Smart Photonic Indicator for Ethanol Detection via Pressure-Responsive Shape Memory Polymers

Abstract

Smart photonic indicators (SPIs) offer a cost-effective and efficient way to monitor and control ethanol concentration, making them suitable for advanced digital informatics systems. The developed sensors can operate even after the removal of external stimuli, featuring exceptional optical memory and reconfigurable nanostructures, which will undoubtedly drive a revolution in colorimetric sensors. The SPI is prepared by polymerizing mixed monomers of poly(ethylene glycol) diacrylate (PEG600DA) and ethoxyethoxyethyl acrylate (EOEOEA) in a silica colloidal crystal template. SPIs contain periodically ordered interconnecting macropores via shape memory polymers (SMPs) that endow the films with structural colors. The evaporation of water can temporarily deform the initial periodic structure. The structure can then be restored by evaporating liquids with lower surface tension, such as water-ethanol solutions. The Laplace pressure generated during solvent evaporation competes with the elasticity of SMPs, driving nanoscale structural transformation. Consequently, the detection range of SPIs for ethanol concentration in water depends on the balance between these two driving forces. Adjusting the size of the macropores expands the detection range allowing differentiation of alcohol concentrations from 5% to 100%. SPIs with selectivity and high sensitivity hold promise for various applications, including information technology, inkless writing, and anticounterfeiting, enhancing the versatility of photonic materials.

Keywords

inverse opals / photonic crystals / shape memory polymers / smart indicators

References

[1] H. T. Luk, C. Mondelli, D. C. Ferré, J. A. Stewart, and J. Pérez-Ramírez, “Status and Prospects in Higher Alcohols Synthesis From Syngas,” Chemical Society Reviews 46, no. 5 (2017): 1358–1426.

[2] X. Ning, Z. Zhang, K. Zheng, X. Wang, and J. Wang, “Experimental and Numerical Studies on the Explosion Characteristics of Ethanol–Air Mixtures Under Aviation Conditions,” Fire 6, no. 9 (2023): 349.

[3] Y. Yu, S. Brandt, N. J. Nicolas, and J. Aizenberg, “Colorimetric Ethanol Indicator Based on Instantaneous, Localized Wetting of a Photonic Crystal,” ACS Applied Materials & Interfaces 12, no. 1 (2020): 1924–1929.

[4] V. I. Kuchuk, I. Y. Shirokova, and E. V. Golikova, “Physicochemical Properties of Water-Alcohol Mixtures of a Homological Series of Lower Aliphatic Alcohols,” Glass Physics and Chemistry 38, no. 5 (2012): 460–465.

[5] Z. J. Derlacki, A. J. Easteal, A. V. J. Edge, L. A. Woolf, and Z. Roksandic, “Diffusion Coefficients of Methanol and Water and the Mutual Diffusion Coefficient in Methanol-Water Solutions at 278 and 298 K,” Journal of Physical Chemistry 89, no. 24 (1985): 5318–5322.

[6] R. J. Jiménez Riobóo, M. Philipp, M. A. Ramos, and J. K. Krüger, “Concentration and Temperature Dependence of the Refractive Index of Ethanol-Water Mixtures: Influence of Intermolecular Interactions,” European Physical Journal E 30, no. 1 (2009): 19.

[7] T. Yarita, R. Nakajima, S. Otsuka, T. Ihara, A. Takatsu, and M. Shibukawa, “Determination of Ethanol in Alcoholic Beverages by High-Performance Liquid Chromatography–Flame Ionization Detection Using Pure Water as Mobile Phase,” Journal of Chromatography A 976, no. 1–2 (2002): 387–391.

[8] K. Sharma, S. P. Sharma, and S. Lahiri, “Novel Method for Identification and Quantification of Methanol and Ethanol in Alcoholic Beverages by Gas Chromatography-Fourier Transform Infrared Spectroscopy and Horizontal Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy,” Journal of AOAC International 92, no. 2 (2009): 518–526.

[9] I. B. Burgess, L. Mishchenko, B. D. Hatton, M. Kolle, M. Lončar, and J. Aizenberg, “Encoding Complex Wettability Patterns in Chemically Functionalized 3D Photonic Crystals,” Journal of the American Chemical Society 133, no. 32 (2011): 12430–12432.

[10] Y. Qi, D. Kou, Y. Sun, et al., “Portable Colorimetric Photonic Indicator for Ethanol Concentration Sensing,” Chemical Engineering Journal 457, no. 1 (2023): 141184.

[11] H. Yuan, Y. Qi, W. Niu, W. Ma, and S. Zhang, “Bioinspired Colorimetric Double Inverse Opal Photonic Crystal Indicators for Ethanol Concentration Sensing in Fermentation Engineering,” Langmuir 40, no. 21 (2024): 11184–11195.

[12] E. Yablonovitch, “Inhibited Spontaneous Emission in Solid-State Physics and Electronics,” Physical Review Letters 58, no. 20 (1987): 2059–2062.

[13] S. John, “Strong Localization of Photons in Certain Disordered Dielectric Superlattices,” Physical Review Letters 58, no. 23 (1987): 2486–2489.

[14] J. M. Weissman, H. B. Sunkara, A. S. Tse, and S. A. Asher, “Thermally Switchable Periodicities and Diffraction From Mesoscopically Ordered Materials,” Science 274, no. 5289 (1996): 959–963.

[15] J. H. Holtz and S. A. Asher, “Polymerized Colloidal Crystal Hydrogel Films as Intelligent Chemical Sensing Materials,” Nature 389 (1997): 829–832.

[16] Y. Nishijima, K. Ueno, S. Juodkazis, et al., “Inverse Silica Opal Photonic Crystals for Optical Sensing Applications,” Optics Express 15, no. 20 (2007): 12979–12988.

[17] R. Jha, J. Villatoro, and G. Badenes, “Ultrastable in Reflection Photonic Crystal Fiber Modal Interferometer for Accurate Refractive Index Sensing,” Applied Physics Letters 93, no. 19 (2008): 191106.

[18] J. Lee, K. Bae, G. Kang, et al., “Graded-Lattice AAO Photonic Crystal Heterostructure for High Q Refractive Index Sensing,” RSC Advances 5, no. 88 (2015): 71770–71777.

[19] M. Ashurov, V. Gorelik, K. Napolskii, and S. Klimonsky, “Anodic Alumina Photonic Crystals as Refractive Index Sensors for Controlling the Composition of Liquid Mixtures,” Photonic Sensors 10, no. 2 (2020): 147–154.

[20] X. Xu, A. V. Goponenko, and S. A. Asher, “Polymerized PolyHEMA Photonic Crystals: pH and Ethanol Sensor Materials,” Journal of the American Chemical Society 130, no. 10 (2008): 3113–3119.

[21] X. Lin, J. Chi, Z. Lian, et al., “One-Droplet Saliva Detection on Photonic Crystal-Based Competitive Immunoassay for Precise Diagnosis of Migraine,” SmartMat 5, no. 5 (2024): e1252.

[22] Z. Pan, J. Ma, J. Yan, M. Zhou, and J. Gao, “Response of Inverse-Opal Hydrogels to Alcohols,” Journal of Materials Chemistry 22, no. 5 (2012): 2018–2025.

[23] C. Fenzl, T. Hirsch, and O. Wolfbeis, “Photonic Crystal Based Sensor for Organic Solvents and for Solvent-Water Mixtures,” Sensors 12, no. 12 (2012): 16954–16963.

[24] Z. Cai, N. L. Smith, J. T. Zhang, and S. A. Asher, “Two-Dimensional Photonic Crystal Chemical and Biomolecular Sensors,” Analytical Chemistry 87, no. 10 (2015): 5013–5025.

[25] G. Huang, Y. Yin, Z. Pan, et al., “Fabrication of 3D Photonic Crystals From Chitosan That are Responsive to Organic Solvents,” Biomacromolecules 15, no. 12 (2014): 4396–4402.

[26] Z. Cai, A. Sasmal, X. Liu, and S. A. Asher, “Responsive Photonic Crystal Carbohydrate Hydrogel Sensor Materials for Selective and Sensitive Lectin Protein Detection,” ACS Sensors 2, no. 10 (2017): 1474–1481.

[27] J. Ge and Y. Yin, “Responsive Photonic Crystals,” Angewandte Chemie International Edition 50, no. 7 (2011): 1492–1522.

[28] Y. Zhao, Z. Xie, H. Gu, C. Zhu, and Z. Gu, “Bio-Inspired Variable Structural Color Materials,” Chemical Society Reviews 41, no. 8 (2012): 3297–3317.

[29] H. Cong, B. Yu, J. Tang, Z. Li, and X. Liu, “Current Status and Future Developments in Preparation and Application of Colloidal Crystals,” Chemical Society Reviews 42, no. 19 (2013): 7774–7800.

[30] C. Fenzl, T. Hirsch, and O. S. Wolfbeis, “Photonic Crystals for Chemical Sensing and Biosensing,” Angewandte Chemie International Edition 53, no. 13 (2014): 3318–3335.

[31] Z. Meng, Y. Liu, H. Huang, and S. Wu, “Flexible Self-Supporting Photonic Crystals: Fabrications and Responsive Structural Colors,” Advances in Colloid and Interface Science 333 (2024): 103272.

[32] Y. L. Ko, H. P. Tsai, K. Y. Lin, Y. C. Chen, and H. Yang, “Reusable Macroporous Photonic Crystal-Based Ethanol Vapor Detectors by Doctor Blade Coating,” Journal of Colloid and Interface Science 487 (2017): 360–369.

[33] D. Shi, X. Zhang, Z. Yang, S. Liu, and M. Chen, “Fabrication of PAM/PMAA Inverse Opal Photonic Crystal Hydrogels by a “Sandwich” Method and Their pH and Solvent Responses,” RSC Advances 6, no. 89 (2016): 85885–85890.

[34] X. Feng, J. Xu, Y. Liu, and W. Zhao, “Visual Sensors of an Inverse Opal Hydrogel for the Colorimetric Detection of Glucose,” Journal of Materials Chemistry B 7, no. 22 (2019): 3576–3581.

[35] M. S. Ashurov, S. A. Ikrami, and S. O. Klimonsky, “Photonic Crystal Sensors for the Composition of Liquids Based on Films With the Structure of Inverse Opal,” Inorganic Materials: Applied Research 12, no. 4 (2021): 915–921.

[36] F. Wang, Z. Zhu, M. Xue, et al., “Cellulose Photonic Crystal Film Sensor for Alcohols,” Sensors and Actuators B: Chemical 220 (2015): 222–226.

[37] M. Ashurov, S. Kutrovskaya, A. Baranchikov, S. Klimonsky, and A. Kavokin, “ETPTA Inverse Photonic Crystals for the Detection of Alcohols,” Condensed Matter 8, no. 3 (2023): 68.

[38] D. Kou, S. Zhang, J. L. Lutkenhaus, L. Wang, B. Tang, and W. Ma, “Porous Organic/Inorganic Hybrid One-Dimensional Photonic Crystals for Rapid Visual Detection of Organic Solvents,” Journal of Materials Chemistry 6, no. 11 (2018): 2704–2711.

[39] I. B. Burgess, N. Koay, K. P. Raymond, M. Kolle, M. Lončar, and J. Aizenberg, “Wetting in Color: Colorimetric Differentiation of Organic Liquids With High Selectivity,” ACS Nano 6, no. 2 (2012): 1427–1437.

[40] A. Lendlein and S. Kelch, “Shape-Memory Polymers,” Angewandte Chemie International Edition 41, no. 12 (2002): 2034–2057.

[41] T. Xie, “Tunable Polymer Multi-Shape Memory Effect,” Nature 464 (2010): 267–270.

[42] A. Espinha, M. C. Serrano, Á. Blanco, and C. López, “Thermoresponsive Shape-Memory Photonic Nanostructures,” Advanced Optical Materials 2, no. 6 (2014): 516–521.

[43] Y. Fang, Y. Ni, S. Y. Leo, C. Taylor, V. Basile, and P. Jiang, “Reconfigurable Photonic Crystals Enabled by Pressure-Responsive Shape-Memory Polymers,” Nature Communications 6 (2015): 7416.

[44] Y. Fang, Y. Ni, B. Choi, et al., “Chromogenic Photonic Crystals Enabled by Novel Vapor-Responsive Shape-Memory Polymers,” Advanced Materials 27, no. 24 (2015): 3696–3704.

[45] Y. Qi and S. Zhang, “Recent Advances in Multifunctional Shape Memory Photonic Crystals and Practical Applications,” Nano Research 17, no. 1 (2024): 79–96.

[46] Y. Qi and S. Zhang, “Recent Progress in Low-Swellable Polymer-Based Smart Photonic Crystal Sensors,” Smart Molecules 1, no. 3 (2023): e20230018.

[47] X. Chen, G. Han, P. Ren, et al., “Shape Memory Photonic Gels Enable Reversible Regulation of Photoluminescence: Towards Multiple Anti-Counterfeiting,” Chemical Engineering Journal 446, no. 1 (2022): 136879.

[48] Y. Fang, S. Y. Leo, Y. Ni, et al., “Reconfigurable Photonic Crystals Enabled by Multistimuli-Responsive Shape Memory Polymers Possessing Room Temperature Shape Processability,” ACS Applied Materials & Interfaces 9, no. 6 (2017): 5457–5467.

[49] Y. Qi, S. Zhang, and A. H. Lu, “Responsive Structural Colors Derived From Geometrical Deformation of Synthetic Nanomaterials,” Small Structures 3, no. 11 (2022): 2200101.

[50] C. H. Hsieh, Y. C. Lu, and H. Yang, “Self-Assembled Mechanochromic Shape Memory Photonic Crystals by Doctor Blade Coating,” ACS Applied Materials & Interfaces 12, no. 32 (2020): 36478–36484.

[51] B. Wei, D. Zhang, D. Ma, et al., “Thermochromic Structural Color Based on Pressure Storage-Release Toward Emerging Applications,” Chemical Engineering Journal 497 (2024): 154637.

[52] Y. Ni, Y. Zhang, S. Y. Leo, et al., “Unconventional Shape Memory Mechanisms of Nanoporous Polymer Photonic Crystals: Implications for Nano-Optical Coatings and Devices,” ACS Applied Nano Materials 1, no. 11 (2018): 6081–6090.

[53] T. Hu, S. Zhang, and Y. Qi, “Unclonable Encryption-Verification Strategy Based on Bilayer Shape Memory Photonic Crystals,” Small 20, no. 49 (2024): 2405243.

[54] S. O. Klimonsky, T. Bakhia, A. V. Knotko, and A. V. Lukashin, “Synthesis of Narrow-Dispersed SiO₂ Colloidal Particles and Colloidal Crystal Films Based on Them,” Doklady Chemistry 457, no. 1 (2014): 115–117.

[55] P. Jiang, J. F. Bertone, K. S. Hwang, and V. L. Colvin, “Single-Crystal Colloidal Multilayers of Controlled Thickness,” Chemistry of Materials 11, no. 8 (1999): 2132–2140.

[56] J. H. Kim, G. H. Lee, J. B. Kim, and S. H. Kim, “Macroporous Hydrogels for Fast and Reversible Switching Between Transparent and Structurally Colored States,” Advanced Functional Materials 30, no. 22 (2020): 2001318.

[57] K. Chen, Y. Zhang, and J. Ge, “Highly Invisible Photonic Crystal Patterns Encrypted in an Inverse Opaline Macroporous Polyurethane Film for Anti-Counterfeiting Applications,” ACS Applied Materials & Interfaces 11, no. 48 (2019): 45256–45264.

[58] Y. Qi, L. Song, C. Zhou, and S. Zhang, “Hydration Activates Dual-Confined Shape-Memory Effects of Cold-Reprogrammable Photonic Crystals,” Advanced Materials 35, no. 16 (2023): 2210753.

[59] D. R. Lide, CRC Handbook of Chemistry and Physics: Section 8: Analytical Chemistry (CRC Press, 2004).

[60] Y. Qi, W. Niu, S. Zhang, et al., “Encoding and Decoding of Invisible Complex Information in a Dual-Response Bilayer Photonic Crystal With Tunable Wettability,” Advanced Functional Materials 29, no. 48 (2019): 1906799.

[61] A. V. Salvekar, W. M. Huang, R. Xiao, et al., “Water-Responsive Shape Recovery Induced Buckling in Biodegradable Photo-Cross-Linked Poly(Ethylene Glycol) (PEG) Hydrogel,” Accounts of Chemical Research 50, no. 2 (2017): 141–150.

[62] C. Löwenberg, M. Balk, C. Wischke, M. Behl, and A. Lendlein, “Shape-Memory Hydrogels: Evolution of Structural Principles to Enable Shape Switching of Hydrophilic Polymer Networks,” Accounts of Chemical Research 50, no. 4 (2017): 723–732.

[63] S. S. Wang, Y. Lin, N. H. Resendiz, L. E. Granados, and H. H. Rodriguez, “Ethanol Concentration Sensor,” SAE Technical Paper no. 2008-01-2452 (2008): 1–8.

[64] T. Arakawa, H. Yasukawa, and K. Fujimoto, “Detection of Alcohol Vapor Using Surface Plasmon Resonance Sensor With Organic-Inorganic Hybrid Layers,” Sensors and Materials 22, no. 4 (2010): 201–209.

[65] C. Kroh, R. Wuchrer, N. Steinke, M. Guenther, G. Gerlach, and T. Härtling, “Hydrogel-Based Plasmonic Sensor Substrate for the Detection of Ethanol,” Sensors 19, no. 6 (2019): 1264.

[66] J. Zhong, M. A. Alibakhshi, Q. Xie, et al., “Exploring Anomalous Fluid Behavior at the Nanoscale: Direct Visualization and Quantification via Nanofluidic Devices,” Accounts of Chemical Research 53, no. 2 (2020): 347–357.

[67] Y. Li, M. A. Alibakhshi, Y. Zhao, and C. Duan, “Exploring Ultimate Water Capillary Evaporation in Nanoscale Conduits,” Nano Letters 17, no. 8 (2017): 4813–4819.

[68] K. Zhong, J. Li, L. Liu, S. Van Cleuvenbergen, K. Song, and K. Clays, “Instantaneous, Simple, and Reversible Revealing of Invisible Patterns Encrypted in Robust Hollow Sphere Colloidal Photonic Crystals,” Advanced Materials 30, no. 25 (2018): 1707246.

RIGHTS & PERMISSIONS

2025 The Author(s). SmartMat published by Tianjin University and John Wiley & Sons Australia, Ltd.