酶响应型菊酯/二氧化硅纳米粒的制备及性质

余圣; 方夏伦; 邹爱华

doi:10.14135/j.cnki.1006-3080.20201010001

酶响应型菊酯/二氧化硅纳米粒的制备及性质

doi: 10.14135/j.cnki.1006-3080.20201010001

华东理工大学化学与分子工程学院，上海 200237

基金项目: 国家自然科学基金(21872051)；国家重点研发计划(2017YFD0200306)

详细信息

作者简介:
余圣：余　圣(1995-)，男，硕士生，主要研究方向为刺激响应型纳米粒的制备。E-mail：ecustys@163.com

通讯作者:
邹爱华，E-mail：aihuazou@ecust.edu.cn

中图分类号: TQ450.1
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出版历程
- 收稿日期: 2020-10-10
- 网络出版日期: 2020-12-16

Preparation and Characterization of Enzyme-Responsive LC/HMS Nanoparticles

School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China

摘要

摘要: 以高效氯氟氰菊酯(LC)为模型药物，通过物理吸附作用将LC负载在氨基化中空介孔二氧化硅(HMSN)纳米粒中，通过酰胺化反应在HMSN表面接枝羧甲基-β-环糊精(CM-β-CD)作为封堵分子，制备得到α-淀粉酶响应型CM-β-CD/LC/HMSN纳米粒。通过傅里叶变换红外光谱(FT-IR)、N₂物理吸附-脱附及Zeta电位测试等实验证实该纳米粒制备的可行性。体外释放实验结果表明，在α-淀粉酶存在的条件下，CM-β-CD/LC/HMSN中LC的释放率可达55%，在无酶条件下LC的释放率仅约为20%，表明该农药配方的酶依赖性较强。分别采用浸叶法和浸虫法测定CM-β-CD/LC/HMSN对黏虫幼虫的杀虫活性，浸叶法测定结果表明CM-β-CD/LC/HMSN对黏虫幼虫具有良好的杀虫效果，但浸虫法效果较差。这一差异的原因可能是CM-β-CD/LC/HMSN在靶标幼虫体内可酶解环糊精从而释放LC，导致黏虫幼虫死亡。
- 控释 /
- 酶响应型 /
- 纳米农药 /
- 介孔二氧化硅 /
- 高效氯氟氰菊酯
Abstract: Smart nano-pesticides have been prepared to efficiently deliver a sufficient amount of active ingredients in response to different stimuli, employing targeted and controlled release mechanisms. In this paper, an enzyme-responsive carrier for controlled release of lambda-cyhalothrin (LC) was prepared through loading LC into aminated hollow mesoporous silica (HMSN) nanoparticles by physical adsorption, and then carboxymethyl-β-cyclodextrin (CM-β-CD) was coated onto the surface of HMSN using amidation reaction as the blocking molecule. A series of physicochemical characterization showed the successful construction of the CM-β-CD/LC/HMSN material. An in vitro release test showed that the LC release amount from CM-β-CD /LC/HMSN reached up to 55% in the presence of α-amylase, while only about 20% could be released in the absence of the enzyme, suggesting that the pesticide release was dependent on enzymatic activity. Biological tests showed that the pesticide formulation had good insecticidal effect on Mythimna separate larvae. Based on the results obtained by different experimental methods, we believe that the nanoparticles would be useful for releasing LC after degradation of cyclodextrin enzymatically in vivo , suppressing the survival of Mythimna separate larvae.
- controlled release /
- enzyme responsiveness /
- nano-pesticide /
- mesoporous silica /
- lambda-cyhalothrin

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图 1 HMSN的透射电镜图

Figure 1. TEM image of HMSN

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图 2 HMS、HMSN和CM-β-CD/HMSN的红外光谱图

Figure 2. FT-IR spectra of HMS, HMSN and CM-β-CD/HMSN

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图 3 HMSN和CM-β-CD/HMSN的N₂吸附-脱附等温线(a)和孔径分布(b)

Figure 3. N₂ Adsorption-desorption isotherm (a) and pore size distribution (b) of HMSN and CM-β-CD/HMSN

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图 4 HMSN和CM-β-CD/HMSN的XRD图谱

Figure 4. XRD patterns of HMSN and CM-β-CD/HMSN

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图 5 CM-β-CD/LC/HMSN的制备过程示意图

Figure 5. Schematic diagram of preparation process of CM-β-CD/LC/HMSN

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图 6 HMS、HMSN、LC/HMSN、CM-β-CD/HMSN和CM-β-CD/LC/HMSN的Zeta电位（图中的误差条代表标准差(n = 3)）

Figure 6. Zeta potential of HMS, HMSN, LC/HMSN, CM-β-CD/HMSN and CM-β-CD/LC/HMSN (Error bars in the graph represent standard deviations (n = 3))

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图 7 HMSN、LC/HMSN和CM-β-CD/LC/HMSN的TGA曲线

Figure 7. TGA curves of HMSN、LC/HMSN and CM-β-CD/LC/HMSN

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图 8 LC/HMSN和CM-β-CD/LC/HMSN在DMF与水混合溶液(体积比6∶4)中的释放曲线（图中的误差条代表标准差(n = 3)）

Figure 8. Release curves of LC/HMSN and CM-β-CD/LC/HMSN in DMF aqueous solution (V(DMF):V(H₂O)=6∶4) (Error bars in the graph represent standard deviations (n = 3))

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图 9 CM-β-CD/LC/HMSN与LC在浸叶法(a)与浸虫法(b)下对黏虫的致死率（图中的误差条代表标准差(n = 3)）

Figure 9. Mortality of CM-β-CD/LC/HMSN and LC for Mythimna separata in leaf dipping method (a) and larva dipping method (b) (Error bars in the graph represent standard deviations (n = 3))

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表 1 HMSN和CM-β-CD/HMSN的孔结构参数

Table 1. Pore structure parameters of HMSN and CM-β-CD/HMSN

Sample	S_BET/(m²·g⁻¹)	V_t/(cm³·g⁻¹)	D_p/nm
HMSN	473.28	0.30	2.45
CM-β-CD/HMSN	51.68	0.08	—

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表 2 采用浸叶法与浸虫法时CM-β-CD/LC/HMSN与LC对黏虫的杀虫活性

Table 2. Insecticidal activity of CM-β-CD/LC/HMSN and LC to Mythimna separata using larva dipping method and leaf dipping method, respectively

Sample	Dipping method	Toxicity regression equation	ρ(LC₅₀)/(mg·L⁻¹)	95% Fiducial limit/(mg·L⁻¹)
CM-β-CD/LC/HMSN	Leaf dipping	Y=2.14+2.19X	20.12	13.06~30.99
CM-β-CD/LC/HMSN	Larva dipping	Y=2.49+1.17X	135.24	115.90~157.81
LC	Leaf dipping	Y=3.59+3.65X	2.43	1.37~4.30
LC	Larva dipping	Y=2.83+1.83X	15.24	13.91~16.70
X=lg ρ(LC₅₀)，Y represents death rates

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