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Ionically cross-linked chitosan–halloysite composite microparticles for sustained drug release

Published online by Cambridge University Press:  27 February 2018

Bojan Čalija*
Affiliation:
Department of Pharmaceutical Technology and Cosmetology, University of Belgrade – Faculty of Pharmacy, Vojvode Stepe 450, Belgrade 11 221, Serbia
Jela Milić
Affiliation:
Department of Pharmaceutical Technology and Cosmetology, University of Belgrade – Faculty of Pharmacy, Vojvode Stepe 450, Belgrade 11 221, Serbia
Jelena Janićijević
Affiliation:
Department of Pharmaceutical Technology and Cosmetology, University of Belgrade – Faculty of Pharmacy, Vojvode Stepe 450, Belgrade 11 221, Serbia
Aleksandra Daković
Affiliation:
Institute for the Technology of Nuclear and Other Mineral Raw Materials, Franše d’Epere 86, Belgrade 11000, Serbia
Danina Krajišnik
Affiliation:
Department of Pharmaceutical Technology and Cosmetology, University of Belgrade – Faculty of Pharmacy, Vojvode Stepe 450, Belgrade 11 221, Serbia

Abstract

This study investigated the potential of halloysite nanotubes (HNTs) to improve the sustained release properties of chitosan (CS) microparticles cross-linked ionically with tripolyphosphate (TPP). Composite CS-HNTs microparticles were obtained by a simple and eco-friendly procedure based on a coaxial extrusion technique. Prior to encapsulation, a water-soluble model drug, verapamil hydrochloride (VH), was adsorbed successfully on HNTs. The microparticles were characterized by optical microscopy, Fourier transform infrared (FTIR) spectroscopy, differential thermal analysis/ thermogravimetric analysis (DTA/TG) and evaluated for encapsulation efficiency and drug-release properties. The composite particles had a slightly deformed spherical shape and micrometric size with average perimeters ranging from 485.4 ± 13.3 to 492.4 ± 11.9 μm. The results of FTIR spectroscopy confirmed non-covalent interactions between CS and HNTs within composite particle structures. The DTA and TG studies revealed increased thermal stability of the composite particles in comparison to the CS-TPP particles. Drug adsorption on HNTs prior to encapsulation led to an increase in encapsulation efficiency from 19.6 ± 2.9 to 84.3 ± 1.9%. In contrast to the rapid release of encapsulated model drug from CS-TPP microparticles, the composite CS-HNTs microparticles released drug in a sustained manner, showing the best fit to the Bhaskar model. The results presented here imply that HNTs could be used to improve morphology, encapsulation efficiency and sustained drug-release properties of CS microparticles cross-linked ionically with TPP.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2017

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References

Anal, A.K. & Stevens, W.F. (2005) Chitosan-alginate multilayer beads for controlled release of ampicillin. International Journal of Pharmaceutics, 290, 4554.Google Scholar
Arcudi, F., Cavallaro, G., Lazzara, G., Massaro, M., Milioto, S., Noto, R. & Riela, S. (2014) Selective functionalization of halloysite cavity by click reaction: structured filler for enhancing mechanical properties of bio-nanocomposite films. The Journal of Physical Chemistry C, 118, 1509515101.CrossRefGoogle Scholar
Azevedo, J.R., Sizilio, R.H., Brito, M.B., Costa, A.M.B., Serafini, M.R., Araújo, A.A.S., Santos, M.R.V., Lira, A.A.M. & Nunes, R.S. (2011) Physical and chemical characterization insulin-loaded chitosan-TPP nano-particles. Journal of Thermal Analysis and Calorimetry, 106, 685689.Google Scholar
Bhardwaj, N. & Kundu, S.C. (2011) Silk fibroin protein and chitosan polyelectrolyte complex porous scaffolds for tissue engineering applications. Carbohydrate Polymers, 85, 325333.CrossRefGoogle Scholar
Bhaskar, R., Murthy, R.S.R., Miglani, B.D. & Viswanathan, K. (1986) Novel method to evaluate diffusion controlled release of drug from resinate. International Journal ofPharmaceutics, 28, 59–66.Google Scholar
Bhumkar, D.R. & Pokharkar, V.B. (2006) Studies on effect of pH on cross-linking of chitosan with sodium tripolyphosphate: a technical note. AAPS PharmSciTech, 7, E138-E143.Google Scholar
Birch, N.P. & Schiffman, J.D. (2014) Characterization of self-assembled polyelectrolyte complex nanoparticles formed from chitosan and pectin. Langmuir, 30, 34413447.CrossRefGoogle ScholarPubMed
Čalija, B., Milic, I, Cekic, N., Krajišnik, D., Daniels, R. & Savic, S. (2013) Chitosan oligosaccharide as prospective cross-linking agent for naproxen-loaded Ca-alginate microparticles with improved pH sensitivity. Drug Development and Industrial Pharmacy, 39, 7788.CrossRefGoogle ScholarPubMed
Čalija, B., Savic, S., Krajišnik, D., Daniels, R., Vučen, S., Markovic, B. & Milic, J. (2015) pH-sensitive polyelec-trolyte films derived from submicron chitosan/Eudragit® L 100-55 complexes: Physicochemical characterization and in vitro drug release. Journal of Applied Polymer Science, 132, E1-E9.CrossRefGoogle Scholar
Cavallaro, G., Lazzara, G. & Milioto, S. (2010) Dispersions of nanoclays of different shapes into aqueous and solid biopolymeric matrices. Extended physicochemical study. Langmuir, 27, 11581167.Google Scholar
Costa, P. & Lobo, J.M.S. (2001) Modeling and comparison of dissolution profiles. European Journal of Pharmaceutical Sciences, 13, 123–133.Google Scholar
Dash, M., Chiellini, F., Ottenbrite, R.M. & Chiellini, E. (2011) Chitosan — Aversatile semi-synthetic polymer in biomedical applications. Progress in Polymer Science, 36, 9811014.Google Scholar
De Silva, R.T., Pasbakhsh, P., Goh, K.L., Chai, S.P. & Ismail, H. (2013) Physico-chemical characterisation of chit-osan/halloysite composite membranes. Polymer Testing, 32, 265271.CrossRefGoogle Scholar
Desai, K.G.H. & Park, H.J. (2005) Preparation and characterization of drug-loaded chitosan—tripolypho-sphate microspheres by spray drying. Drug Development Research, 64, 114128.CrossRefGoogle Scholar
Dhawan, S., Singla, A.K. & Sinha, V.R. (2004) Evaluation of mucoadhesive properties of chitosan microspheres prepared by different methods. AAPS PharmSciTech, 5, 122128.Google Scholar
Fan, W., Yan, W., Xu, Z. & Ni, H. (2012) Formation mechanism of monodisperse, low molecular weight chitosan nanoparticles by ionic gelation technique. Colloids and Surfaces B: Biointerfaces, 90, 2127.CrossRefGoogle ScholarPubMed
Freundlich, H. (1932) Of the adsorption of gases. Section II. Kinetics and energetics of gas adsorption. Introductory paper to section II. Transactions of the Faraday Society, 28, 195201.Google Scholar
Hanif, M., Jabbar, F., Sharif, S., Abbas, G., Farooq, A. & Aziz, M. (2016) Halloysite nanotubes as a new drug-delivery system: a review. Clay Minerals, 51, 469477.Google Scholar
Jana, S., Manna, S., Nayak, A.K., Sen, K.K. & Basu, S.K. (2014) Carbopol gel containing chitosan-egg albumin nanoparticles for transdermal aceclofenac delivery. Colloids and Surfaces B: Biointerfaces, 114, 36-44.Google Scholar
Janicijevic, I, Krajišnik, D., Čalija, B., Vasiljevic, B.N., Dobričic Y, Dakovic, A., Antonijevic, M.D. & Milic, J. (2015) Modified local diatomite as potential functional drug carrier - A model study for diclofenac sodium. International Journal of Pharmaceutics, 496, 466-474.Google Scholar
Joussein, E., Petit, S., Churchman, J., Theng, B., Righi, D. & Delvaux, B. (2005) Halloysite clay minerals - a review. Clay Minerals, 40, 383426.Google Scholar
Kadi, S., Lellou, S., Marouf-Khelifa, K., Schott, J., Gener-Batonneau, I. & Khelifa, A. (2012) Preparation, characterisation and application of thermally treated Algerian halloysite. Microporous and Mesoporous Materials, 158, 4754.Google Scholar
Kim, J.Y., Choi, S.J., Oh, J.M., Park, T. & Choy, J.H. (2007) Anticancer drug-inorganic nanohybrid and its cellular interaction. Journal of Nanoscience and Nanotechnology, 7, 37003705.Google Scholar
Knaul, J.Z., Hudson, S.M. & CreberK.A. (1999) Improved mechanical properties of chitosan fibers. Journal of Applied Polymer Science, 72, 17211732.Google Scholar
Ko, J.A., Park, H.J., Hwang, S.J., Park, J.B. & Lee, J.S. (2002) Preparation and characterization of chitosan microparticles intended for controlled drug delivery. International Journal of Pharmaceutics, 249, 165174.CrossRefGoogle ScholarPubMed
Kurkuri, M.D., Kulkarni, A.R., Kariduraganavar, M.Y. & Aminabhavi, T.M. (2001) In vitro release study of verapamil hydrochloride through sodium alginate interpenetrating monolithic membranes. Drug Development and Industrial Pharmacy, 27, 11071114.CrossRefGoogle ScholarPubMed
Langmuir, I. (1918) The adsorption of gases on plane surfaces of glass, mica and platinum. Journal of the American Chemical Society, 40, 13611403.Google Scholar
Lawrie, G., Keen, I., Drew, B., Chandler-Temple, A., Rintoul, L., Fredericks, P. & Grøndahl, L. (2007) Interactions between alginate and chitosan biopoly-mers characterized using FTIR and XPS. Biomacromolecules, 8, 2533–2541.Google Scholar
Li, X., Ouyang, J., Yang, H. & Chang, S. (2016) Chitosan modified halloysite nanotubes as emerging porous microspheres for drug carrier. Applied Clay Science, 126, 306–312.Google Scholar
Liu, M., Zhang, Y., Wu, C., Xiong, S. & Zhou, C. (2012) Chitosan/halloysite nanotubes bionanocomposites: structure, mechanical properties and biocompatibility. International Journal of Biological Macromolecules, 51, 566575.Google Scholar
Liu, M., Wu, C., Jiao, Y., Xiong, S. & Zhou, C. (2013) Chitosan—halloysite nanotubes nanocomposite scaf-folds for tissue engineering. Journal of Materials ChemistryB, 1, 20782089.Google Scholar
Liu, M., He, R., Yang, J., Long, Z., Huang, B., Liu Y & Zhou, C. (2016) Polysaccharide-halloysite nanotube compo-sites for biomedical applications: a review. Clay Minerals, 51, 457467.CrossRefGoogle Scholar
Lvov, Y. & Abdullayev, E. (2013) Functional polymer—clay nanotube composites with sustained release of chemical agents. Progress in Polymer Science, 38, 16901719.Google Scholar
Lvov, Y.M., DeVilliers, M.M. & FakhrullinR.F. (2016) The application of halloysite tubule nanoclay in drug delivery. Expert Opinion on Drug Delivery, 13, 977986.Google Scholar
Paluszkiewicz, C., Stodolak, E., Hasik, M. & Blazewicz, M. (2011) FT-IR study of montmorillonite-chitosan nanocomposite materials. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 79, 784788.CrossRefGoogle ScholarPubMed
Pasbakhsh, P., De Silva, R., Vahedi V & Churchman, J. (2016) Halloysite nanotubes: prospects and challenges of their use as additives and carriers-A focused review. Clay Minerals, 51, 479487.Google Scholar
Peng, Q., Liu, M., Zheng, J. & Zhou, C. (2015) Adsorption of dyes in aqueous solutions by chitosan—halloysite nanotubes composite hydrogel beads. Microporous and Mesoporous Materials, 201, 190201.Google Scholar
Rooj, S., Das, A., Thakur, V., Mahaling, R.N., Bhowmick, A.K. & Heinrich, G. (2010) Preparation and properties of natural nanocomposites based on natural rubber and naturally occurring halloysite nanotubes. Materials and Design, 31, 21512156.Google Scholar
Shah, S., Qaqish, R., Patel Y & Amiji, M. (1999) Evaluation of the factors influencing stomach-specific delivery of antibacterial agents for Helicobacter pylori infection. Journal ofPharmacy and Pharmacology, 51,667—672.Google Scholar
Shu, X.Z. & Zhu, K.J. (2000) A novel approach to prepare tripolyphosphate/chitosan complex beads for con-trolled release drug delivery. International Journal of Pharmaceutics, 201, 5158.Google Scholar
Shukla, S.K., Mishra, A.K., Arotiba, O.A. & Mamba, B.B. (2013) Chitosan-based nanomaterials: A state-of-the-art review. International Journal of Biological Macromolecules, 59, 4658.Google Scholar
Silva, S.M.L., Braga, C.R.C., Fook, M.V.L., Raposos, C.M.O., Carvalho, L.H. & Canedo, E.L. (2012) Application of infrared spectroscopy to analysis of chitosan/clay nanocomposites. Pp. 43—62 in: Materials Science, Engineering and Technology (T. Theophile, editor). In Tech, Rijeka, Croatia.Google Scholar
Słomkiewicz, P.M., Szczepanik, B. & GarnuszekM. (2015) Determination of adsorption isotherms of aniline and 4-chloroaniline on halloysite adsorbent by inverse liquid chromatography. Applied Clay Science, 114, 221228.Google Scholar
Soares, E.L., Sousa, A.I., Silva IC, Ferreira, I.M., Novo, C.M. & Borges, J.P. (2016) Chitosan-based nanoparticles as drug delivery systems for doxorubicin: Optimization and modelling. Carbohydrate. Polymers, 147, 304–312.CrossRefGoogle ScholarPubMed
Szczepanik, B., Słomkiewicz, P., Garnuszek, M., Czech, K., Banaś D., Kubala-Kukuś A. & Stabrawa, I. (2015) The effect of chemical modification on the physico-chemical characteristics of halloysite: FTIR, XRF, and XRD studies. Journal of Molecular Structure, 1084, 1622.Google Scholar
Uswatta, S.P., Okeke, I.U. & Jayasuriya, A.C. (2016) Injectable porous nano-hydroxyapatite/chitosan/tripo-lyphosphate scaffolds with improved compressive strength for bone regeneration. Materials Science and Engineering: C, 69, 505512.CrossRefGoogle ScholarPubMed
Xu, Y & Du, Y (2003) Effect of molecular structure of chitosan on protein delivery properties of chitosan nanoparticles. International Journal of Pharmaceutics, 250, 215226.Google Scholar
Yao, J., Wang, Q., Wang, Y., Zhang, Y., Zhang, B. & Zhang, H. (2015) Immobilization of laccase on chitosan-halloysite hybrid porous microspheres for phenols removal. Desalination and Water Treatment, 55, 12931301.Google Scholar
Yu, C.Y., Yin, B.C., Zhang, W., Cheng, S.X., Zhang, X.Z. & Zhuo, R.X. (2009) Composite microparticle drug delivery systems based on chitosan, alginate and pectin with improved pH-sensitive drug release property. Colloids and Surfaces B: Biointerfaces, 68, 245249.Google Scholar
Yuan, P., Tan, D. & Annabi-Bergaya, F. (2015) Properties and applications of halloysite nanotubes: recent research advances and future prospects. Applied Clay Science, 112, 7593.Google Scholar
Zhai, R., Zhang, B., Wan, Y., Li, C., Wang, J. & Liu, J. (2013) Chitosan—halloysite hybrid-nanotubes: Horseradish peroxidase immobilization and applications in phenol removal. Chemical Engineering Journal, 214, 304309.CrossRefGoogle Scholar
Zhang, X.Z., Tian, F.J., Hou, Y.M. & Ou, Z.H. (2015) Preparation and in vitro in vivo characterization of polyelectrolyte alginate-chitosan complex based microspheres loaded with verapamil hydrochloride for improved oral drug delivery. Journal of Inclusion Phenomena and Macrocyclic Chemistry, 81, 429440.Google Scholar