贻贝壳在不同方法下合成羟基磷灰石多孔微球的性能研究
PDF下载 (393)李超群,顾忠旗,黄 继,石 娟,周丽萍,王 晴,娄永江.贻贝壳在不同方法下合成羟基磷灰石多孔微球的性能研究[J].宁波大学学报(理工版),2021,34(5):1-8.DOI:
LI Chaoqun,GU Zhongqi,HUANG Ji,SHI Juan,ZHOU Liping,WANG Qing,LOU Yongjiang.Study on the synthesis and properties of porous hydroxyapatite microspheres from mussel shells with various methods[J].Journal of Ningbo University(Natural Science & Engineering Edition),2021,34(5):1-8.DOI:
| Title: | Study on the synthesis and properties of porous hydroxyapatite microspheres from mussel shells with various methods |
| 作者: | 李超群, 顾忠旗, 黄 继, 石 娟, 周丽萍, 王 晴, 娄永江 |
| Author(s): | LI Chaoqun, GU Zhongqi, HUANG Ji, SHI Juan, ZHOU Liping, WANG Qing, LOU Yongjiang |
| 关键词: | 贻贝壳; 碳酸钙; 羟基磷灰石多孔微球; 载银量 |
| Keywords: | mussel shells; calcium carbonate; hydroxyapatite porous microspheres; silver loading |
| 分类号: | TB34 |
| 文献标识码: | A |
| 摘要: | 选用舟山市贻贝壳为原料制备羟基磷灰石(HA)多孔微球, 球形HA较其他形状的HA有更多的药物和金属负载量, 可以合成特殊的功能性材料. 实验过程为: 采用贻贝壳提取CaCO3, 以贻贝壳的CaCO3为原料用水热法、沉淀法、十六烷基三甲基溴化铵模板剂法及反相微乳液法制备HA, 经比较确定可行方案, 并对制备出的样品进行银离子吸附实验. 研究结果表明: 通过扫描电子显微镜表征观察得出水热法制备的产物为球形; X射线粉末衍射仪和傅里叶红外光谱仪测得水热法制得的产物为HA, 其他产物为方解石型CaCO3/HA复合材料; 比表面积及微孔孔隙分析表征得出水热法制备的产物介孔结构和比表面积最优; 电感耦合等离子体发射光谱仪检测产物的钙磷比及载银量, 确定水热法制备的样品为缺磷型HA, 该HA的银离子吸附率达75.10%. 表明贝壳制备HA多孔微球是可行的, 采用水热法可将贝壳CaCO3合成球形多孔HA, 且在转化程度和载银效果方面较其他方法更有优势. |
| Abstract: | Mussel shells of Zhoushan City were selected as raw materials for preparing hydroxyapatite (HA) porous microspheres. Compared with HA in other shapes, spherical HA possesses more drug and metal loading capacities, and can be used to synthesize materials with special functions. The experimental process was as follows: CaCO3 was extracted from mussel shells and used as raw material to prepare HA with hydrothermal method, pecipitation method, sixteen alkyl three methyl ammonium bromide template method and inverse micro-emulsion method. The study was aimed to determine the feasible method and implement the silver loading experiment on prepared samples. Shown by scanning electron microscopy, HA prepared by hydrothermal method was spherical. Shown by X-ray powder diffractometer and fourier transform infrared spectrometer (FTIR), one product prepared by hydrothermal method was HA and the other products were calcite type CaCO3/HA composites. The micro pore analysis showed that the product prepared by hydrothermal method was provided with optimal mesoporous structure. Inductively coupled plasma emission spectrometer was used to detect the ratio of calcium to phosphorus and silver loading capacity of the product. The sample prepared by hydrothermal method was phosphorus deficient HA and the silver ion adsorption rate was 75.10%. The results show that it is feasible to prepare HA porous microspheres from shells. Using hydrothermal method, shell CaCO3 can be fully utilized and synthesized into spherical porous HA with great silver loading effect. |
| 参考文献 /References: | [1] 张静, 李泓, 高海明, 等. 水热法制备方糖状CaCO3@HA颗粒药物控释载体[J]. 硅酸盐学报, 2019, 47(12): 1792-1800. [2] Klein C P A T, Driessen A A, de Groot K. Relationship between the dégradation behaviour of calcium phosphate ceramics and their physical-chemical characteristics and ultrastructural geometry[J]. Biomaterials, 1984, 5(3):157-160. [3] 赵宏, 陈瑶, 李正明, 等. 废弃贝壳制备纳米带状羟基磷灰石的研究[J]. 甘肃科技, 2016, 32(17):50-52. [4] Lin K L, Chen L Y, Liu P, et al. Hollow magnetic hydroxyapatite microspheres with hierarchically mesoporous microstructure for pH-responsive drug delivery[J]. Crystengcomm, 2013, 15(15):2999. [5] Ono I, Yamashita T, Jin H Y, et al. Combination of porous hydroxyapatite and cationic liposomes as a vector for BMP-2 gene therapy[J]. Biomaterials, 2004, 25(19): 4709-4718. [6] Zhu S H, Huang B Y, Zhou K C, et al. Hydroxyapatite nanoparticles as a novel gene carrier[J]. Journal of Nanoparticle Research, 2004, 6(2):307-311. [7] Deville S, Saiz E, Tomsia A P. Freeze casting of hydroxyapatite scaffolds for bone tissue engineering[J]. Biomaterials, 2006, 27(32):5480-5489. [8] 马高, 朱伟, 史云松, 等. 羟基磷灰石及其复合材料增材制造研究现状[J]. 硅酸盐学报, 2017, 45(3):393-401. [9] 张月, 王瑾, 刘克达, 等. 纳米羟基磷灰石/胶原复合材料在口腔骨缺损中的应用及研究进展[J]. 中国实用口腔科杂志, 2020, 13(6):375-378. [10] Tank K P, Chudasama K S, Thaker V S, et al. Cobalt- doped nanohydroxyapatite: Synthesis, characterization, antimicrobial and hemolytic studies[J]. Journal of Nanoparticle Research, 2013, 15(5):1-11. [11] Ozawa M, Kanahara S. Removal of aqueous lead by fish-bone waste hydroxyapatite powder[J]. Journal of Materials Science, 2005, 40(4):1037-1038. [12] 杨喆云, 梁敏, 张中, 等. 以贝壳为钙源的绿色综合化学实验研究探索[J]. 实验技术与管理, 2013, 30(8):43-45; 49. [13] Nagata F, Miyajima T, Yokogawa Y. A method to fabricate hydroxyapatite/poly(lactic acid) microspheres intended for biomedical application[J]. Journal of the European Ceramic Society, 2006, 26(4/5):533-535. [14] Tomoda K, Ariizumi H, Nakaji T, et al. Hydroxyapatite particles as drug carriers for proteins[J]. Colloids and Surfaces B: Biointerfaces, 2010, 76(1):226-235. [15] 邓超, 陈彰旭, 谢曙光, 等. 纳米羟基磷灰石应用研究进展[J]. 广东化工, 2009, 36(3):45-46; 132. [16] 王润南, 张丹丹, 王璇, 等. 贝壳粉制备球形羟基磷灰石[J]. 化工时刊, 2015, 29(4):7-9. [17] Singh G, Jolly S S, Singh R P. Investigation of surfactant role in synthesis of hydroxyapatite nanorods under microwave and hydrothermal conditions[J]. Materials Today: Proceedings, 2020, 26:2701-2710. [18] Aggarwal A, Jolly S S, Singh R P. Synthesis and characterization of mesoporous microspherical particles for drug delivery applications[J]. Materials Today: Proceedings, 2020, 28:1916-1919. [19] 刘子阳, 耿振, 李朝阳. 牡蛎壳为原料制备医用CaCO3/HA复合生物材料[J]. 无机材料学报, 2020, 35(5):601-607. [20] 杨叶辉. 利用水产品加工副产物开发羟基磷灰石的研究进展[J]. 食品安全质量检测学报, 2016, 7(1):263-268. [21] 赵科. 生物活性纳米羟基磷灰石的合成与自组装[D]. 扬州: 扬州大学, 2019. [22] 高平章, 艾杨城, 钟榕榕, 等. 牡蛎壳超细球霰石碳酸钙的制备与表征[J]. 食品与发酵工业, 2020, 46(17):151-157. [23] Lin K L, Wu C T, Chang J. Advances in synthesis of calcium phosphate crystals with controlled size and shape[J]. Acta Biomaterialia, 2014, 10(10):4071-4102. [24] Lei L, Zheng L, Xiao H, et al. Wear mechanism of human tooth enamel: The role of interfacial protein bonding between HA crystals[J]. Journal of the Mechanical Behavior of Biomedical Materials, 2020, 110:103845. [25] 黎香惠, 韦刘晓, 梁小静, 等. 利用贝壳粉制备球形碳酸钙模板剂的工艺[J]. 大众科技, 2020, 22(1):32-35. [26] 陈银霞, 纪献兵, 晋利, 等. 扇形分级微纳米碳酸钙的可控合成与表征[J]. 无机盐工业, 2018, 50(4):30-32. [27] 关欣. 微纳米碳酸钙的制备及表征[D]. 南宁: 广西民族大学, 2017. [28] 孟德营. 羟基磷灰石粉体及多孔块体的制备技术[D]. 济南: 山东轻工业学院, 2010. [29] 陈文金, 彭希珑, 何宗健. 羟基磷灰石涂层石灰石对水溶液中Cu(Ⅱ)的去除[J]. 南昌大学学报(工科版), 2019, 41(3):221-227. [30] 胡蓓蓓, 李雪微, 白海, 等. 新型纳米HAP复合改性材料制备及其防龋性能研究[J]. 实用口腔医学杂志, 2020, 36(1):86-90. [31] 袁秋华, 陈泽汇, 万磊, 等. 锶掺杂羟基磷灰石-石墨烯复合材料制备与表征[J]. 深圳大学学报(理工版), 2020, 37(3):298-304. [32] 宫珊珊, 钱鹏飞, 管孝梅, 等. 介孔结构的羟基磷灰石纳米微球的制备及对水中Pb2+、Cu2+和Zn2+的吸附研究[J]. 合肥师范学院学报, 2018, 36(3):23-26. [33] Hokkanen S, Repo E, Westholm L J, et al. Adsorption of Ni2+, Cd2+, PO43- and NO3- from aqueous solutions by nanostructured microfibrillated cellulose modified with carbonated hydroxyapatite[J]. Chemical Engineering Journal, 2014, 252:64-74. [34] Zanin H, Saito E, Marciano F R, et al. Fast preparation of nano-hydroxyapatite/superhydrophilic reduced graphene oxide composites for bioactive applications[J]. Journal of Materials Chemistry B, 2013, 1(38):4947-4955. [35] 宋萃, 戚明颖, 刘金芳, 等. Ag3PO4/羟基磷灰石复合光催化剂的制备及对亚甲基蓝的高效降解[J]. 复合材料学报, 2020, 37(6):1418-1425. [36] 范海林. 不同钙磷比羟基磷灰石的制备及吸附性能研究[D]. 沈阳: 沈阳大学, 2015. [37] 陈华军, 徐伏秋, 薛冬, 等. 银掺杂纳米羟基磷灰石抗菌粉体的水热合成及结构表征[J]. 化学学报, 2012, 70(12):42-46. |
| 备注/Memo: | 收稿日期: 2020－12－19. 宁波大学学报（理工版）网址: http://journallg.nbu.edu.cn/ 基金项目: 浙江省教育厅科研项目（2018C02025）. 第一作者: 李超群（1995－）, 女, 山东东营人, 在读硕士研究生, 主要研究方向: 水产的高值化利用. E-mail: 1731779125@qq.com *通信作者: 娄永江（1965－）, 男, 浙江嵊州人, 教授, 主要研究方向: 水产品加工与贮藏. E-mail: louyongjiang@nbu.edu.cn 宁波大学学报（理工版）网址：http://journallg.nbu.edu.cn/ |
