银掺杂介孔氧化铝抗菌剂的一步合成与表征

doi:10.7503/cjcu20160111

摘要/Abstract

摘要：

以Al(NO₃)₃·9H₂O和AgNO₃为原料, 采用水热法制备了介孔氧化铝纳米粒子(Mesoporous Al₂O₃ NPs)和银掺杂介孔氧化铝纳米粒子(Mesoporous Ag/Al₂O₃ NPs), 通过X射线衍射(XRD)、场发射扫描电子显微镜(FE-SEM)、 X射线荧光光谱(XRF)、能量分散X射线衍射(EDX)和低温N₂吸附-脱附等手段对产物进行了表征, 通过最低抑菌浓度和抑菌圈实验研究了材料的抗菌性能. XRD分析表明在介孔Ag/Al₂O₃ NPs中Al₂O₃是唯一结晶相, Ag掺杂后, 介孔Ag/Al₂O₃ NPs晶格常数和半高峰宽增大, 晶面间距[(111), (400)和(440)面]减小. FE-SEM形貌分析表明掺杂后的介孔Ag/Al₂O₃ NPs颗粒直径减小而孔径增大. EDX和XRF分析表明介孔Ag/Al₂O₃ NPs中O/Al摩尔比为1.5, 与Al₂O₃ NPs中O/Al摩尔比相同. 综合XRD和XRF分析结果认为, Ag进入介孔Al₂O₃晶格间隙形成间隙固溶体. 低温N₂吸附-脱附分析表明掺杂后的介孔Ag/Al₂O₃ NPs比表面积、孔体积和孔径增大. 曝气抗菌实验结果表明介孔Ag/Al₂O₃ NPs的抗菌机理是活性氧和金属银的协同作用. 介孔Ag/Al₂O₃ NPs对革兰氏阴性菌(大肠杆菌)和革兰氏阳性菌(金黄色葡萄球菌)具有明显的抗菌效果, 对大肠杆菌和金黄色葡萄球菌的最低抑菌浓度(MIC)均为80 μg/mL, 抑菌圈直径分别为26 mm和24 mm.

关键词: 银掺杂, 介孔氧化铝, 革兰氏菌, 抗菌性能

Abstract:

Metallic sliver-doped mesoporous Al₂O₃ nanoparticles(mesoporous Ag/Al₂O₃ NPs) were synthesized via hydrothermal method using AgNO₃ and Al(NO₃)₃·9H₂O as precursors. Powder X-ray diffraction(XRD), field-emission scanning electron microscopy(FE-SEM), X-ray fluorescence(XRF), energy dispersive spectrometry(EDS) and N₂ adsorption-desorption techniques were used to characterize mesoporous Ag/Al₂O₃ NPs, and the tests of minimum inhibitory concentration(MIC) and inhibition zone were carried out to evaluate antimicrobial efficiency of mesoporous Ag/Al₂O₃ NPs. XRD analysis identified Al₂O₃ as an unique crystalline phase in mesoporous Ag/Al₂O₃ NPs, and the lattice parameters modified significantly after doping with silver, in the meantime, the FWHM of mesoporous Ag/Al₂O₃ NPs increased while the (111), (400) and (440) interplanar spacing decreased. The FE-SEM images of mesoporous Al₂O₃ NPs and mesoporous Ag/Al₂O₃ NPs illustrate the diameter of mesoporous Ag/Al₂O₃ NPs decreased while the pore diameter increased after doping with silver. The XRF and EDX spectra of mesoporous Ag/Al₂O₃ NPs confirmed that the atomic ratio of O/Al was 1.5. Insightful analyses of XRD and XRF spectra of mesoporous Ag/Al₂O₃ NPs showed that metallic silver occupied interstitial positions of Al₂O₃ lattice and interstitial solid solution was achieved. N₂ adsorption-desorption analysis illustrates the specific surface area, pore volume and average pore diameter of mesoporous Ag/Al₂O₃ NPs increased significantly after doping with silver. The MIC of mesoporous Ag/Al₂O₃ NPs was less than 80 μg/mL against Escherichia coli and Staphylococcus aureus. The diameter of inhibition zone for mesoporous Ag/Al₂O₃ NPs was 26 mm against Escherichia coli and 24 mm against Staphylococcus aureus.

Key words: Silver doping, Mesoporous Al2O3, Gram, Antimicrobial efficiency

中图分类号:

O614

TrendMD:

陈华军, 席晓晶, 丁梧秀. 银掺杂介孔氧化铝抗菌剂的一步合成与表征. 高等学校化学学报, 2016, 37(6): 1036.

CHEN Huajun, XI Xiaojing, DING Wuxiu. One-pot Synthesis and Antimicrobial Performance of Metallic Silver-doped Mesoporous Al₂O₃ Nanoparticles^†. Chem. J. Chinese Universities, 2016, 37(6): 1036.

图/表 10

Fig.1 XRD patterns of mesoporous Al2O3 NPs(a) and mesoporous Ag/Al2O3 NPs(b)

Table 1 FWHM, lattice fringes, peak value and lattice parameters of mesoporous Al2O3 NPs and Ag/Al2O3 NPs

Sample	FWHM,Lattice fringes(d/nm) and peak value[2θ/(°)]			Lattice constant a=b=c/nm
Sample	(111) Interface		(400) Interface	(440) Interface
Mesoporous Al₂O₃ NPs	0.243/4.6156/19.214	0.896/1.9730/45.961	0.829/1.3942/67.074	0.788859
Mesoporous Ag/Al₂O₃ NPs	0.714/4.5775/19.375	0.959/1.9688/46.065	0.925/1.3914/67.231	0.790039

Fig.2 FESEM images of mesoporous Al2O3 NPs(A) and Ag/Al2O3 NPs(B, C)

Fig.3 Low-angle XRD patterns of mesoporous Al2O3 NPs(a) and Ag/Al2O3 NPs(b)

Fig.4 Energy dispersive X-ray spectroscopy of mesoporous Ag/Al2O3 NPs

Table 2 Results of X-ray fluorescence analysis of mesoporous Ag/Al2O3 NPs

Element	Mass fraction(%)	Atomic fraction(%)
O	36.32	56.82
Al	40.84	37.88
Ag	22.84	5.30

Fig.5 Nitrogen absorption-desorption isothermals(A) and BJH pore size distributions(B) of mesoporous Al2O3 NPs(a) and mesoporous Ag/Al2O3 NPs(b)

Table 3 Mesoporous parameters of Al2O3 NPs and Ag/Al2O3 NPs

Sample	S_BET/(m²·g^-1)	V_t/(cm³·g^-1)	D_p/nm
Mesoporous Al₂O₃ NPs	189.899	0.329	7.879
Mesoporous Ag/Al₂O₃ NPs	276.339	0.432	9.715

Fig.6 Influence of aeration on bactericidal effect of mesoporous Al2O3 NPs and Ag/Al2O3 NPs against Staphylococcus aureusa. Ag/Al2O3 NPs-O2; b. Ag/Al2O3 NPs-air;c. Ag/Al2O3 NPs-N2; d. Al2O3 NPs-O2.

Table 4 Antibacterial activity(cfu·mL-1) of mesoporous Ag/Al2O3 NPs on Escherichia coli and Staphylococcus aureus

Antimicrobials concentration/(μg·mL^-1)	Escherichia coli	Golden staphylococcus
0	5.00×10⁷	5.00×10⁷
20	3.80×10⁶	4.20×10⁵
40	9.60×10⁵	3.20×10⁴
60	1.36×10³	1.06×10²
80	80	0

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