Synthesis and Characterization of Hydroxyapatite/Alginate Composites: Study of pH and Sintering Influenced on the Structural, Morphological, and Clindamycin Release Behavior

Wulandari Wulandari; Dini Muthi'ah Islami; Novesar Jamarun; Diana Vanda Wellia; Emriadi Emriadi

doi:10.22146/ijc.84558

Synthesis and Characterization of Hydroxyapatite/Alginate Composites: Study of pH and Sintering Influenced on the Structural, Morphological, and Clindamycin Release Behavior

https://doi.org/10.22146/ijc.84558

Wulandari Wulandari⁽¹⁾, Dini Muthi'ah Islami⁽²⁾, Novesar Jamarun^(3*), Diana Vanda Wellia⁽⁴⁾, Emriadi Emriadi⁽⁵⁾

(1) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Andalas, Limau Manis, Padang 25163, Indonesia
(2) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Andalas, Limau Manis, Padang 25163, Indonesia
(3) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Andalas, Limau Manis, Padang 25163, Indonesia
(4) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Andalas, Limau Manis, Padang 25163, Indonesia
(5) Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Andalas, Limau Manis, Padang 25163, Indonesia
(*) Corresponding Author

Abstract

The hydroxyapatite/alginate (HAp/Alg) composite was synthesized using an in-situ precipitation route. The effect of pH (8, 9, 10, and 11) and calcination temperature (300, 500, 700, and 900 °C) were studied by characterization techniques such as X-ray diffraction (XRD), Fourier-transform infrared (FTIR), and scanning electron microscopy with energy-dispersive X-ray (SEM with EDAX). XRD results show the hexagonal crystal system of HAp for each pH value and the biphase (HAp and whitelockite) for the sintering temperature at 700 and 900 °C. The FTIR spectra show no impurity peaks. SEM images revealed spherical-like (HAp/Alg-11) and flake-like (HAp/Alg-900) particles with good homogeneity, size, and shape that could be notable for biomedical utilization, such as drug delivery material. Drug loading and release ability of pure HAp, HAp/Alg-11, and HAp/Alg-900 composites have been investigated with clindamycin hydrochloride as the drug model. The maximum clindamycin HCl release from HAp, HAP/Alg-11, and HAp/Alg-900 reached 74.48, 92.75, and 69.65% in the 8^th hour. HAp/Alg-11 has the highest release because it has the largest surface area of 162.584 m²/g. Antibacterial test results showed HAp/Alg-11 has antibacterial activity against Staphylococcus aureus and Escherichia coli, confirming that HAp/Alg-11 composite has the potential to be applied as drug delivery.

Keywords

alginate; clindamycin hydrochloride; composite; drug release; hydroxyapatite

Full Text:

Full Text PDF

References

[1] Lu, Y., Dong, W., Ding, J., Wang, W., and Wang, A., 2019, “Hydroxyapatite Nanomaterials: Synthesis, Properties, and Functional Applications” in Nanomaterials from Clay Minerals: A New Approach to Green Functional Materials, Eds. Wang, A., and Wang, W., Elsevier, Cambridge, MA, US, 485–536.

[2] Labanni, A., Zulhadjri, Z., Handayani, D., Ohya, Y., and Arief, S., 2020, Size controlled synthesis of well-distributed nano-silver on hydroxyapatite using alkanolamine compounds, Ceram. Int., 46 (5), 5850–5855.

[3] Kumar, G.S., Karunakaran, G., Girija, E.K., Kolesnikov, E., Van Minh, N., Gorshenkov, M.V., and Kuznetsov, D., 2018, Size and morphology-controlled synthesis of mesoporous hydroxyapatite nanocrystals by microwave-assisted hydrothermal method, Ceram. Int., 44 (10), 11257–11264.

[4] Hariani, P.L., Rachmat, A., Said, M., and Salni, S., 2021, Modification of fishbone-based hydroxyapatite with MnFe₂O₄ for efficient adsorption of Cd(II) and Ni(II) from aqueous solution, Indones. J. Chem., 21 (6), 1471–1483.

[5] Islami, D.M., Wulandari, W., Jamarun, N., Syukri, S., and Sisca, V., 2023, In-situ hydrothermal method for graphene oxide/hydroxyapatite synthesis from scallop shells, Rasayan J. Chem., 16 (1), 456–462.

[6] Haider, A., Haider, S., Han, S.S., and Kang, I.K., 2017, Recent advances in the synthesis, functionalization and biomedical applications of hydroxyapatite: A review, RSC Adv., 7 (13), 7442–7458.

[7] Ali, A., Hasan, A., and Negi, Y.S., 2022, Effect of carbon based fillers on xylan/chitosan/nano-HAp composite matrix for bone tissue engineering application, Int. J. Biol. Macromol., 197, 1–11.

[8] Noviyanti, A.R., Akbar, N., Deawati, Y., Ernawati, E.E., Malik, Y.T., Fauzia, R.P., and Risdiana, R., 2020, A novel hydrothermal synthesis of nanohydroxyapatite from eggshell-calcium-oxide precursors, Heliyon, 6 (4), e03655.

[9] Wulandari, W., Islami, D.M., Wellia, D.V., Emriadi, E., Sisca, V., and Jamarun, N., 2023, The effect of alginate concentration on crystallinity, morphology, and thermal stability properties of hydroxyapatite/alginate composite, Polymers, 15 (3), 614.

[10] Lazić, V., Smičiklas, I., Marković, J., Lončarević, D., Dostanić, J., Ahrenkiel, S.P., and Nedeljković, J.M., 2018, Antibacterial ability of supported silver nanoparticles by functionalized hydroxyapatite with 5-aminosalicylic acid, Vacuum, 148, 62–68.

[11] Wan, F., Ping, H., Wang, W., Zou, Z., Xie, H., Su, B.L., Liu, D., and Fu, Z., 2021, Hydroxyapatite-reinforced alginate fibers with bioinspired dually aligned architectures, Carbohydr. Polym., 267, 118167.

[12] Madhumathi, K., Binulal, N.S., Nagahama, H., Tamura, H., Shalumon, K.T., Selvamurugan, N., Nair, S.V., and Jayakumar, R., 2009, Preparation and characterization of novel β-chitin–hydroxyapatite composite membranes for tissue engineering applications, Int. J. Biol. Macromol., 44 (1), 1–5.

[13] Abdulkareem, M.H., Abdalsalam, A.H., and Bohan, A.J., 2019, Influence of chitosan on the antibacterial activity of composite coating (PEEK/HAp) fabricated by electrophoretic deposition, Prog. Org. Coat., 130, 251–259.

[14] Apriliyanto, Y.B., Sugiarti, S., and Sukaryo, S.G., 2020, Enhancing thermal and mechanical properties of UHMWPE/HA composite as tibial tray, Indones. J. Chem., 20 (3), 597–607.

[15] Sanchez, A.G., Prokhorov, E., Luna-Barcenas, G., Hernández-Vargas, J., Román-Doval, R., Mendoza, S., and Rojas-Chávez, H., 2021, Chitosan-hydroxyapatite-MWCNTs nanocomposite patch for bone tissue engineering applications, Mater. Today Commun., 28, 102615.

[16] Adhikari, J., Perwez, M.S., Das, A., and Saha, P., 2021, Development of hydroxyapatite reinforced alginate–chitosan based printable biomaterial-ink, Nano-Struct. Nano-Objects, 25, 100630.

[17] Rahyussalim, A.J., Aprilya, D., Handidwiono, R., Whulanza, Y., Ramahdita, G., and Kurniawati, T., 2022, The use of 3D polylactic acid scaffolds with hydroxyapatite/alginate composite injection and mesenchymal stem cells as laminoplasty spacers in rabbits, Polymers, 14 (16), 3292.

[18] Tiraton, T., Suwantong, O., Chuysinuan, P., Ekabutr, P., Niamlang, P., Khampieng, T., and Supaphol, P., 2022, Biodegradable microneedle fabricated from sodium alginate-gelatin for transdermal delivery of clindamycin, Mater. Today Commun., 32, 104158.

[19] Nigam, A., and Pawar, S.J., 2020, Structural, magnetic, and antimicrobial properties of zinc doped magnesium ferrite for drug delivery applications, Ceram. Int., 46 (4), 4058–4064.

[20] Yuvaraj, S., Muthukumarasamy, N., Flores, M., Rajesh, G., Paraskevopoulos, K.M., Pouroutzidou, G.K., Theodorou, G.S., Ioannidou, K., Lusvarghi, L., Velauthapillai, D., and Yoganand, C.P., 2021, Incorporation of nanosized carbon over hydroxyapatite (HAp) surface using DC glow discharge plasma for biomedical application, Vacuum, 190, 110300.

[21] Sun, Y., Yang, H., and Tao, D., 2011, Microemulsion process synthesis of lanthanide-doped hydroxyapatite nanoparticles under hydrothermal treatment, Ceram. Int., 37 (7), 2917–2920.

[22] Zheng, Y., Wang, L., Bai, X., Xiao, Y., and Che, J., 2022, Bio-inspired composite by hydroxyapatite mineralization on (bis)phosphonate-modified cellulose-alginate scaffold for bone tissue engineering, Colloids Surf., A, 635, 127958.

[23] Prekajski Đorđević, M., Maletaškić, J., Stanković, N., Babić, B., Yoshida, K., Yano, T., and Matović, B., 2018, In-situ immobilization of Sr radioactive isotope using nanocrystalline hydroxyapatite, Ceram. Int., 44 (2), 1771–1777.

[24] Sirajudheen, P., Karthikeyan, P., Vigneshwaran, S., Basheer, M.C., and Meenakshi, S., 2021, Complex interior and surface modified alginate reinforced reduced graphene oxide-hydroxyapatite hybrids: Removal of toxic azo dyes from the aqueous solution, Int. J. Biol. Macromol., 175, 361–371.

[25] Jariya, S.A.I., Padmanabhan, V.P., Kulandaivelu, R., Prakash, N., Mohammad, F., Al-Lohedan, H.A., Paiman, S., Schirhagl, R., Hossain, M.A.M., and Sagadevan, S., 2021, Drug delivery and antimicrobial studies of chitosan-alginate based hydroxyapatite bioscaffolds formed by the Casein micelle assisted synthesis, Mater. Chem. Phys., 272, 125019.

[26] Laput, O.A., Zuza, D.A., Vasenina, I.V., Savkin, K.P., and Kurzina, I.A., 2020, Effect of silver ION implantation on surface physicochemical properties of composite materials based on polylactic acid and hydroxyapatite, Vacuum, 175, 109251.

[27] Bera, M., Gupta, P., and Maji, P.K., 2018, Facile one-pot synthesis of graphene oxide by sonication assisted mechanochemical approach and its surface chemistry, J. Nanosci. Nanotechnol., 18 (2), 902–912.

[28] Victoria, E.C., and Robinson M, C., 2019, Comparative studies on synthesis and sintering studies of biologically derived hydroxyapatite from Capria hircus (Goat) and Bos primigenius (Bovine), Vacuum, 160, 378–383.

[29] Palanivelu, R., Mary Saral, A., and Ruban Kumar, A., 2014, Nanocrystalline hydroxyapatite prepared under various pH conditions, Spectrochim. Acta, Part A, 131, 37–41.

[30] Rodríguez-Lugo, V., Karthik, T.V.K., Mendoza-Anaya, D., Rubio-Rosas, E., Villaseñor Cerón, L.S., Reyes-Valderrama, M.I., and Salinas-Rodríguez, E., 2018, Wet chemical synthesis of nanocrystalline hydroxyapatite flakes: Effect of pH and sintering temperature on structural and morphological properties, R. Soc. Open Sci., 5 (8), 180962.

[31] Jarudilokkul, S., Tanthapanichakoon, W., and Boonamnuayvittaya, V., 2007, Synthesis of hydroxyapatite nanoparticles using an emulsion liquid membrane system, Colloids Surf., A, 296 (1), 149–153.

[32] Chen, B.H., Chen, K.I., Ho, M.L., Chen, H.N., Chen, W.C., and Wang, C.K., 2009, Synthesis of calcium phosphates and porous hydroxyapatite beads prepared by emulsion method, Mater. Chem. Phys., 113 (1), 365–371.

[33] Lakrat, M., Jodati, H., Mejdoubi, E.M., and Evis, Z., 2023, Synthesis and characterization of pure and Mg, Cu, Ag, and Sr doped calcium-deficient hydroxyapatite from brushite as precursor using the dissolution-precipitation method, Powder Technol., 413, 118026.

[34] Czarnecka, B., and Nicholson, J.W., 2013, The use of alginate impression material for the controlled release of sodium fusidate, Dent. Forum, XLI (1), 11–14.

[35] Hasnain, M.S., Nayak, A.K., Singh, M., Tabish, M., Ansari, M.T., and Ara, T.J., 2016, Alginate-based bipolymeric-nanobioceramic composite matrices for sustained drug release, Int. J. Biol. Macromol., 83, 71–77.

[36] Pradid, J., Keawwatana, W., Boonyang, U., and Tangbunsuk, S., 2017, Biological properties and enzymatic degradation studies of clindamycin-loaded PLA/HAp microspheres prepared from crocodile bones, Polym. Bull., 74 (12), 5181–5194.

[37] Seidenstuecker, M., Ruehe, J., Suedkamp, N.P., Serr, A., Wittmer, A., Bohner, M., Bernstein, A., and Mayr, H.O., 2017, Composite material consisting of microporous β-TCP ceramic and alginate for delayed release of antibiotics, Acta Biomater., 51, 433–446.

DOI: https://doi.org/10.22146/ijc.84558