Antibacterial and Antifungal Properties of halloysite nanotubes by loaded Linalool
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摘要: 芳樟醇具有良好的抗菌和抗氧化性，但易挥发且热稳定性差。埃洛石纳米管(HNTs)存在特殊中空孔道结构并具有保护和释放活性物质的功能，常作为纳米载体。因此，开展HNTs负载芳樟醇(LNL)的研究并进行抗菌试验。采用真空负压法将LNL负载到3 mol/L盐酸酸化后的埃洛石纳米管(AC-HNTs)管腔内部，制备出芳樟醇-酸化埃洛石纳米管(L-AC-HNTs)新型防霉抗菌剂。以竹制品中常见的大肠杆菌(Escherichia coli)、金黄色葡萄球菌(Staphylococcus aureus)、黑曲霉菌(Aspergillus niger)、桔青霉菌(Penicillium oryzae)为目标菌种，考察不同添加量L-AC-HNTs的抑菌效果，测试其热稳定性和缓释性并进行表征分析。结果表明，添加1.5%(W/V)的L-AC-HNTs对以上几种细菌和霉菌的抑菌效果最佳，抑菌率均达到了100%。L-AC-HNTs的热分解速率峰值温度达到279.9 ℃，比纯LNL提高了81.5 ℃，AC-HNTs在50 ℃下挥发72 h后对LNL的保留率仍为94.6%，仅损失了3.4%，而纯LNL保留率为8%，酸化刻蚀后LNL负载量从5.0%最高提升至15.6%。L-AC-HNTs具有广谱抑菌性和热稳定性，为其在竹制品中的应用提供参考。Abstract: Linalool has good antibacterial and antifungal properties, but is volatile and thermally unstable. Halloysite nanotubes (HNTs) are often used as nanocarriers because of their special hollow pore structure and their ability to protect and release active substances. Therefore, the study of HNTs loaded with linalool (LNL) was carried out and antimicrobial tests were performed. Preparation of linalool acidified halloysite nanotubes (L-AC-HNTs) as a novel antibacterial and antifungal agent by loading LNL into the lumen of 3 mol/L hydrochloric acid acidified halloysite nanotubes (AC-HNTs) using a vacuum-negative pressure method. The inhibitory effects of different additive amounts of L-AC-HNTs were investigated on Escherichia coli, Staphylococcus aureus, Aspergillus niger, and Penicillium oryzae, which are commonly found in bamboo products. The thermal stability and slow-release properties of the additive were also tested and characterised. The results showed that 1.5% (W/V) of L-AC-HNTs had the best inhibitory effect on the above bacteria and fungi, and the inhibition rate reached 100%. The peak thermal decomposition rate of L-AC-HNTs reached 279.9℃, which was 81.5℃ higher than that of the pure LNL, and the retention rate of LNL after volatilisation of the AC-HNTs at 50℃ for 72 h was 94.6%, with only the loss of LNL. 94.6%, with only 3.4% loss, while the retention rate of pure LNL was 8%, and the LNL loading increased from 5.0% to 15.6% at the highest after acid etching.The broad-spectrum bacteriostatic property and thermal stability of L-AC-HNTs provide references to its application in bamboo products.
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Key words:
- Halloysite /
- Linalool /
- Antibacterial and antifungal /
- Load /
- Thermal stability
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图 1 芳樟醇-酸化埃洛石纳米管(L-AC-HNTs)防霉抗菌剂制备流程
Figure 1. linalool acidified halloysite nanotubes (L-AC-HNTs) antibacterial and antifungal agent preparation process
图 3 不同添加量L-AC-HNTs 对(a)Aspergillus Niger；(b) Penicillium citrinsis；(c)Colibacillus；(d)Staphylococcus Aureus的防霉抗菌效果
Figure 3. Antibacterial and antifungal effects of different levels of L-AC-HNTs on (a) Aspergillus Niger; (b) Penicillium citrinsis; (c) Escherichia coli; (d) Staphylococcus Aureus
图 4 HNTs、L-AC-HNTs、LNL的(a)热重曲线；(b)微商热重曲线图；(c)LNL负载前后保留率
Figure 4. (a) Thermogravimetric profiles of HNTs, L-AC-HNTs, LNL; (b) Microcommercial thermogravimetric profiles; (c) Retention before and after LNL loading
图 5 (a)LNL红外光谱图；(b)HNTs、AC-HNTs、L-AC-HNTs红外光谱图
Figure 5. (a) Infrared spectra of LNL; (b) Infrared spectra of HNTs、AC-HNTs、L-AC-HNTs
图 6 (a) HNTs；(b) AC-HNTs；(c) L-AC-HNTs的扫描电镜(能量色散X射线光谱)
Figure 6. SEM (EDX) images of (a) HNTs; (b) AC-HNTs; (c) L-AC-HNTs
图 7 (a) HNTs；(b) AC-HNTs；(c) L-AC-HNTs的高倍率透射电镜(能量色散X射线光谱)
Figure 7. TEM(EDX) images of (a) HNTs; (b) AC-HNTs; (c) L-AC-HNTs
图 8 LNL、HNTs、AC-HNTs、L-AC-HNTs的X-射线衍射图
Figure 8. XRD patterns of LNL、HNTs、AC-HNTs、L-AC-HNTs
图 9 (a) HNTs、AC-HNTs、L-AC-HNTs的XPS全谱；(b) Al2p的XPS光谱；(c) Si2p的XPS光谱
Figure 9. (a) XPS full spectrum of HNTs, AC-HNTs, L-AC-HNTs; (b) XPS spectrum of Al2p; (c) XPS spectrum of Si2p
图 10 (a) HNTs、AC-HNTs、L-AC-HNTs的氮气等温吸附-脱附曲线；(b)酸化前后HNTs对不同添加量LNL负载量
Figure 10. (a) Nitrogen isothermal adsorption-desorption curves of HNTs、AC-HNTs、L-AC-HNTs; (b) Loadings of HNTs to different additions of LNL before and after acidification
表 1 HNTs，AC-HNTs和L-AC-HNTs中Si、Al和C元素含量
Table 1. Content of Si、Al and C elements in HNTs, AC-HNTs and L-AC-HNTs
Samples Si Atomic/% Al Atomic /% C Atomic /% HNTs 14.20% 12.39% 14.83% AC-HNTs 14.18% 12.26% 13.19% L-AC-HNTs 12.84% 11.2% 24.59% 
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表 2 HNTs，AC-HNTs和L-AC-HNTs的比表面积和孔径结构数据
Table 2. SBET and porosity data of HNTs, AC-HNTs and L-AC-HNTs
Samples SBET/(m2·g−1) Vpore/(cm3·g−1) HNTs 13.5389 0.04 AC-HNTs 37.2893 0.09 L-AC-HNTs 28.8100 0.08 Notes：SBET is the specific surface area，Vpore is the total pore volume.
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