Preparation and Drug Delivery of Graphene Oxide Decorated Hollow Magnetic Nanoparticles
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摘要: 以纳米碳球和十六烷基三甲基溴化铵（CTAB）为双模板合成了具有介孔核-壳结构的纳米复合材料；并通过刻蚀法，制备了磁性介孔纳米空心球（HMNPs)；在交联剂1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐（EDC）和N-羟基硫代琥珀酰亚胺（NHS）的作用下，制备了氧化石墨烯（GO）功能化的磁性介孔纳米空心球（HMNPs-GO)。利用红外光谱（FT-IR)、X-射线粉末衍射（XRD)、拉曼光谱（Raman)、扫描电镜（SEM)、透射电镜（TEM）和振动样品磁强计（VSM）等方法进行了表征。通过研究HMNPs-GO对藤黄酸（GA）的吸附等温线，得出HMNPs-GO对GA的吸附主要为两者之间的π-π堆积，且属于Freundlich吸附。同时，基于Bhaskar模型和准一级、准二级动力学模型，分别探讨了HMNPs-GO中GA药物分子的扩散机理和缓释动力学，得出GA在HMNPs-GO中的缓释具有pH依赖性，且在不同pH下的缓释更适合于准二级动力学模型。Abstract: A mesoporous shell structure was synthesized using carbon spheres and cetyltrimethylammonium bromide (CTAB) as dual templates, and hollow magnetic nanoparticles (HMNPs) were subsequently prepared by etching. Hollow magnetic nanoparticles functionalized by graphene oxide (HMNPs-GO) were synthesized via the functionalization of HMNPs with NH2 groups and the activation of carboxyl groups of graphene oxide by N-ethyl-NO-(3-(dimethylamino)propyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS). HMNPs and HMNPs-GO were characterized by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM). Upon the investigations on the adsorption isotherm of HMNPs-GO, it was found that the adsorption of GA by HMNPs-GO was mainly attributed to the π-π accumulation between each other and was refer to Freundlich adsorption. The diffusion mechanism and release kinetics of GA in HMNPs-GO were studied based on Bhaskar model, quasi-first-order, and quasi-second-order kinetic model, respectively. The release of GA showed pH dependence in HMNPs-GO, and the sustained release at different pH followed the quasi-second-order dynamics model.
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Key words:
- hollow magnetic nanoparticles /
- graphene oxide /
- drug release
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图 3 GO (a), HMNPs (b), HMNPs-GO (c～d)的SEM图
Figure 3. SEM images of GO (a), HMNPs (b), HMNPs-GO (c～d)
图 4 (a) GO, mSiO2和HMNPs-GO的XRD; (b) GO, Fe3O4, HMNPs和HMNPs-GO的红外谱图
Figure 4. (a) XRD patterns of GO, mSiO2 and HMNPs-GO; (b) FT-IR spectra of GO, Fe3O4, HMNPs and HMNPs-GO
图 6 HMNPs的N2吸附-脱附曲线与孔径分布图
Figure 6. N2 adsorption-desorption isotherm and pore size distribution of HMNPs
图 7 HMNPs和HMNPs-GO的磁滞回线
Figure 7. Magnetization hysteresis curves of HMNPs and HMNPs-GO
图 9 HMNPs-GO对GA的Langmuir (a)和Freundlich (b)等温吸附负载线性拟合
Figure 9. Langmuir isotherm model (a) and Freundlich isotherm model (b) for adsorption and loading of GA on HMNPs-GO
图 10 (a) HMNPs-GO对GA在pH=7.4时的负载率和(b) HMNPs-GO-GA对GA在pH=5.7和7.4时的缓释率
Figure 10. (a) GA loading rate of HMNPs-GO at pH=7.4; (b) GA released rate of HMNPs-GO-GA at pH=5.7 and 7.4
图 11 在pH=5.7 (a)和pH=7.4 (b)时，GA从HMNPs-GO中的缓释率与t0.65的关系
Figure 11. Released rate of GA from HMNPs-GO vs. t0.65 at pH=5.7 (a) and pH=7.4 (b)
图 12 不同pH环境下的HMNPs-GO准一级和准二级动力学曲线
Figure 12. Kinetics curves of Quasi-first-order reaction and quasi-second-order reaction for the release of GA from HMNPs-GO at different pH
表 1 HMNPs-GO和HMNPs对不同质量GA的负载（37 ℃, pH=7.4）
Table 1. Loading of HMNPs-GO and HMNPs for different mass of GA
m(GA)/mg HMNPs-GO HMNPs Drug loading/mg Effective loading/(mg·g−1) Drug loading/mg 1.0 0.94 47.11 0.56 1.5 1.25 62.60 0.79 2.5 1.80 89.82 1.01 5.0 2.18 109.20 1.21 7.5 2.62 130.95 1.39 10 3.28 163.80 1.74 
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表 2 不同pH下GA释放的的准二级方程拟合参数
Table 2. Fitting parameters of quasi-second-order reaction kinetics for GA releasing at different pH
pH Equation R2 Qe′/(mg·g−1) v0/ (mg·(g·h)−1) 5.7 y=0.006 1x+0.056 4 0.998 1 162.866 4 17.727 7.4 y=0.014 9x+0.065 1 0.999 3 67.249 5 15.370
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