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Abstract
Surface imprinting is an effective and simple method to fabricate and retain imprinted templates and recognizable nanocavities after template extraction. The imprinted effects can be controlled depending on the surface morphological changes. In general, a planar film has a limited area compared to a structured film with relatively higher surface-to-volume (S/V) ratio (A/A0), leading to the conventional sensing response upon the functionality of monomers in a fixed chemical composition. To increase the limited sensing properties and develop simple fabrication of porous arrays on a large area, we herein demonstrate the 2,4-dichlorophenoxyacetic acid (2,4-D, herbicide)-imprinted porous thin film lithographically patterned using photopolymerization and silica colloidal array as a master mold, derived by a unidirectional rubbing method. The resonant frequency changes with respect to the adsorption of 2,4-D molecules on a template-extracted porous poly(MAA-co-EGDMA) (MIP) film in a 10−1 mM aqueous solution of 2,4-D for 1 h, and when compared to the planar MIP film, the higher sensing response (Δf = −283 ± 7 Hz ≈ 1543 ± 38 ng/cm2) appears on the porous MIP film due to the specific recognition toward the more accessible templated cavities of the structured porous array, indicating an imprinting effect (If) value of 3.5. In addition, a higher selectivity for 2,4-D was also displayed on the porous MIP film compared to other herbicides. From these results, it was revealed that these improved sensing properties can be determined from the effects of various parameters (template functionality, film structuring, hydroxyl groups of silica colloids, etc.).
Highlights
To date, various herbicides have been used extensively to increase agricultural production.the risks of large amounts of consumption threaten natural purification and ecosystems.Among the mostly used herbicides, in particular, 2,4–dichlorophenoxyacetic acid (2,4-D) is one of important phenoxy herbicides, commonly known and remarked as a priority pollutant [1]
In order to prepare monodispersed silica colloidal particles having a uniform size distribution, a few parameters were precisely controlled, including reaction temperature and concentration of TEOS, ethanol, and ammonia according to the Stöber method [32]
The size-defined silica particles were produced with an average diameter of 490 ± 14 nm under the optimized synthetic condition (Figure S1)
Summary
Various herbicides have been used extensively to increase agricultural production.the risks of large amounts of consumption threaten natural purification and ecosystems.Among the mostly used herbicides, in particular, 2,4–dichlorophenoxyacetic acid (2,4-D) is one of important phenoxy herbicides, commonly known and remarked as a priority pollutant [1]. Polymers 2019, 11, 1332 that long-term exposure to 2,4-D gives rise to serious health hazards for humans, leading to damages in multiple organ systems [1]. For these reasons, various methods of 2,4-D removal have been studied including electrochemical, advanced oxidation, and radiolytic decomposition processes. There are many conventional techniques for detecting low concentrations of 2,4-D such as chromatography or mass spectrometry [2,3,4] These techniques often require extensive sample preparations, high cost equipment, and separation procedures, which are time-consuming processes
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