In situ synthesis and characterization of nano-hydroxyapatite/starch composites

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Nano-hydroxyapatite/starch composite was synthesized using in situ precipitation. Starch concentration effect on the structure of composite was examined. Characterization of the obtained samples, The X-ray diffraction and Fourier transform infrared spectroscopy demonstrated the purity of the formed nano-HA in the starch matrix. Morphology studies of the samples, checked by field emission scanning electron microscope and transmission electron microscope, show the effects of starch on the size, shape, and morphology of hydroxyapatite nanoparticles.

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Nội dung Text: In situ synthesis and characterization of nano-hydroxyapatite/starch composites

Cite this paper: Vietnam J. Chem., 2023, 61(S1), 51-56 Research article DOI: 10.1002/vjch.202200213 In situ synthesis and characterization of nano-hydroxyapatite/starch composites Nguyen Thi Lan Huong1*, Phan Dinh Tuan1, Phan Thi Ngoc Bich2, Nguyen Minh Thao3, Mai Thanh Tung4 Ho Chi Minh University of Natural Resources and Environment, 1 236B, Le Van Sy, Ward 1, Tan Binh District, Ho Chi Minh City 70000, Viet Nam 2 Institute of Chemistry, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Cau Giay, Hanoi 10000, Viet Nam 3Dong Thap University, 783 Pham Huu Lau, Ward 6, Cao Lanh city, Dong Thap Province 81000, Viet Nam 4 Hanoi University of Sciences and Technology, No. 1, Dai Co Viet, Hai Ba Trung Hanoi 10000, Viet Nam Submitted November 24, 2022; Revised February 22, 2023; Accepted March 13, 2023 Abstract Nano-hydroxyapatite/starch composite was synthesized using in situ precipitation. Starch concentration effect on the structure of composite was examined. Characterization of the obtained samples, The X-ray diffraction and Fourier transform infrared spectroscopy demonstrated the purity of the formed nano-HA in the starch matrix. Morphology studies of the samples, checked by field emission scanning electron microscope and transmission electron microscope, show the effects of starch on the size, shape, and morphology of hydroxyapatite nanoparticles. Keywords. Composite, hydroxyapatite, starch, in situ precipitation. 1. INTRODUCTION engineering. Compared with other polymers, this polymer is biodegradable, biocompatible, and Hydroxyapatite (Ca10(PO4)6(OH)2 - HA) is an helpful inexpensive.[13,14] In HA/starch composites, the polar biomaterial with potential orthopedic, dental, and character of starch providing strong support for maxillofacial applications, because of its valuable adhesion between the HA and starch. In this work, in biocompatibility, bioactivity, and osteoconductivity. situ precipitation of HA/starch composite, starch HA, with similarity in chemical and structural concentration effect on the final structure and characterization considering inorganic component of characterization of the prepared composites are bone, enamel, and dentin has received considerable reported. attention from the biologists and biomaterial scientists.[1] In recent years, many interests have been 2. EXPERIMENTAL attracted by HA which is embedded in polymer matrixes to enhance its applications.[2-4] Organic 2.1. Materials and methods materials surfaces could be modified achieve different properties, such as the ability of carrying The chemical used in this study including Ca(OH)2, functional groups, chelate to metal ions by their H3PO4, starch, absolute ethanol were pure for analysis functional groups and hydrophilicity.[5-8] A composite (China). They were used without any further biomaterial of HA and polymer therefore is awaited purification. to show HA nanoparticles dispersed uniformly in the HA/starch nanocomposites containing various polymer matrix and increase biocompatibility, HA contents (10, 40, and 70 wt.% samples were biodegradation.[9-12] named as HA-10, HA-40 and HA-70, respectively) In biomedical field, biopolymers are an important were synthesized using in situ precipitation at room materials source. Starch is useful biopolymer for temperature. At first, starch was dissolved in double - some applications such as bone replacement implants, distilled water at a concentration of 5 %w/v, and bone cements, drug delivery and scaffolds for tissue stirred for 30 min at 70oC. The Ca(OH)2 suspension 51 Wiley Online Library © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH
25728288, 2023, S1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202200213 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry Nguyen Thi Lan Huong et al. and H3PO4 solution in double - distilled water were 3. RESULTS AND DISCUSSION prepared separately. The Ca(OH)2 suspension was added to the starch solution and stirred for 5 h. Then, 3.1. Formation mechanism of HA/starch H3PO4 solution was added the above suspension. The nanocomposite ethanol was after that dropped into the above mixture to crystallize product. The entire mixture was stirred Figure 1 (a) shows the structure of starch, figure 1 (b) for 15 hours, then centrifuged, washed several times shows chemical structure of hydroxyapatite – HA and with double- distilled water and ethanol. The resultant figure 1 (c) shows schematic representation of the precipitate was dried 48 hours at 50 OC. Pure HA synthesis of HA/starch nanocomposite. Starch is powder was also experimented in the absence of mostly the composition of two homopolymers of D- starch to compare. Reactants quantities were glucose: amylose, a mainly linear α-D(1,4)-glucan optimized to provide a Ca/P molar ratio of 1.67 in all and branched amylopectin, having the same backbone experiments. structure as amylose but with many α-1,6-linked 4 branch points (Fig. 1a). Many hydroxyl groups on Characterization methods of HA and HA/starch starch chains were observed, two secondary hydroxyl composites groups at C-2 and C-3 of each glucose residue, as well By using CuK radiation, X-ray diffraction (XRD) as one primary hydroxyl group at C-6 when it is not patterns were observed on a D8 Advance Brucker. bonded.[15] The dissolution and dissociation of a small Infrared spectrophotometry (FTIR) was implemented part of Ca(OH)2 were observed after the addition of on Affinity-S1, Shimadzu. The morphology pictures Ca(OH)2 to the starch solution. The Ca2+ ions were were captured by the field emission scanning electron attached with OH- group in the starch matrix. The microscope (FESEM, S4800-Hitachi) and mainly of Ca(OH)2 was dissociated when adding transmission electron microscope (TEM, JEOL JEM- H3PO4 into the above mixed solution, then the 1010, sonication of sample in distillation water for 30 combination of Ca2+, OH-, and PO3- ions formed HA min and the deposition of sample on carbon-coated crystals. The links in the network structure of the copper grid were carried out). Thermogravimetric starch were limited growth of HA crystal nucleation. analysis (TGA) and differential thermal analysis In addition, PO 3- ions bind to the – OH-Ca2+ group in (DTA) were performed from room temperature to the starch matrix to form hydroxyapatite particles and 800oC in air atmosphere with heating rate of 10oC/min the starch matrix controls the growth of HA on Setaram Labsys Evo thermal analyzer. nanoparticle. (c) PO43- Ca2+ -OH ` OH- HA starch (b) Figure 1: (a) Structure of starch; (b) Chemical structure of hydroxyapatite – HA and (c) Schematic representation of HA/starch composite formation 3.2. XRD pattern all samples have characteristic peaks of crystalline HA (compared to JCPDS file 00-024-0033). The Figure 2 shows the reflection planes which results were observed and provides evidence of no correspond to the characteristic XRD peaks of HA characteristic diffraction angles from other calcium and HA/starch nanocomposites. The XRD patterns of phosphate phases are detected. The main diffraction © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 52
25728288, 2023, S1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202200213 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry In situ synthesis and characterization of… peaks were discovered for the HA and HA/starch matrix. It was found that the extensive broadening composites at angles 25.89º, 31.91º, 32.95º, 34.08º, and overlapping of the peaks of XRD patterns of the 39.85º, and 46.71º represents, respectively the planes composites, which indicated that the HA crystals of (002), (211), (300), (202), and (310). the composites were small size and low A comparison of the observed diffracted pattern of crystallinity.[8,16] The presence of starch limited the the HA and HA/starch composites reveals a similar growth in size and crystallinity of HA nanoparticles. which demonstrates the formation of HA in starch Figure 2: XRD patterns of HA and HA/starch composites 3.3. FT-IR spectra The SEM images of HA, starch, and HA/starch composite samples with various contents of starch are Figure 3 shows the FT-IR spectra of HA, starch and illustrated in figure 4. The figure 4a of HA shows that HA/starch composites. The bands located at 1121- particles exhibit nanorod-like morphology. It shows 1045 and 603-562 cm-1 are assigned respectively to evidence of the presence of agglomerations of the the ν3 and ν4 P-O vibration modes of regular particles, which are because of high specific surface tetrahedral PO43- groups. Observation of the ν1 energy of HA nanoparticles. In the case of composites symmetric stretching mode of phosphate group can be (Fig. 4b, c, d), the morphology is obviously change seen at 949 cm-1. The bands at 1423 and 880 cm-1 and very different from smooth surface of the starch were observed because of the stretching mode of (Fig. 4e). Further, it reveals that the HA particle size carbonate, which might be result of air acquiring decreases with the increase in starch content. The during precipitation process. The small peaks at 3570 particles size of HA is about 75 nm in length and 15 and 660 cm-1 can be considered respectively the OH- nm in width. In the HA-70 composite (Fig. 4b), they stretching and bending vibration modes. In the starch are about 40 nm and 18 nm; their aggregations spectrum, the wide band observed at 3386 cm-1 is decrease. For HA-40 (Fig. 4c) the length and the attributed to the O-H stretching and its width ascribed width of HA particle are 20 nm and 8 nm respectively. to the formation of inter- and intramolecular Unlike the above samples, for the HA-10 (Fig. hydrogen bonds which overlap the –OH of the HA in 4d), the length of the HA particles is reduced in size, composites spectrum.[17] The band at 1630 cm-1 is the particles exhibit sphere morphology, diameter is attributed to the –OH group of the water. The band approximately 12 nm. Thus, increasing in the starch observed between 2929-2850 cm-1 corresponds to C- content leads to a change in their morphology from H stretching band of starch. There are the small shifts rod-like to sphere. The presence of starch in the position of absorption bands for the HA significantly affects to the morphology of the prepared in composites, indicating of dissociation and composite because of interaction between the -OH interaction of starch with HA crystals.[18] groups of starch and the Ca2+ ions in the solution; this existence also affects the orientation of the crystal 3.4. SEM images nucleation of HA on the starch chain. © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 53
25728288, 2023, S1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202200213 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry Nguyen Thi Lan Huong et al. Wave number (cm-1) Figure 3: FT-IR spectrums of (a) starch, (b) HA-70, (c) HA-40, (d) HA-10 and (e) HA samples (a) (b) (c) (d) (e) Figure 4: SEM images of (a) HA, (b) HA-70, (c) HA-40, (d) HA-10 and (e) starch samples 3.5. TEM images composite. Observed from image, HA particles display nanorod morphology. The particles size of Figure 5 shows TEM images of HA and HA-40 HA (Fig. 5a) is 75 nm in length and 15 nm in width. 54 Wiley Online Library © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH
25728288, 2023, S1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202200213 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry In situ synthesis and characterization of… In the HA-40 composite (Fig. 5b), the parameter is temperature to 235°C corresponds to the initial about 20 nm and 8 nm respectively. The SEM endothermic peak in the DTA curve, the weight loss pictures show the sample surface. However, based on was attributed to the vaporization of residual water. A TEM analysis, the homogeneous dispersion of mass loss of 33.99% in the range from 235 to 455°C, particles was observed in polymer matrix. Further, the was assigned to the thermal decomposition of starch, micro image does not show any reliable evidence of corresponding the next strong two exothermic peaks agglomeration existence. in the DTA curve (318.6 and 406.0oC). Meanwhile, for starch samples, the decomposition peaks are 3.6. Thermal analysis observed at the obviously higher temperature, 407.4 and 536.5oC, respectively. The degradation The thermal analysis measurement (DTA, TGA) of temperature was moved to lower temperatures HA, starch and composite samples was performed indicating a decreased thermal stability, possibly from room temperature to 800°C in air atmosphere relating to the interaction between the HA molecule with heating rate 10o/min. Figure 6 shows the thermal and starch chain. The third step from 455oC onwards, decomposition behaviour of composites is similar. the weight loss was attributed to the thermal For the composite (HA-40), in the TGA curve, decomposition of CO32- and chemisorbed water in the threesteps were observed. The first step from room composite.[19] (a) (b) Figure 5: TEM images of (a) HA and (b) HA-40 composite The nano-HA particles are uniformly dispersed in starch matrix, do not agglomerate and significantly changed morphology. Increasing concentration of starch led to reduced HA nanoparticles size because of interaction between the -OH groups of starch and the Ca2+ ions of HA and the orientation of the crystal nucleation of HA on the starch chain. REFERENCES 1. Khandan A., Karamian E., Bonakdarchian M. Mechanochemical synthesis evaluation of nanocrystalline bone derived bioceramic powder using for bone tissue engineering, Dent Hypotheses, Figure 6: DTA-TGA curves of (a) HA, (b) HA-70, 2014, 5(4), 155-161. (c) HA-40, (d) HA-10, (e) starch samples 2. D. A. Wahl, J. T. Czernuszka. Collagen- hydroxyapatite composites for hard tissue repair, 4. CONCLUSION European Cells and Materials, 2006, 11, 43-56. 3. Carlos Peniche, Yaimara Solís, Natalia Davidenco, The HA/starch composites with different contents of Raúl García. Chitosan/hydroxyapatite-based HA (10, 40, 70 wt.%) is synthesized by simple composites, Biotecnología Aplicada, 2010, 27(3), chemical process using starch as a template matrix 202-210. facilitating in-situ precipitation of HA nanoparticles. 4. M. Sivakumar, K. Panduranga Rao. Preparation, © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 55
25728288, 2023, S1, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/vjch.202200213 by Readcube (Labtiva Inc.), Wiley Online Library on [01/05/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License Vietnam Journal of Chemistry Nguyen Thi Lan Huong et al. characterization and in vitro release of gentamicin Composites with Various Ratio of Hydroxyapatite to from coralline hydroxyapatite-gelatin composite Starch, IOP Conf. Series: Materials Science and microspheres, Biomaterials, 2002, 23, 3175-3181. Engineering, 2020 864. 5. Djalila Boudemagh, Pierre Venturini, Solenne 12. Beh Chong You, Cheng Ee Meng, Nashrul Fazli Fleutot, Franck Cleymand. Elaboration of Mohd Nasir, Emma Ziezie Mohd Tarmizi, Khor hydroxyapatite nanoparticles and Shing Fhan, Eng Swee Kheng, Mohd Shukry Abdul chitosan/hydroxyapatite composites: a present status, Majid, Mohd Ridzuan Mohd Jamir. Dielectric and Polymer Bulletin, 2019, 76, 2621-2653. biodegradation properties of biodegradable nano- 6. Vijaykiran N., Narwade Rajendra S., Khairnar Vanja hydroxyapatite/starch bone scaffold, Journal of Koko. In situ Synthesized Hydroxyapatite-Cellulose Materials Research and Technology, 2022, 18, 3215- Nanofirils as Biosorbents for Heavy Metal Ions 3226. Removal, J Polym Environ, 2018, 26, 2130-2141. 13. J. F. Mano, A. Sousa Rui, F. Boesel Luciano, M. 7. I. Manjubala, Poulami Basu, U. Narendrakumar. In Neves Nuno, L. Reis Rui. Bioinert biodegradable and situ synthesis of hydroxyapatite/carboxymethyl injectable polymeric matrix composites for hard cellulose composites for bone regeneration tissue replacement: state of the art and recent applications, Colloid Polym Sci., 2018, 296, 1729- developments, Composites Science and Technology, 1737. 2004, 64. 8. M. S. Sadjadi, M. Meskinfam, H. Jazdarreh. 14. James BeMiller, Roy Whistler, Starch: Chemistry and Hydroxyapatite–starch nano biocomposites synthesis Technology, Third Ed., Academic Press, Elsevier, and characterization, International Journal of Nano 2009. Dimension, 2010, 1(1), 57-63. 15. C. M. Ott, D. F. Day. Polymer modification: 9. N. Pramanik, D. Mishra, I. Banerjee, T. K. Maiti, P. Principles techniques, and applications, Marcel Bhargava, P. Pramanik. Chemicals Synthesis, Dekker, Inc., New York, 2000. Characterization, and biocompatibility study of 16. W. Y. Choi, H. E. Kim, S. Y. Oh, Y. H. Koh. hydroxyapatite/chitosan phosphate nanocomposite Synthesis of poly(-caprolactone)/hydroxyapatite for bone tissue engineering applications, nanocomposites using in-situ co-precipitation, International Journal of Biomaterials, 2009, 15, 218- Materials Science and Engineering C, 2010, 30. 225. 17. F. Huang, Y. Shen, A. Xie, J. Zhu, C. Zhang, S. Li, 10. Qiaoling Hu, Baoqiang Li, Mang Wang, Jiacong and J. Zhu. Study on synthesis and properties of Shen. Preparation and characterization of hydroxyapatite nanorods and its complex containing biodegradable chitosan/hydroxyapatite biopolymer, Journal of Materials Science, 2007, 42. nanocomposite rods via in situ hybridization: a 18. H. W. Kim, J. C. Knowles, H. E. Kim. potential material as internal fixation of bone fracture, Gelatin/hydroxyapatite nanocomposite scaffolds for Biomaterial, 2004, 25, 779-785. bone repair, J. Biomed. Mater. Res., 2005, 72A. 11. Beh Chong You, Cheng Ee Meng, Shahriman Abu 19. M. Markovic, B. O. Fowler, M. S. Tung. Preparation Bakar, Nashrul Fazli Mohd Nasir, Eng Swee Kheng, and Comprehensive Characterization of a Calcium Mohd Shukry Abdul Majid, Mohd Ridzuan Mohd Hydroxyapatite Reference Materials, Journal Jamir and Khor Shing Fhan. Microwave Dielectric Research of the National Institute of Standards and Analysis on Porous Hydroxyapatite/Starch Technology, 2004, 109(6). Corresponding author: Nguyen Thi Lan Huong Ho Chi Minh University of Natural Resources and Environment 236B, Le Van Sy, Ward 1 Tan Binh District, Ho Chi Minh City 70000, Viet Nam E-mail: ntlhuong@hcmunre.edu.vn; Tel.: +84- 913961333. © 2023 Vietnam Academy of Science and Technology, Hanoi & Wiley-VCH GmbH www.vjc.wiley-vch.de 56