光栅结构对智能凝胶光栅传感器检测性能的影响规律

doi:10.16085/j.issn.1000-6613.2024-0387

摘要/Abstract

摘要：

深入研究光栅几何结构参数对智能凝胶光栅传感器检测性能的定量影响规律是实现其结构优化设计的重要前提。本文设计了一种由N-异丙基丙烯酰胺（NIPAM）单体与大分子交联剂四臂聚乙二醇丙烯酰胺（tetra-arm-PEGAAm）聚合而成的温度响应型智能凝胶光栅传感器，并采用微接触印刷法制备了3种不同槽深的凝胶光栅，由此研究光栅结构对检测性能的影响规律。研究结果表明，制备得到的凝胶光栅在干态和湿态下其表面微观结构均表现出高度的规整和有序性，且其具有高透明度，并能实现实时可逆响应。此外，在相同的温度刺激下，PNIPAM凝胶光栅的高度越大，衍射信号越强，呈现出更显著的衍射效率变化和信号放大效应。相关研究结果可为智能凝胶光栅传感器的结构优化设计提供理论指导。

关键词: 智能凝胶, 光栅结构, 温度响应, 体积相变, 智能检测

Abstract:

A thorough investigation on the quantitative impacts of grating geometric parameters on the detection performance of smart hydrogel grating sensors is an essential prerequisite for rationally designing their geometric structures. In this study, the N-isopropylacrylamide (NIPAM) monomers and tetra-arm polyethylene glycol acrylamide (tetra-arm-PEGAAm) regarded as large-molecule cross-linking agent were used to synthetize temperature-responsive smart hydrogel grating sensor, and three various heights of hydrogel gratings were fabricated by microcontact printing to explore their influences on the detection performances. The results indicated that, the fabricated hydrogel gratings exhibited highly regular and ordered surface microstructures under both dry and wet conditions, and always possessing with high transparency and real-time reversible response properties. Besides, as the height of hydrogel grating increased, the diffraction signals of smart hydrogel grating sensors could be obviously enhanced under the same temperature stimulus, thus exhibiting more pronounced changes in diffraction efficiency and signal amplification. These findings in this study provided valuable guidance for the rational design of the geometric structures of smart hydrogel grating sensors.

Key words: smart hydrogels, grating structures, thermo-responsive, volume phase transition, intelligent detection

中图分类号:

TQ317

赖俊华, 潘大伟, 巨晓洁, 刘壮, 谢锐, 汪伟, 褚良银. 光栅结构对智能凝胶光栅传感器检测性能的影响规律[J]. 化工进展, 2025, 44(3): 1578-1587.

LAI Junhua, PAN Dawei, JU Xiaojie, LIU Zhuang, XIE Rui, WANG Wei, CHU Liangyin. Effects of grating structures on detection performances of smart hydrogel grating sensors[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1578-1587.

图/表 13

图1 微接触印刷法制备凝胶光栅的过程

图2 凝胶光栅光学检测系统及不同槽深凝胶光栅发生衍射示意图

图3 不同槽深PNIPAM凝胶光栅的形貌表征

图4 不同槽深凝胶光栅在干态和湿态下光栅的结构表征

图5 不同槽深的PNIPAM凝胶光栅随温度升高的AFM微观结构变化

图6 不同初始槽深凝胶光栅的周期和槽深随温度升高的变化规律

图7 不同槽深PNIPAM凝胶光栅随温度升高的透光率变化

图8 PNIPAM凝胶光栅的实时温度响应测试结果

图9 PNIPAM凝胶光栅的可重复性能测试结果

图10 不同槽深PNIPAM凝胶光栅响应温度的衍射光强度变化规律

图11 不同槽深PNIPAM凝胶光栅响应温度升高的衍射效率变化规律及其相关分析

图12 温度升高对纯水和PNIPAM凝胶折射率的影响

图13 温度升高时的(ng-ns)2、h2 的相对变化对[(ng-ns)h]2的影响

参考文献 36

1	ZHAO Jiajia, WANG Wei, CAI Quanwei, et al. Efficient detection of hyperkalemia with highly transparent and ion-recognizable hydrogel grating sensors[J]. Industrial & Engineering Chemistry Research, 2022, 61(6): 2483-2493.
2	ZHAO Jiajia, WANG Wei, WANG Fang, et al. Smart hydrogel grating immunosensors for highly selective and sensitive detection of human-IgG[J]. Industrial & Engineering Chemistry Research, 2020, 59(22): 10469-10475.
3	YE Gang, YANG Canqiang, WANG Xiaogong. Sensing diffraction gratings of antigen-responsive hydrogel for human immunoglobulin-G detection[J]. Macromolecular Rapid Communications, 2010, 31(15): 1332-1336.
4	LUCÍO María Isabel, MONTOTO Andy Hernández, Estrella FERNÁNDEZ, et al. Label-free detection of C-reactive protein using bioresponsive hydrogel-based surface relief diffraction gratings[J]. Biosensors & Bioelectronics, 2021, 193: 113561.
5	WANG Xiaoqi, WANG Xiaogong. Aptamer-functionalized hydrogel diffraction gratings for the human thrombin detection[J]. Chemical Communications, 2013, 49(53): 5957-5959.
6	YE Gang, WANG Xiaogong. Glucose sensing through diffraction grating of hydrogel bearing phenylboronic acid groups[J]. Biosensors & Bioelectronics, 2010, 26(2): 772-777.
7	YE Gang, LI Xinyang, WANG Xiaogong. Diffraction grating of hydrogel functionalized with glucose oxidase for glucose detection[J]. Chemical Communications, 2010, 46(22): 3872-3874.
8	TIAN Xiaoyu, SUN Mengwei, WEN Guoyu, et al. Ultrasensitive hydrogel grating detector for real-time continuous-flow detection of trace threat Pb²⁺ [J]. Journal of Hazardous Materials, 2023, 443: 130289.
9	PENG Hanyu, WANG Wei, GAO Fuhua, et al. Ultrasensitive diffraction gratings based on smart hydrogels for highly selective and rapid detection of trace heavy metal ions[J]. Journal of Materials Chemistry C, 2018, 6(42): 11356-11367.
10	WANG Xiaoqi, YE Gang, WANG Xiaogong. Hydrogel diffraction gratings functionalized with crown ether for heavy metal ion detection[J]. Sensors and Actuators B: Chemical, 2014, 193: 413-419.
11	LIU Yuqiong, JU Xiaojie, ZHOU Xinglong, et al. A novel chemosensor for sensitive and facile detection of strontium ions based on ion-imprinted hydrogels modified with guanosine derivatives[J]. Journal of Hazardous Materials, 2022, 421(2022): 126801.
12	TIAN Xiaoyu, ZHANG Tingting, WEN Guoyu, et al. Highly sensitive hydrogel gratings for real-time detection of trace hexavalent chromium ions in water[J]. Industrial & Engineering Chemistry Research, 2023, 62(30): 11885-11893.
13	张婷婷, 潘大伟, 巨晓洁, 等. Hg²⁺响应型智能凝胶检测光栅的构建与性能[J]. 化工进展, 2023, 42(8): 4143-4152.
	ZHANG Tingting, PAN Dawei, JU Xiaojie, et al. Fabrication and performance of Hg²⁺-responsive smart hydrogel grating detector[J]. Chemical Industry and Engineering Progress, 2023, 42(8): 4143-4152.
14	LI Xu, TANG Bo, WU Bing, et al. Highly sensitive diffraction grating of hydrogels as sensors for carbon dioxide detection[J]. Industrial & Engineering Chemistry Research, 2021, 60(12): 4639-4649.
15	BERNARD André, DELAMARCHE Emmanuel, SCHMID Heinz, et al. Printing patterns of proteins[J]. Langmuir, 1998, 14(9): 2225-2229.
16	TANAKA Toyoichi, FILLMORE David J. Kinetics of swelling of gels[J]. The Journal of Chemical Physics, 1979, 70(3): 1214-1218.
17	TANAKA Toyoichi, SATO Eriko, HIROKAWA Yoshitsugu, et al. Critical kinetics of volume phase transition of gels[J]. Physical Review Letters, 1985, 55(22): 2455-2458.
18	刘壮, 谢锐, 巨晓洁, 等. 具有快速响应特性的环境响应型智能水凝胶的研究进展[J]. 化工学报, 2016, 67(1): 202-208.
	LIU Zhuang, XIE Rui, JU Xiaojie, et al. Progress in stimuli-responsive smart hydrogels with rapid responsive characteristics[J]. CIESC Journal, 2016, 67(1): 202-208.
19	ZHOU Xinglong, ZHOU Changhai, GONG Jueying, et al. Novel thermo and ion-responsive copolymers based on metallo-base pair directed host-guest complexation for highly selective recognition of Hg²⁺ in aqueous solution[J]. Journal of Hazardous Materials, 2023, 445: 130610.
20	LIU Yuqiong, JU Xiaojie, PU Xingqun, et al. Visual detection of trace lead(Ⅱ) using a forward osmosis-driven device loaded with ion-responsive nanogels[J]. Journal of Hazardous Materials, 2021, 404(2021): 124157.
21	KISHORE P V N, SHANKAR M SAI, SATYANARAYANA M. Detection of trace amounts of chromium(Ⅵ) using hydrogel coated Fiber Bragg grating[J]. Sensors and Actuators B: Chemical, 2017, 243: 626-633.
22	谢诗婷, 刘壮, 谢锐, 等. 聚(N-异丙基丙烯酰胺-共聚-烯丙基硫脲)智能微凝胶的制备及其Hg²⁺响应性能的研究[J]. 化工学报, 2023, 74(6): 2689-2698.
	XIE Shiting, LIU Zhuang, XIE Rui, et al. Study on preparation of poly(N-isopropylacrylamide-co-allylthiourea) smart microgels and responsive performance of Hg²⁺ [J]. CIESC Journal, 2023, 74(6): 2689-2698.
23	PENG Hanyu, WANG Wei, GAO Fuhua, et al. Smart hydrogel gratings for sensitive, facile, and rapid detection of ethanol concentration[J]. Industrial & Engineering Chemistry Research, 2019, 58(38): 17833-17841.
24	BARRIOS C A, ZHENHE C, NAVARRO-VILLOSLADA F, et al. Molecularly imprinted polymer diffraction grating as label-free optical bio(mimetic)sensor[J]. Biosensors and Bioelectronics, 2011, 26(5): 2801-2804.
25	ACHARYA Ghanashyam, CHANG Chunli, HOLLAND David P, et al. Rapid detection of S-adenosyl homocysteine using self-assembled optical diffraction gratings[J]. Angewandte Chemie International Edition, 2008, 47(6): 1051-1053.
26	NELSON Keith A, CASALEGNO Roger, DWAYNE MILLER R J, et al. Laser-induced excited state and ultrasonic wave gratings: Amplitude and phase grating contributions to diffraction[J]. The Journal of Chemical Physics, 1982, 77(3): 1144-1152.
27	FAYER M D. Dynamics of molecules in condensed phases: Picosecond holographic grating experiments[J]. Annual Review of Physical Chemistry, 1982, 33: 63-87.
28	WANG Xiaoqi, LIU Xiyang, WANG Xiaogong. Hydrogel diffraction grating as sensor: A tool for studying volume phase transition of thermo-responsive hydrogel[J]. Sensors and Actuators B: Chemical, 2014, 204: 611-616.
29	SEO Jeong Hyun, CHEN Lijung, VERKHOTUROV Stanislav V, et al. The use of glass substrates with bi-functional silanes for designing micropatterned cell-secreted cytokine immunoassays[J]. Biomaterials, 2011, 32(23): 5478-5488.
30	CHEN Yongjun, KANG E T, NEOH K G, et al. Electroless metallization of glass surfaces functionalized by silanization and graft polymerization of aniline[J]. Langmuir, 2001, 17(23): 7425-7432.
31	KOPECEK Jindrich. Polymer chemistry: Swell gels[J]. Nature, 2002, 417(6887): 388-389.
32	ZHAO Yu, JU Xiaojie, ZHANG Liping, et al. Transparent thermo-responsive poly(N-isopropylacrylamide)-l-poly(ethylene glycol)acrylamide conetwork hydrogels with rapid deswelling response[J]. New Journal of Chemistry, 2019, 43(24): 9507-9515.
33	SCHILD H. G. Poly(N-isopropylacrylamide): Experiment, theory and application[J]. Progress in Polymer Science, 1992, 17(2): 163-249.
34	LI Yong, TANAKA Toyoichi. Phase transitions of gels[J]. Annual Review of Materials Science, 1992, 22(1): 243-277.
35	HIROKAWA Yoshitsugu, TANAKA Toyoichi. Volume phase transition in a nonionic gel[J]. The Journal of Chemical Physics, 1984, 81(12): 6379-6380.
36	HIROTSU Shunsuke, HIROKAWA Yoshitsugu, TANAKA Toyoichi. Volume-phase transitions of ionized N-isopropylacrylamide gels[J]. The Journal of Chemical Physics, 1987, 87(2): 1392-1395.

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