YUAN Qiuhua,SHI Xin,LIANG Jinren,et al.Preparation and antibacterial properties of cerium-zinc co-doped hydroxyapatite-graphene composite[J].Journal of Shenzhen University Science and Engineering,2021,38(3):280-286.[doi:10.3724/SP.J.1249.2021.03280]





Preparation and antibacterial properties of cerium-zinc co-doped hydroxyapatite-graphene composite
深圳大学化学与环境工程学院,广东深圳 518060
YUAN Qiuhua SHI Xin LIANG Jinren WAN Lei JIAN Youliang YANG Yuan LI Ruilong DAI Xiaoyi and WU Wenshan
College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong Province, P.R.China
biomaterials Ce ion (Ce3+) Zn ion (Zn2+) hydroxyapatite graphene co-doping hydrothermal method antibacterial property
铈(Ce)和锌(Zn)都是人体中常见的微量元素,Ce-Zn共掺杂的羟基磷灰石(hydroxyapatite, HA)复合材料在生物医用领域有良好的应用价值.通过一锅水热法成功合成Ce-Zn共掺杂的HA-石墨烯(graphene, GP)复合粉体材料.借助X射线衍射、傅里叶红外光谱、拉曼红外光谱、场发射扫描电子显微镜、能量色散X射线光谱和透射电子显微镜等技术对合成的复合材料进行表征分析.结果表明,通过水热法可成功制备Ce-Zn共掺杂HA-GP复合粉体材料,铈离子和锌离子成功替代部分钙离子进入HA的晶格中.由于铈离子、锌离子与钙离子半径不同,随着铈离子和锌离子掺杂摩尔分数的增加,复合材料中无定形相晶型增多,并且开始出现团聚现象;通过抗菌性能测试,发现引入铈离子和锌离子的HA-GP复合材料的抗菌性得到较大提高,当铈离子和锌离子掺杂摩尔分数均增至10%时,Ce-Zn-HA-GP复合材料的杀菌率达到93.2%.Ce-Zn共掺杂HA-GP复合材料有良好的抗菌应用前景.
Cerium (Ce) and zinc (Zn) are common trace elements in human bodies. Ce-Zn co-doped hydroxyapatite (HA) composites has good application value in biomedical field. In this study, Ce-Zn co-doped hydroxyapatite-graphene (HA-GP) composite powders are successfully synthesized by a one-pot hydrothermal method. Then, the Ce-Zn co-doped hydroxyapatite-graphene composites are characterized by a set of techniques including X-ray diffraction (XRD), Fourier transform infrared (FTIR), Raman infrared (Raman), field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDX) and transmission electron microscopy (TEM). The results show that Ce and Zn ions have been successfully doped into HA lattice by replacing partial Ca ions. However, due to the difference between the radii of Ce, Zn and Ca ions, the amorphous phases in the obtained composites increase with the increase of doping ratios, and the agglomeration phenomenon begins to appear as well. The antibacterial tests show that doping of Ce and Zn ions greatly improves the antibacterial properties of the composites. The sterilization rate reaches up to 93.2% as the doping content is increased to 10% (molar ratio), which implies that Ce-Zn co-doped HA-GP composite has a good antibacterial application prospect.


[1] AL-BAKHSH B A J, SHAFIEI F, HASHEMIAN A, et al. In-vitro bioactivity evaluation and physical properties of an epoxy-based dental sealer reinforced with synthesized fluorine-substituted hydroxyapatite, hydroxyapatite and bioactive glass nanofillers[J]. Bioactive Materials, 2019, 4: 322-333.
[2] MOREJN-ALONSO L, MOCHALES C, NASCIMENTO L,et al.Electrochemical deposition of Sr and Sr/Mg-co-substituted hydroxyapatite on Ti-40Nb alloy[J]. Materials Letters,2019,248:65-68.
[3] IZQUIERDO-BARBA I, SANTOS-RUIZ L, BECERRA J,et al.Synergistic effect of Si-hydroxyapatite coating and VEGF adsorption on Ti6Al4V-ELI scaffolds for bone regeneration in an osteoporotic bone environment[J].Acta Biomaterialia,2019,83:456-466.
[4] LIU Debao, XU Guangquan, JAMALI S S,et al.Fabrication of biodegradable HA/Mg-Zn-Ca composites and the impact of heterogeneous microstructure on mechanical properties, in vitro degradation and cytocompatibility[J].Bioelectrochemistry,2019,129:106-115.
[5] CIOBANU G, HARJA M.Cerium-doped hydroxyapatite/collagen coatings on Titanium for bone implants[J].Ceramics International,2019,45(2):2852-2857.
[6] WANG Pengjun, YU Tengbo, L Qiulan,et al.Fabrication of hydroxyapatite/hydrophilic graphene composites and their modulation to cell behavior toward bone Reconstruction engineering[J].Colloids and Surfaces B: Biointerfaces,2019,173:512-520.
[7] ELAYAKUMAR K, DINESH A, MANIKANDAN A,et al.Structural, morphological, enhanced magnetic properties and antibacterial bio-medical activity of rare earth element (REE) cerium (Ce3+) doped CoFe2O4 nanoparticles[J].Journal of Magnetism and Magnetic Materials,2019,476:157-165.
[8] ZHOU Guoqiang, LI Yang, ZHENG Baofeng, et al. Cerium oxide nanoparticles protect primary osteoblasts against hydrogen peroxide induced oxidative damage[J]. Micro-Nano Letters, 2014, 9(2): 91-96.
[9] MNDEZ-LOZANO N, VELZQUEZ-CASTILLO R, RIVERA-MUOZ E M,et al.Crystal growth and structural analysis of hydroxyapatite nanofibers synthesized by the hydrothermal microwave-assisted method[J].Ceramics International,2017,43(1):451-457.
[10] PANDEY A, MIDHA S, SHARMA R K,et al.Antioxidant and antibacterial hydroxyapatite-based biocomposite for orthopedic applications[J].Materials Science & Engineering C - Materials for Biological Applications,2018,88:13-24.
[11] YANG Hongtao, QU Xinhua, LIN Wenjiao, et al. In vitro and in vivo studies on zinc-hydroxyapatite composites as novel biodegradable metal matrix composite for orthopedic applications[J].Acta Biomaterialia,2018,71:200-214.
[12] SERGI R, BELLUCCI D, CANDIDATO R T, et al. Bioactive Zn-doped hydroxyapatite coatings and their antibacterial efficacy against Escherichia coli and Staphylococcus aureus[J].Surface and Coatings Technology,2018,352:84-91.
[13] YU Xiaoqing, ZHANG Wensi, ZHANG Panpan, et al. Fabrication technologies and sensing applications of graphene-based composite films: advances and challenges[J].Biosensors & Bioelectronics,2017,89:72-84.
[14] KUMAR S, SHIKANDAR D B, SUPRIYA S, et al.Electrochemical sensors and biosensors based on graphene functionalized with metal oxide nanostructures for healthcare applications[J].ChemistrySelect,2019,4(18):5322-5337.
[15] GOONEH-FARAHANI S, NAIMI-JAMAL M R, NAGHIB S M. Stimuli-responsive graphene-incorporated multifunctional chitosan for drug delivery applications:a review[J].Expert Opinion on Drug Delivery,2019,16(1):79-99.
[16] WEI Gang, GONG Coucong, HU Keke, et al. Biomimetic hydroxyapatite on graphene supports for biomedical applications: a review[J].Nanomaterials,2019,9(10):1435.
[17] LEE H, CHOI T K, LEE Y B, et al. A graphene-based electrochemical device with thermoresponsive microneedles for diabetes monitoring and therapy[J].Nature Nanotechnology,2016,11(6):566-572.
[18] 沈萍,陈向东.微生物学实验[M].4版.北京:高等教育出版社,2007:5-35.
SHEN Ping, CHEN Xiangdong. Microbiology experiment[M]. 4th ed. Beijing: Higher Education Press, 2007:5-35.(in Chinese)
[19] DHAND V, RHEE K Y, PARK S J. The facile and low temperature synthesis of nanophase hydroxyapatite crystals using wet chemistry[J].Materials Science & Engineering C-Materials for Biological Applications,2014,36:152-159.
[20] ZHANG Leilei, LI Hejun, LI Kezhi, et al. Preparation and characterization of carbon/SiC nanowire/Na-doped carbonated hydroxyapatite multilayer coating for carbon/carbon composites[J].Applied Surface Science,2014,313:85-92.
[21] ROBLES-AGUILA M J, REYES-AVENDAFLO J A, MENDOZA M E. Structural analysis of metal-doped (Mn, Fe, Co, Ni, Cu, Zn) calcium hydroxyapatite synthetized by a sol-gel microwave-assisted method[J]. Ceramics International, 2017, 43(15): 12705-12709.


 LIU Yi,LIN Xiao-dong,ZHANG Lei,et al.Study on preparation,structures and anticoagulation properties of diamond-like carbon films[J].Journal of Shenzhen University Science and Engineering,2008,25(3):287.
 Ni Zhuo,Yang Sha,Wang Ying,et al.Research methods and advances on bone substitute materials[J].Journal of Shenzhen University Science and Engineering,2015,32(3):331.[doi:10.3724/SP.J.1249.2015.04331]
 Ni Zhuo,Yang Sha,Wu Gengfeng,et al.Thermal stability and biotoxicity of PES-HA biocomposites[J].Journal of Shenzhen University Science and Engineering,2017,34(3):313.[doi:10.3724/SP.J.1249.2017.03313]
 JIANG Yifeng,YANG Shili,WEI Wei,et al.Effect of nitrogen control on the coupling system of brewery waste water and microalgae cultivation[J].Journal of Shenzhen University Science and Engineering,2020,37(3):528.[doi:10.3724/SP.J.1249.2020.05528]
 HE Huan,XIE Ruolan,DING Senxu,et al.Screening of cadmium resistant bacteria and their effects on plant growth promotion and remediation in soil[J].Journal of Shenzhen University Science and Engineering,2021,38(3):374.[doi:10.3724/SP.J.1249.2021.04374]


Foundation:Shenzhen Basic Research Foundation (JCYJ20190808110613626); National Natural Science Foundation of China(21471102)
Corresponding author:Associate professor YUAN Qiuhua.E-mail: yuanqiuh@szu.edu.cn
Citation:YUAN Qiuhua, SHI Xin, LIANG Jinren, et al. Preparation and antibacterial properties of cerium-zinc co-doped hydroxyapatite-graphene composite[J]. Journal of Shenzhen University Science and Engineering, 2021, 38(3): 280-286.(in Chinese)
基金项目:深圳市基础研究计划资助项目(JCYJ201908081106 13626);国家自然科学基金资助项目(21471102)
引文:袁秋华,石鑫,梁进仁,等. 铈锌共掺杂HA-GP复合物合成及抗菌性研究[J]. 深圳大学学报理工版,2021,38(3):280-286.
更新日期/Last Update: 2021-05-30