2,4-D/CMC接枝物纳米粒子的制备与缓释性能研究

doi:10.11949/j.issn.0438-1157.20181292

摘要/Abstract

摘要：

以羧甲基纤维素钠（CMC）为基材，甲基丙烯酸甲酯（MMA）和二甲基二烯丙基氯化铵（DMDAAC）为改性单体，通过乳液聚合制备了CMC-g-P(MMA-DMDAAC)共聚物，采用自组装方法负载2,4-二氯苯氧乙酸（2,4-D）得到2,4-D/CMC-g-P(MMA-DMDAAC)纳米药物缓释体系。利用傅里叶红外光谱（FTIR）、差示扫描量热法（DSC）、热重分析（TGA）、扫描电镜（SEM）、粒度分析仪对其结构和形貌进行表征，并探究其载药性能和缓释性能。结果表明，2,4-D/CMC-g-P(MMA-DMDAAC)载药粒子呈笼状结构，粒度分布为160～425 nm；其载药率随着CMC∶MMA∶DMDAAC的摩尔比增大而提高，最高可达40.8%；其药物累计释放率随CMC∶MMA∶DMDAAC的摩尔比增大而降低，其释放行为符合Weibull模型，遵循Fick扩散机理。

关键词: 羧甲基纤维素钠, 2,4-二氯苯氧乙酸, 二甲基二烯丙基氯化铵, 缓释

Abstract:

CMC-g-P(MMA-DMDAAC) was prepared by emulsion copolymerization and trapping as well as encapsulation of 2,4-D via self-assembly resulted in the formation of 2,4-D/CMC-g-PDMDAAC nanoparticles. Its structure and morphology were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron (SEM) and dynamic light scattering (DLS). Furthermore, the encapsulation efficiency and sustained-release characteristics were investigated. The results demonstrated that the 2,4-D/CMC-g-P(MMA-DMDAAC) drug-loaded particles showed a cage structure with a particle size distribution from 160 nm to 425 nm. Moreover, the encapsulation efficiency increased as the molar ratio of monomers increased, which could reach up to 40.8%. In addition, the higher molar ratio of the monomers was, the lower cumulative release rate of the drug exhibited. Overall, the mechanism of release of 2,4-D from nanocarriers was consistent with Fickian behavior.

Key words: sodium carboxymethyl cellulose, 2,4-dichlorophenoxyacetic acid, dimethyl diallyl ammonium chloride, sustained release

中图分类号:

TQ 450.6

邱松发, 许斌华, 林冠权, 周新华, 陈铧耀, 周红军. 2,4-D/CMC接枝物纳米粒子的制备与缓释性能研究[J]. 化工学报, 2019, 70(5): 2007-2015.

Songfa QIU, Binhua XU, Guanquan LIN, Xinhua ZHOU, Huayao CHEN, Hongjun ZHOU. Preparation and sustained release performance of 2,4-D/grafted CMC nanoparticles[J]. CIESC Journal, 2019, 70(5): 2007-2015.

图/表 13

图1 CMC-g-P(MMA-DMDAAC)合成示意图

Fig.1 Schematic diagram of CMC-g-P (MMA-DMDAAC) synthesis

图2 CMC(a)、CMC-g-P(MMA-DMDAAC)(b)、2,4-D/CMC-g-P(MMA-DMDAAC)(c)和2,4-D(d)的红外光谱图

Fig.2 Infrared spectra of CMC(a), CMC-g-P(MMA-DMDAAC)(b), 2,4-D/CMC-g-P(MMA-DMDAAC)(c) and 2,4-D(d)

图3 CMC-g-P(MMA-DMDAAC(a)和CMC(b)的DSC图

Fig.3 DSC diagrams of CMC-g-P (MMA-DMDAAC(a) and CMC(b)

图4 CMC(a)、CMC-g-P (MMA-DMDAAC)(b)的TGA图

Fig.4 TGA diagrams of CMC(a) and CMC-g-P (MMA-DMDAAC)(b)

图5 CMC(a)、CMC-g-P(MMA-DMDAAC)(b)的DTG图

Fig.5 DTG diagrams of CMC(a) and CMC-g-P(MMA-DMDAAC)(b)

图6 CMC-g-P(MMA-DMDAAC)(a)和2,4-D/CMC-g-P(MMA-DMDAAC)(b)的扫描电镜图

Fig.6 SEM images of CMC-g-P (MMA-DMDAAC)(a) and 2,4-D/CMC-g-P (MMA-DMDAAC)(b)

图7 不同CMC∶MMA∶DMDAAC的CMC-g-P(MMA-DMDAAC)在黄瓜叶上的接触角

Fig.7 Contact angle of CMC-g-P(MMA-DMDAAC) with different CMC∶MMA∶DMDAAC on cucumber leaves

表1 不同CMC∶MMA∶DMDAAC载药前后的平均粒径与电势

Table 1 Mean particle size and potential before and after drug loading with different molar ratios of CMC∶MMA∶DMDAAC

CMC∶MMA∶DMDAAC （molar ratio）	Before drug loading		After drug loading
CMC∶MMA∶DMDAAC （molar ratio）	Average particle size/nm	Zeta potential/mV	Average particle size/nm	Zeta potential/mV
1∶1∶1	104.35	?15.33	160.06	?13.75
1∶2∶2	145.40	?19.21	141.46	?4.42
1∶4∶4	283.49	?11.65	264.75	4.60
1∶6∶6	315.94	2.12	286.90	11.37
1∶8∶8	338.88	13.20	328.10	16.48
1∶12∶12	532.84	20.32	425.97	24.67

表2 载体用量对包封率与载药率的影响

Table 2 Effect of carrier dosage on encapsulation efficiency and drug loading rate

1∶6∶6 emulsion dosage/ml	Encapsulation efficiency/%	Drug loading rate/%
0.5	3.69	22.5
1	12.33	32.65
1.5	19.53	33.86
2	26.72	34.44
3	27.44	26.45
4	28.88	22.11
5	28.16	18.13
6	28.88	15.92

表3 不同载体的包封率与载药率

Table 3 Encapsulation efficiency and drug loading rate of different carriers

CMC∶MMA∶DMDAAC(molar ratio)	Encapsulation efficiency/%	Drug loading rate/%
1∶1∶1	5.85	19.30
1∶2∶2	9.45	23.37
1∶4∶4	19.53	32.93
1∶6∶6	29.60	36.79
1∶8∶8	38.24	40.80

图8 不同摩尔比的载药体系中载药纳米粒子药物释放曲线

Fig.8 Release curves of drug-loaded nanoparticles in different carriers

图9 动力学模型拟合图

Fig.9 Fit of release curves of 2,4-D/CMC-g-P(MMA-DMDAAC)

表4 载药纳米粒子药物释放拟合结果

Table 4 Fitting results for release curves of 2,4-D/CMC-g-P(MMA-DMDAAC)

Sample	Zero-order		First-order		Weibull
Sample	R ²	K ₀	R ²	K ₁	R ²	b
1∶2∶2	0.2042	0.5518	0.9247	1.0093	0.9244	0.28474
1∶6∶6	0.2241	0.4795	0.9164	0.8190	0.9053	0.23555
1∶12∶12	0.2593	0.4075	0.9107	0.6478	0.9012	0.21463

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