HA:RE(RE=Eu3+、Tb3+)纳米棒的制备与细胞毒性研究

doi:10.3724/SP.J.1077.2013.12336

无机材料学报 ›› 2013, Vol. 28 ›› Issue (5): 557-560.DOI: 10.3724/SP.J.1077.2013.12336 CSTR: 32189.14.SP.J.1077.2013.12336

HA:RE(RE=Eu³⁺、Tb³⁺)纳米棒的制备与细胞毒性研究

陶婷婷, 王进贤, 董相廷, 于文生, 李庆丽

(长春理工大学化学与环境工程学院，应用化学与纳米技术吉林省高校重点实验室, 长春 130022)

收稿日期:2012-05-22 修回日期:2012-08-05 出版日期:2013-05-10 网络出版日期:2013-04-22
作者简介:陶婷婷(1986–), 女, 硕士研究生.
基金资助:
国家自然科学基金(50972020);博士点基金(20102216110002, 20112216120003)

Synthesis of Europium or Terbium Doped Hydroxyapatite Nanorods and Their Cytotoxicity

TAO Ting-Ting, WANG Jing-Xian, DONG Xiang-Ting, YU Wen-Sheng, LI Qing-Li

(Key Laboratory of Applied Chemistry and Nanotechnology at Universities of Jilin Province, School of Chemistry and Environmental Engineering, Changchun University of Science and Technology, Changchun 130022, China)

Received:2012-05-22 Revised:2012-08-05 Published:2013-05-10 Online:2013-04-22
About author:TAO Ting-Ting.
Supported by:
National Natural Science Foundation of China (NSFC 50972020);PhD Programs Foundation of the Ministry of Education of China (20102216110002, 20112216120003)

摘要/Abstract

摘要：

采用EDTA为模板, 以CaCO₃、NH₄H₂PO₄、Eu₂O₃、Tb₇O₄、HNO₃为原料, 用NH₃·H₂O调节pH值, 成功制备了掺铕羟基磷灰石(HA:Eu³⁺)及掺铽羟基磷灰石(HA:Tb³⁺)纳米棒, 并采用XRD、场发射环境扫描电子显微镜、荧光光谱、酶联监测仪等对其荧光及细胞毒性进行了研究。结果表明: 制备的HA:Eu³⁺纳米棒最强发射峰位于617 nm处, 发射出明亮的红光; 制备的HA:Tb³⁺纳米棒最强发射峰位于544 nm处, 发射出明亮的绿光; 细胞毒性研究表明HA:RE (RE=Eu³⁺、Tb³⁺)纳米棒是一种良好的生物示踪材料。

关键词: HA:Eu³⁺, HA:Tb³⁺, EDTA, 纳米棒, 细胞毒性

Abstract:

Using CaCO₃, Eu₂O₃, Tb₇O₄, HNO₃and NH₄H₂PO₄ as starting materials, regulating pH value by NH₃·H₂O, europium-doped and terbium-doped hydroxyapatite (HA:Eu³⁺/ HA:Tb³⁺) nanorods were prepared by hydrothermal method using EDTA as a template. The synthesized materials were systematically characterized by XRD and FESEM. Their luminescence properties and cytotoxicity were studied by fluorescence analysis and MTT assay, respectively. The results show that the main emission peaks of HA:Eu³⁺ and HA:Tb³⁺ nanorods occur at 617 and 544 nm, which can emit bright red and green light, respectively. The cell survival curves show that the prepared HA:Eu³⁺ and HA:Tb³⁺ nanorods can be used as ideal biological tracer materials.

Key words: HA:Eu³⁺, HA:Tb³⁺, EDTA, nanorods, cytotoxicity

中图分类号:

陶婷婷, 王进贤, 董相廷, 于文生, 李庆丽. HA:RE(RE=Eu³⁺、Tb³⁺)纳米棒的制备与细胞毒性研究[J]. 无机材料学报, 2013, 28(5): 557-560.

TAO Ting-Ting, WANG Jing-Xian, DONG Xiang-Ting, YU Wen-Sheng, LI Qing-Li. Synthesis of Europium or Terbium Doped Hydroxyapatite Nanorods and Their Cytotoxicity[J]. Journal of Inorganic Materials, 2013, 28(5): 557-560.

图/表 7

图1 a、b分别是HA:Eu3+及HA:Tb3+的X射线衍射图谱, 结果与PDF 09-0432一致, 属六方晶系。图中没有发现Eu3+和Tb3+的化合物衍射峰, 说明Eu3+和Tb3+分散良好, 没有形成Eu2O3、Tb4O7的凝聚相。在HA:Eu3+(Tb3+)纳米棒的形成过程中, EDTA是最常用的多齿络合剂之一, 两端的羧基为亲水基团, 中间为疏水基团, 在水溶液中形成了具有胶束结构的模板, 同时起络合剂和软模板的作用, 可表示为[(OOCCH2)2NHCH2CH2NH(CH2COO)24-[19]。因此, EDTA与Ca2+作用发生络合反应, 有效地控制了Ca2+的浓度, 在碱性环境中, H2PO4-加入后与Ca2+在原位发生有序的化学反应[20]并使EDTA缓慢释放, 同时, 由于Eu3+、Tb3+的离子半径远小于Ca2+的离子半径, 能够轻易地取代Ca2+[21], 水热条件进一步促进了晶核沿着特定方向生长, 晶粒不断增大延伸, 最终形成了HA:Eu3+及HA:Tb3+纳米棒.

图1 HA:Eu3+ (a)与HA:Tb3+ (b)纳米棒的XRD图谱

Fig. 1 XRD patterns of HA:Eu3+ and HA:Tb3+ nanorods

图2 a、b分别为HA:Eu3+和HA:Tb3+纳米棒的FESEM照片, HA:Eu3+纳米棒和HA:Tb3+纳米棒的平均直径为20 nm, 长度为100~200 nm, 分散性良好.

图2 HA:Eu3+ (a)和HA:Tb3+ (b)纳米棒的FESEM照片

Fig. 2 FESEM images of HA:Eu3+(a) and HA:Tb3+(b) nanorods

图3 HA:Eu3+纳米棒的激发和发射光谱图

Fig. 3 Emission and excitation spectra of HA:Eu3+ nanorods

图4 HA:Tb3+纳米棒的激发和发射光谱图

Fig. 4 Emission and excitation spectra of HA:Tb3+ nanorods

图5 细胞存活率曲线

Fig. 5 Curves of cell survival rate

参考文献 21

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HA:RE(RE=Eu³⁺、Tb³⁺)纳米棒的制备与细胞毒性研究

Synthesis of Europium or Terbium Doped Hydroxyapatite Nanorods and Their Cytotoxicity

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