智能二维光子晶体水凝胶精准检测Hg2+

doi:10.6023/A23100443

摘要/Abstract

结合二维光子晶体的德拜衍射效应和水凝胶的体积相转变特性, 开发了一种智能二维光子晶体水凝胶, 用于精准检测Hg²⁺. 采用“三明治”法制备了聚苯乙烯二维光子晶体阵列嵌入的聚(丙烯酰胺-烯丙基硫脲)水凝胶. 水凝胶链上功能基团的N、O、S等原子与Hg²⁺选择性配位, 缩短了水凝胶链之间的距离, 增加了水凝胶的交联密度, 使其收缩, 导致二维光子晶体的聚苯乙烯微球间距缩小, 德拜衍射环直径变大. 通过监测二维光子晶体水凝胶响应前后的德拜衍射环直径, 获知微球间距变化, 实现了高灵敏、高选择性、快速、可逆检测Hg²⁺. 线性检测范围为10~100 nmol/L和25~200 μmol/L, 最低检测限3.32 nmol/L. 所制智能二维光子晶体水凝胶已成功应用于化妆品及水样中Hg²⁺的检测. 该方法测试简单, 只需激光笔和刻度尺, 无需精密的仪器设备, 可实现便携式检测, 为金属离子检测提供了新思路.

关键词: 二维光子晶体, 德拜衍射效应, 智能水凝胶, 体积相转变, 汞离子

A smart two-dimensional photonic crystal (2DPC) hydrogel was developed for accurate detection of Hg²⁺ by combining the Debye diffraction effect of 2DPC and the volume phase transition characteristic of hydrogel. The polystyrene (PS) 2DPC arrays were first fabricated by needle-tip-flow method, in which the monodispersed PS microspheres were orderly self-assembled on the water surface to form PS 2DPC and then transferred to glass slide. The poly(acrylamide-allylthiourea) hydrogels embedded with the PS 2DPC arrays were fabricated by “sandwich” method, in which the polymerization precursor solution including monomers acrylamide and allylthiourea was added to the PS 2DPC surface and covered with a glass slide, followed by photopolymerization. The atoms including N, O and S from functional groups on the hydrogel chains selectively coordinated with Hg²⁺, shortening the distance between the hydrogel chains and increasing the crosslinking density of the hydrogel. As a result, the hydrogel shrank and the PS microsphere spacing of the 2DPC decreased, which increased the diameter of the Debye diffraction ring. The microsphere spacing changes were acquired by monitoring Debye diffraction ring diameters before and after the response of the 2DPC hydrogel, achieving the highly sensitive, selective, reversible and fast detection of Hg²⁺. The linear detection ranges were in 10~100 nmol/L and 25~200 μmol/L, and the limit of detection was found to be 3.32 nmol/L. The prepared smart 2DPC hydrogel was used to detect Hg²⁺ in cosmetics and water samples to evaluate its practicability. The recovery for the detection of Hg²⁺ was 98.8%~102.6% and the relative standard deviation was 0.57%~1.09% for a commercially lipstick, and they were 97.2%~103.4% and 0.61%~0.99% for the tap water, respectively. The results demonstrated that our constructed smart 2DPC hydrogels have good applicability, accuracy and reliability for the detection of Hg²⁺ in real samples. The method is simple for testing, only requiring a laser pointer and a ruler, without needing sophisticated instruments, and it can realize portable detection, providing a new strategy for detecting metal ions.

Key words: two-dimensional photonic crystals, Debye diffraction effect, smart hydrogel, volume phase transition, mercury ions

引用此文

史雨晴, 储名珠, 韩波, 马豪杰, 李然, 侯雪艳, 张玉琦, 王记江. 智能二维光子晶体水凝胶精准检测Hg²⁺[J]. 化学学报, 2024, 82(1): 9-15.

Yuqing Shi, Mingzhu Chu, Bo Han, Haojie Ma, Ran Li, Xueyan Hou, Yuqi Zhang, Ji-Jiang Wang. Smart Two-dimensional Photonic Crystal Hydrogel for Accurate Detection of Hg²⁺[J]. Acta Chimica Sinica, 2024, 82(1): 9-15.

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图/表 6

图1. SEM图像: (a, b) 玻璃基底上的PS 2DPC; (c) 初始制备的P(AAm-ATU)-PS 2DPCH; (d) 在PBS缓冲液中达到溶胀平衡的P(AAm-ATU)-PS 2DPCH. 插图: 相应薄膜的光学照片

Figure 1. SEM images: (a, b) PS 2DPC on glass slide; (c) the freshly prepared P(AAm-ATU)-PS 2DPCH; (d) the P(AAm-ATU)-PS 2DPCH after equilibration in PBS solution. Insets: the photographs of the corresponding films

图2. P(AAm-ATU)-PS 2DPCH和PAAm-PS 2DPCH 与不同溶液作用后的微球间距变化

Figure 2. The particle spacing changes of P(AAm-ATU)-PS 2DPCH and PAAm-PS 2DPCH after reaction with various solutions

图3. (a) P(AAm-ATU)水凝胶聚合反应及其与Hg2+作用示意图. 以AAm和ATU为单体, BIS为交联剂, 光引发聚合制备水凝胶. 水凝胶链上的N、O、S等原子与Hg2+配位, 导致水凝胶体积收缩. 已配位的Hg2+可被HCl水溶液洗脱, 使传感薄膜再生; (b) P(AAm-ATU)-PS 2DPCH与Hg2+作用示意图以及相对应的德拜衍射环照片. d为微球间距, D为德拜衍射环直径. 水凝胶与Hg2+作用后收缩, 使嵌入其中的PS 2DPC阵列的微球间距减小(从d到d'), 对应的德拜衍射环直径从D增大到D'

Figure 3. (a) The polymerization reaction of P(AAm-ATU) hydrogel and the interaction with Hg2+. Hydrogels were prepared by photoinitiated polymerization using AAm and ATU as monomers and BIS as crosslinker. The atoms including N, O, and S on the chains of the hydrogel coordinate with Hg2+, leading to volume shrinkage of the hydrogel. The coordinated Hg2+ can be eluted by HCl aqueous solution to regenerate the sensing film. (b) The schematic illustration for interaction of P(AAm-ATU)-PS 2DPCH and Hg2+, and the photographs of the corresponding Debye diffraction rings. The d represents the microsphere spacing and D represents the diameter of the Debye diffraction ring. The hydrogel shrinks after reaction with Hg2+, resulting in a decrease in microsphere spacing of the embedded PS 2DPC array (from d to d'). The corresponding Debye diffraction ring diameter increases from D to D'

图4. (a) 不同浓度的BIS和(b) AAm/ATU不同质量比条件下制备的各种P(AAm-ATU)-PS 2DPCH与不同浓度的Hg2+作用响应的微球间距变化

Figure 4. After response to Hg2+ at different concentrations, the microsphere spacing changes of the various P(AAm-ATU)-PS 2DPCH fabricated from (a) BIS at different concentrations and (b) different mass ratio of AAm/ATU

图5. (a) P(AAm-ATU)-PS 2DPCH的微球间距变化对Hg2+浓度的依赖性; (b, c) 微球间距变化与Hg2+浓度的线性关系; (d) P(AAm-ATU)-PS 2DPCH与不同金属离子溶液(200 μmol/L)作用的微球间距变化. 插图: P(AAm-ATU)-PS 2DPCH与Hg2+响应前后的光学照片; (e) P(AAm-ATU)-PS 2DPCH在不同浓度Hg2+溶液中的微球间距变化的时间依赖性; (f) P(AAm-ATU)-PS 2DPCH交替与200 μmol/L的Hg2+和 1 mol/L的HCl溶液反应后的微球间距

Figure 5. (a) Dependence of microsphere spacing change of P(AAm-ATU)-PS 2DPCH on the concentration of Hg2+; (b, c) linear relationship between microsphere spacing change and the concentration of Hg2+; (d) microsphere spacing changes for the P(AAm-ATU)-PS 2DPCH in various metal ions solutions (200 μmol/L). Inset: the photographs of P(AAm-ATU)-PS 2DPCH before and after response to Hg2+; (e) time dependence of microsphere spacing changes for the P(AAm-ATU)-PS 2DPCH in Hg2+ at different concentrations; (f) the particle spacing of P(AAm-ATU)-PS 2DPCH after alternate reaction to Hg2+ (200 μmol/L) and HCl (1 mol/L)

Sample	Added	Found	Recovery/%	RSD/% (n=3)
口红	50 nmol/L	50.2 nmol/L	100.4	0.76
	50 µmol/L	51.3 μmol/L	102.6	1.09
	100 µmol/L	98.8 μmol/L	98.8	0.57
自来水	50 nmol/L	50.2 nmol/L	100.4	0.61
	50 µmol/L	51.7 μmol/L	103.4	0.99
	100 µmol/L	97.2 μmol/L	97.2	0.86

表1. 实际样品中Hg2+的检测

Table 1. The detection of Hg2+ in real samples

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智能二维光子晶体水凝胶精准检测Hg²⁺

Smart Two-dimensional Photonic Crystal Hydrogel for Accurate Detection of Hg²⁺

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