磁组装法简单制备均匀显色的葡萄糖响应型光子晶体凝胶

doi:10.6023/A24030080

摘要/Abstract

选用化学稳定性良好的3-丙烯酰胺基苯硼酸(3-APBA)为葡萄糖响应共聚单体、聚(乙烯吡咯烷酮)包覆的磁性纳米颗粒(Fe₃O₄@PVP MCNCs)作为磁组装单元, 在磁场和紫外光照共同作用下引发预聚液聚合形成内部含有有序的一维光子晶体链的葡萄糖响应型光子晶体凝胶. 系统探究了MCNCs粒径、浓度、磁场强度及测试环境pH对其响应性能的影响. 结果显示, 添加了MCNCs (浓度为4 g/L、粒径为181 nm)的预聚液, 于8 mT的磁场强度下制备的光子晶体凝胶具有最佳的葡萄糖响应性能. 该凝胶能够在0到50 mmol/L的葡萄糖溶液中由蓝色变为橙黄色, 达到100 nm衍射波长的迁移, 并具有良好的重复使用性能. 基于一维磁组装的葡萄糖响应型光子晶体凝胶具有制备工艺简便、结构色均匀和响应稳定可逆等优势, 在葡萄糖的可视化检测领域具有潜在的应用前景.

关键词: 磁组装, 光子晶体, 葡萄糖响应, 水凝胶, 可视化

To efficiently prepare glucose-responsive photonic crystal gels with homogeneous coloration is still a challenge. A glucose-responsive gel embedded with ordered one-dimensional photonic crystal chains is fabricated by curing the precursors under both magnetic field and UV light. The chemically stable 3-acrylamidophenylboronic acid (3-APBA) is selected as the glucose-responsive co-monomer, which is negatively charged after recognizing glucose and makes the gel swelling. However, poly(vinylpyrrolidone)-coated magnetic colloidal nanoparticles (Fe₃O₄@PVP MCNCs) are prepared by solvothermal method and used as the magnetic assembly elements for the construction of the one-dimensional photonic crystal structure. MCNCs suspended in dimethyl sulfoxide/ethylene glycol (DMSO/EG) mixed solvent reach equilibrium by both spatial repulsion of PVP shell polymer and magnetic attraction along the direction of applied magnetic field, rapidly arranging into one-dimensional chain-like structures; while in the direction perpendicular to the magnetic field, magnetic particles repel each other and maintain the independent chains. When the total monomer concentration is 2.5 mol/L, the feeding molar ratio of 3-APBA and crosslinker to monomers are respectively 20% and 0.2%, the resultant hydrogel has satisfactory glucose-responsive swelling properties. The effects of MCNCs size, concentration, magnetic field strength and environmental pH on the glucose-responsive performance are investigated systematically. The diffraction wavelength of the photonic crystal gels will be red-shifted with the increase of the particle size and concentration of the MCNCs, the decrease of the applied magnetic field strength, and the enhancement of the test environment alkalinity. The results show that the photonic crystal gel, prepared by polymerizing the precursor solution containing MCNCs concentration of 4 g/L and a particle size of 181 nm at a moderate magnetic field strength of 8 mT, has the optimal glucose-responsive performance. It is able to change from blue to orange in glucose solutions from 0 to 50 mmol/L with satisfactory reusability, reaching a diffraction wavelength migration of nearly 100 nm. The glucose-responsive photonic crystal gel based on one-dimensional magnetic assembly chains has the advantages of facile preparation process, homogeneous structural color as well as stable and reversible responsiveness, and therefore, it has potential applications in the field of visual detection of glucose.

Key words: magnetic assembly, photonic crystal, glucose response, hydrogel, visualization

引用此文

胡亚琴, 巨晓洁, 汪伟, 刘壮, 潘大伟, 谢锐, 褚良银. 磁组装法简单制备均匀显色的葡萄糖响应型光子晶体凝胶[J]. 化学学报, 2024, 82(7): 782-789.

Yaqin Hu, Xiaojie Ju, Wei Wang, Zhuang Liu, Dawei Pan, Rui Xie, Liangyin Chu. Efficient Preparation of Homogeneous Chromogenic Glucose-responsive Photonic Crystal Gels by Magnetic Assembly Method[J]. Acta Chimica Sinica, 2024, 82(7): 782-789.

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图/表 8

图1. (a~c)不同粒径的MCNCs的场发射扫描电镜图及(d)在水溶液中的粒径分布: 湿态粒径分别为157 (a)、181 (b)及208 nm (c)

Figure 1. (a~c) FESEM images of MCNCs with different particle sizes and (d) their particle size distribution in aqueous solution: The particle sizes in the wet state are 157 (a), 181 (b) and 208 nm (c)

图2. MCNCs在DMSO/EG混合溶液中的光学性能: 湿态粒径分别为157 (a, d)、181 (b, e)和208 nm (c, f); MCNCs浓度为4 g/L, 溶剂体积比为1∶1

Figure 2. Optical properties of MCNCs nanoparticles in the mixture of DMSO/EG: The particle sizes in the wet state are 157 (a, d), 181 (b, e) and 208 nm (c, f) respectively. The concentration of MCNCs is 4 g/L, and the volume ratio of solvent is 1∶1

Sample	Size of MCNCs/nm	Concentration of MCNCs/(g•L⁻¹)
HAB	—	0
PHAB-1	157	4
PHAB-2	181	4
PHAB-3	208	4
PHAB-4	181	2
PHAB-5	181	6

表1. 葡萄糖响应型凝胶的组成

Table 1. Composition of glucose responsive gels

图3. 葡萄糖响应型空白凝胶(a)和光子晶体凝胶(b~d)断面的FESEM图及EDS谱图: 添加MCNCs的粒径分别为157 (b)、181 (c)及208 nm (d), 凝胶聚合时的磁场强度为8 mT

Figure 3. Cross-sectional FESEM images and EDS spectra of glucose-responsive blank gel (a) and photonic crystal gels (b~d): The particle sizes of embedded MCNCs are 157 (b), 181 (c) and 208 nm (d), respectively. The magnetic strength of 8 mT is used to polymerize the hydrogels

图4. MCNCs粒径及磁场强度对光子晶体凝胶响应性能的影响: MCNCs的粒径分别为157 (a, d)、181 (b, e)和208 nm (c, f); 所有测试溶液的pH恒定在7.36, 温度恒定在37 ℃

Figure 4. Effect of MCNCs particle size and magnetic field strength on the response properties of photonic crystal gels: The particle sizes of MCNCs are 157 (a, d), 181 (b, e) and 208 nm (c, f), respectively. The pH of all tested solutions is constant at 7.36 and the temperature is 37 ℃

图5. MCNCs添加浓度分别为2 (a, d)、4 (b, e)和6 g/L (c, f)时对光子晶体水凝胶的响应性能的影响: 所有测试溶液的pH恒定在7.36, 温度恒定在37 ℃

Figure 5. Effect of the MCNCs with the feed concentrations of 2 (a, d), 4 (b, e) and 6 g/L (c, f) on the response properties of photonic crystal gels: The pH of all solutions tested is constant at 7.36 and the temperature is 37 ℃

图6. pH对光子晶体凝胶葡萄糖响应性能的影响, 标尺为0.5 cm

Figure 6. Effect of pH on the glucose-responsive performance of photonic crystal gels, the scale bars are 0.5 cm

图7. 光子晶体凝胶在浓度为0~50 mmol/L的葡萄糖溶液中的重复使用性能

Figure 7. Reusability performance of photonic crystal gels in response to glucose concentration with 0~50 mmol/L

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