosan-based nanoparticles using polyphosphoric acid or hexametaphosphate for tandem ionotropic/covalent crosslinking and subsequent investigation as novel vehicles for drug delivery, front. Bioeng Biotechnol 8:1–21. https://doi.org/10.3389/fbioe.2020.00004
Sell SA, Wolfe PS, Garg K, McCool JM, Rodriguez IA, Bowlin GL (2010) The use of natural polymers in tissue engineering: a focus on electrospun extracellular matrix analogues. Polymers (basel) 2:522–553. https://doi.org/10.3390/polym2040522
Shi Y, Xiong D, Liu Y, Wang N, Zhao X (2016) Swelling, mechanical and friction properties of PVA/PVP hydrogels after swelling in osmotic pressure solution. Mater Sci Eng C 65:172–180. https://doi.org/10.1016/j.msec.2016.04.042
Sobhanian P, Khorram M, Hashemi SS, Mohammadi A (2019) Development of nanofibrous collagen-grafted poly (vinyl alcohol)/gelatin/alginate scaffolds as potential skin substitute. Int J Biol Macromol 130:977–987. https://doi.org/10.1016/j.ijbiomac.2019.03.045
Subramanian UM, Kumar SV, Nagiah N, Sivagnanam UT (2014) Fabrication of polyvinyl alcohol-polyvinylpyrrolidone blend scaffolds via electrospinning for tissue engineering applications. Int J Polym Mater Polym Biomater 63:476–485. https://doi.org/10.1080/00914037.2013.854216
Sun P, Liu G, Lv D, Dong X, Wu J, Wang D (2015) Effective activation of halloysite nanotubes by piranha solution for amine modification via silane coupling chemistry. RSC Adv 5:52916–52925. https://doi.org/10.1039/c5ra04444h
Veena G, Lobo B (2018) Experimental investigations on potassium permanganate doped polyvinyl alcohol—polyvinyl pyrrolidone blend. AIP Conf Proc. https://doi.org/10.1063/1.5029164
Yao Q, Li W, Yu S, Ma L, Jin D, Boccaccini AR, Liu Y (2015) Multifunctional chitosan/polyvinyl pyrrolidone/45S5 Bioglass® scaffolds for MC3T3-E1 cell stimulation and drug release. Mater Sci Eng C 56:473–480. https://doi.org/10.1016/j.msec.2015.06.046
Zhou WY, Guo B, Liu M, Liao R, Rabie ABM, Jia D (2010) Poly(vinyl alcohol)/Halloysite nanotubes bionanocomposite films: properties and in vitro osteoblasts and fibroblasts response. J Biomed Mater Res—Part a 93:1574–1587. https://doi.org/10.1002/jbm.a.32656
Acknowledgements
The authors were thankful to DST-PURSE, Mangalore University, and the VGST (Vision group of science and technology-Karnataka government) for the instrumentation facility. Sabia kouser is grateful to Directorate of Minorities (DOM), Government of Karnataka for providing fellowship. The authors are grateful to Dr. Saraswasti P. Masti, Investigator Principal (DST-SERB, Project No.SB/EMEQ-213/2014), Department of Chemistry, Karnataka Science College, Dharwad-580001, for providing UTM instrument facility.
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Kouser, S., Prabhu, A., Prashantha, K. et al. In vitro evaluation of modified halloysite nanotubes with sodium alginate-reinforced PVA/PVP nanocomposite films for tissue engineering applications. Appl Nanosci 12, 3529–3545 (2022). https://doi.org/10.1007/s13204-022-02684-3
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DOI: https://doi.org/10.1007/s13204-022-02684-3