硼酸盐玻璃的原位转化及对浸泡液酸碱度的影响

doi:10.15541/jim20150126

无机材料学报 ›› 2015, Vol. 30 ›› Issue (10): 1069-1074.DOI: 10.15541/jim20150126 CSTR: 32189.14.10.15541/jim20150126

硼酸盐玻璃的原位转化及对浸泡液酸碱度的影响

朱开平¹, 王德平^1,2, 范宏圆¹, 王会¹, 姚爱华¹, 叶松¹

(同济大学 1. 材料科学与工程学院；2. 先进土木工程材料教育部重点实验室，上海 201804)

收稿日期:2015-03-13 修回日期:2015-04-28 出版日期:2015-10-20 网络出版日期:2015-09-30
作者简介:朱开平(1991–), 男, 硕士研究生. E-mail: zkp10580@126.com
基金资助:
上海市科委基础研究重点项目(12JC1408500)

In-situ Transformation of Borate Glass and Its Effect on pH of Soaking-liquid

ZHU Kai-Ping¹, WANG De-Ping^1,2, FAN Hong-Yuan¹, WANG Hui¹, YAO Ai-Hua¹, YE Song¹

(1. School of Materials Science and Engineering, Tongji University, Shanghai 201804, China; 2. Key Laboratory of Advanced Civil Engineering Materials, Ministry of Education, Tongji University, Shanghai 201804, China)

Received:2015-03-13 Revised:2015-04-28 Published:2015-10-20 Online:2015-09-30
About author:ZHU Kai-Ping. E-mail: zkp10580@126.com

摘要/Abstract

摘要：

采用火焰喷球法制备了组成为10Na₂O-10CaO-80B₂O₃(wt%)和19Na₂O-17CaO-64B₂O₃(wt%)的钠钙硼(NCB)玻璃(分别记为S1和S2)微球, 通过pH计、XRD、SEM、SEM-EDS、FTIR和BET研究了两种微球原位转化为中空羟基磷灰石(HA)微球及对浸泡液酸碱度的影响, 并以万古霉素为模型药物, 进一步研究了中空HA微球的缓释性能。结果表明, S1-HA微球具有较大的空腔体积和较好的药物负载性能, 其载药量和载药率分别达到13.5 mg/g和16.8%; 而S2微球对浸泡液pH的影响相对较强, S2-HA微球呈现显著的层状结构, 且具有较好的缓释性能, 其缓释时间可达到60 h。

关键词: 硼酸盐玻璃, 酸碱度, 中空羟基磷灰石微球, 药物缓释

Abstract:

The Na-Ca-B glass microspheres with composition of 10Na₂O-10CaO-80B₂O₃(wt%) and 19Na₂O-17CaO- 64B₂O₃(wt%) were prepared (denoted by S1 and S2, respectively) by flame spray ball method. The in-situ transformation of the microspheres into hollow hydroxyapatite(HA) and the influence on the pH value of the soaking-liquid were investigated by using pH meter, XRD, SEM, SEM-EDS, FTIR and BET measurements. In addition, the vancomycin was used as model drug to further investigate the sustained-release performance of hollow HA. The results indicate that S1-HA has larger cavity volume and better drug loading performance with 13.5 mg/g and 16.8% for its drug loading amount and efficiency, respectively. S2 microspheres can greatly influence the pH value of the soaking-liquid. Meanwhile, S2-HA present remarkable multilayered structure and better sustained-release performance with the release time of 60 h.

Key words: borate glass, pH value, hollow hydroxyapatite microspheres, drug sustained release

中图分类号:

TQ171

朱开平, 王德平, 范宏圆, 王会, 姚爱华, 叶松. 硼酸盐玻璃的原位转化及对浸泡液酸碱度的影响[J]. 无机材料学报, 2015, 30(10): 1069-1074.

ZHU Kai-Ping, WANG De-Ping, FAN Hong-Yuan, WANG Hui, YAO Ai-Hua, YE Song. In-situ Transformation of Borate Glass and Its Effect on pH of Soaking-liquid[J]. Journal of Inorganic Materials, 2015, 30(10): 1069-1074.

图/表 10

图1 NCB玻璃微球对PBS浸泡液pH的影响

Fig. 1 Effect on pH of PBS of NCB glass microspheres

图2 NCB玻璃微球对PBS酸碱度的多次影响效果

Fig. 2 Multiple effect of glass microspheres on pH of PBS (a) S1 microspheres; (b) S2 microspheres

图3 NCB玻璃微球对浸泡液酸碱度的影响原理

Fig. 3 Effect principle of NCB glass microspheres on pH of soaking liquid

图4 不同热处理温度下中空HA微球的XRD图谱

Fig. 4 XRD patterns of hollow HA microspheres heat-treated at different temperatures. (a) S1-HA microspheres; (b) S2-HA microspheres

图5 中空HA微球的红外光谱

Fig. 5 Infrared spectra of hollow HA microspheres

图6 NCB玻璃微球反应前后的SEM照片

Fig. 6 SEM images of NCB glass microspheres before and after reaction. (a) S1 microspheres before reaction; (b) Fractured section of S1-HA microspheres; (c) Fractured section of S2-HA microspheres

图7 中空HA微球表面的SEM形貌以及能谱图

Fig. 7 SEM images (a,c) and EDS spectrum (b,d) of the surface of S1-HA microspheres (a, b) and S2-HA microspheres (c, d). Insets in (a, c) show the high magnification images of the surface. The white boxed areas indicate the positions where the EDS spectrum were taken

表1 样品的表面特性和孔结构参数

Table 1 Surface characteristics and pore structure parameters of the sample

Sample	SA/(m²·g^-1)	PV/(cm³·g^-1)	PS/nm	ZP/mV
S1-HA	38.79	0.12	11.44	-4.98
S2-HA	31.17	0.17	28.29	-3.37

表2 中空HA微球载药释药性能

Table 2 Performance of drug-loading and drug-release for hollow HA microspheres

Sample	DLA/(mg·g^-1)	DLE/%	CRE/%
S1-HA	13.5±0.5	16.8±0.6	87.3±1.3
S2-HA	10.6±0.3	13.2±0.4	81.9±1.8

图8 载药中空HA微球在PBS中的药物累积释放曲线

Fig. 8 Cumulative drug release curve in PBS of the drug- loaded hollow HA microspheres

参考文献 17

[1]	HUANG WEN-HAI, DAY DE, KITTIRATANAPIBOON KANISA, et al.Kinetics and mechanisms of the conversion of silicate (45S5), borate, and borosilicate glasses to hydroxyapatite in dilute phosphate solutions.Journal of Materials Science: Materials in Medicine, 2006, 17(7): 583-596.
[2]	ZHANG XIN, JIA WEI-TAO, GU YI-FEI, et al.Borate bioglass based drug delivery of teicoplan in for treating osteomyelitis.Journal of Inorganic Materials, 2010, 25(3): 293-298.
[3]	ZHANG XIN, JIA WEI-TAO, HUANG WEN-HAI, et al.Teicoplanin- loaded borate bioactive glass implants for treating chronic bone infection in a rabbit tibia osteomyelitis model.Biomaterials, 2010, 31(22): 5865-5874.
[4]	FU QIANG, RAHAMAN MN, FU HAI-LUO, et al.Silicate, borosilicate, and borate bioactive glass scaffolds with controllable degradation rate for bone tissue engineering applications. Preparation and in vitro degradation.Journal of Biomedical Materials Research-Part A, 2011, 95(1): 164-171.
[5]	LIANG WEN, RAHAMAN MN, DAY DE, et al.Bioactive borate glass scaffold for bone tissue engineering.Journal of Non-Crystalline Solids, 2008, 354(15/16): 1690-1696.
[6]	RAHAMAN MN, DAY DE, Bal BS, et al.Bioactive glass in tissue engineering.Acta Biomater., 2011, 7(6): 2355-2373.
[7]	RAHAMAN MN, BROWN RF, DAY DE, et al.Bioactive glasses for non-bearing applications in total joint replacement.Semin Arthroplasty, 2007, 17(3/4): 102-112.
[8]	XU TENG, SU HANG, GANAPATHY SUTHAKAR, et al.Modulation of autophagic activity by extracellular pH.Autophagy, 2011, 7(11): 1316-1322.
[9]	FU HAI-LUO, RAHAMAN MN, BROWN RF, et al.Evaluation of BSA protein release from hollow HA microspheres into PEG hydrogel.Mater. Sci. Eng. C, 2013, 33(4): 2245-2250.
[10]	ZHANG LI-FANG, YANG DE-JUAN, CHEN HE-CHUN, et al.An ionically crosslinked hydrogel containing vancomycin coating on a porous scaffold for drug delivery and cell culture.Int. J. Pharm., 2008, 353(1/2): 74-87.
[11]	FU HAI-LUO, RAHAMAN MN, DAY DE, et al.Hollow hydroxyapatite microspheres as a device for controlled delivery of proteins. J. Mater. Sci. Mater. Med., 2011, 22(3): 579-591.
[12]	JIANG FEI, WANG DE-PING, YE SONG, et al.Strontium-substituted, luminescent and mesoporous hydroxyapatite microspheres for sustained drug release.J. Mater. Sci: Mater. Med., 2014, 25(2): 391-400.
[13]	WANG QING, HUANG WEN-HAI, WANG DE-PING, et al.Preparation of hollow hydroxyapatite microspheres.J. Mater. Sci: Mater. Med., 2006, 17(1): 641-646.
[14]	WANG YIN-CHUN, YAO AI-HUA, HUANG WEN-HAI, et al.In situ fabrication of hollow hydroxyapatite microspheres by phosphate solution immersion.Journal of Crystal Growth, 2011, 327(1): 245-250.
[15]	PAN HAO-BO, ZHAO XIAN-LIANG, ZHANG XIN, et al.Strontium- borate glass: potential biomaterial for bone regeneration.J. R. Soc. Interface, 2010, 7(48): 1025-1031.
[16]	XIAO WEI, FU HAI-LUO, RAHAMAN MN, et al.Hollow hydroxyapatite microspheres: A novel bioactive and osteoconductive carrier for controlled release of bone morphogenetic protein-2 in bone regeneration.Acta Biomaterialia, 2013, 9(9): 8374-8383.
[17]	YAO AI-HUA, XU WEI, AI FAN-RONG, et al.Study on hollow hydroxyapatite microspheres as delivery system for human bone morphogenetic protein.Journal of Inorganic Materials, 2011, 26(9): 974-978.

硼酸盐玻璃的原位转化及对浸泡液酸碱度的影响

In-situ Transformation of Borate Glass and Its Effect on pH of Soaking-liquid

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