异丙基丙烯酰胺水凝胶纳米微球粒径的控制及其对多肽吸附的影响

doi:10.11949/0438-1157.20200517

摘要/Abstract

摘要：

采用沉淀聚合法制备了一系列聚（N-异丙基丙烯酰胺-co-N-叔丁基丙烯酰胺-co-丙烯酸）（P-NIPAm-tBAm-AAc）水凝胶纳米微球（NPs），分散性好且粒径可控。通过调整配方，其水动力学直径可控制在71~304 nm之间，经动态光散射（DLS）表征，PDI值均小于0.1。由于电荷斥力的作用，亲电单体丙烯酸（AAc）的用量从5%增加到50%（摩尔分数），粒径从71 nm增大至219 nm；而疏水单体叔丁基丙烯酰胺（tBAm）的使用，使微球的粒径趋于变小；表面活性剂十二烷基磺酸钠（SDS）的量增大，NPs的粒径逐渐减小，最小可达71 nm。将所制备的NPs用于多肽（LEVLFQGP）的吸附，结果表明，吸附率随NPs粒径的减小而增大，并且与聚合物的配方有关，当AAc的摩尔分数为20%、粒径为128 nm时，吸附率为90%。经DLS表征，NPs的体积相变温度（LCST）为(20±2)℃，因此分别在35℃和5℃下对多肽进行吸附/解吸，5次循环实验后，吸附率降低小于7%。本研究探索了水凝胶纳米微球粒径的影响因素及粒径对目标多肽亲和性的影响，可作为制备尺寸均一、粒径可控水凝胶纳米微球的参考。

关键词: 异丙基丙烯酰胺, 水凝胶纳米微球, 水动力学直径, 吸附, 纳米粒子, 粒度分布

Abstract:

A library of poly(N-isopropylacrylamide-co-N-tert-butylacrylamide-co-acrylic acid) (P-NIPAm-tBAm-AAc) hydrogel nanoparticles with good dispersion and uniform size were prepared by precipitation polymerization method. Their hydrodynamic diameters were controlled from 71 nm to 304 nm proved by dynamic light scattering (DLS) with adjusting the polymerization formulation, while the PDI values are all below 0.1. Due to the charge repulsion, the particle size increased from 71 nm to 219 nm when the feeding of electrophilic monomer AAc increased from 5% to 50%(mol) in polymerization. Meanwhile, the inverse effect was also revealed on the hydrophobic monomer tBAm, that is, the nanoparticle size decreased along with increasing its feeding ratio. Besides, the increased usage of the surfactant SDS resulted in the microspheres being smaller to 71 nm. It is proved that the NPs size greatly affected their affinity to the target peptides (LEVLFQGP), and the results showed that the adsorption rate increased with decreasing the nanoparticle size. When the molar ratio of AAc was 20% and the diameter was 128 nm, the adsorption rate could reach 90%. Furthermore, the adsorption and desorption experiment was performed with changing the environmental temperature from 35℃ to 5℃ since the volume phase transition temperature (LCST) of NPs is (20±2)℃ proved by DLS. After five times adsorption/desorption circulation experiments, the reduction of NPs adsorption rate on target peptide was below 7%. Therefore, the prepared and screened NPs are size controlled and reusable.

Key words: N-isopropylacrylamide, hydrogel nanoparticles, hydrodynamic diameter, adsorption, nanoparticles, particle size distribution

中图分类号:

O 648.17

侯雅琦, 沈敬尧, 易达, 王哲, 康玲玲, 孟子晖, 薛敏. 异丙基丙烯酰胺水凝胶纳米微球粒径的控制及其对多肽吸附的影响[J]. 化工学报, 2020, 71(S2): 267-272.

Yaqi HOU, Jingyao SHEN, Da YI, Zhe WANG, Lingling KANG, Zihui MENG, Min XUE. Influences on diameter of isopropylacrylamide hydrogel nanoparticles and its effect on peptide affinity[J]. CIESC Journal, 2020, 71(S2): 267-272.

图/表 8

图1 NPs对多肽的吸附解吸循环示意图

Fig.1 Schematic diagram of adsorption and desorption cycles of fluoride by NPs

表1 不同AAc比例的水凝胶纳米微球的zeta电位和粒径数据

Table 1 Zeta potential and particle size data of NPs with different AAc ratios

样品	AAc用量/ %(mol)	水动力学直径/nm	PDI值	zeta电位值
1	5	71.15	0.012	-25.5
2	10	103.81	0.033	-27.4
3	15	111.95	0.051	-28.8
4	20	128.24	0.027	-31
5	25	157.67	0.056	-32.5
6	30	159.17	0.015	-34.1
7	35	161.92	0.046	-36.2
8	40	165.33	0.071	-37.3
9	50	219.31	0.064	-38.6

图2 水凝胶纳米微球的水动力学直径与tBAm用量之间的关系

Fig.2 The hydrodynamic diameter of NPs with different ratio of tBAm

图3 水凝胶纳米微球的结构示意图

Fig.3 The sketch of the NPs microstructure

图4 水凝胶纳米微球的水动力学直径与SDS用量的关系

Fig.4 The hydrodynamic diameter of NPs with different ratio of quality of SDS

图5 水凝胶纳米微球的水动力学直径与其对多肽吸附率的关系

Fig.5 Relationship between particle size of NPs and its affinity to the target peptide

图6 水凝胶的温度敏感性

Fig.6 Temperature sensitivity of hydrogel

图7 水凝胶纳米微球的重复利用性

Fig.7 Reusability study of the hydrogel nanoparticles

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