Molecular Imprinting of Bisphenol A on Silica Skeleton and Gold Pinhole Surfaces in 2D Colloidal Inverse Opal through Thermal Graft Copolymerization

Abstract

This study successfully fabricated BPA-imprinted poly(4-vinylpyridine-co-ethylene glycol dimethacrylate) (poly(4-VP-co-EGDMA)) quartz crystal microbalance (MIP-QCM) sensors on a silica skeleton surface and gold pinholes of silica inverse opal through surface-initiated atom transfer radical polymerization (SI-ATRP). The sensing features of the two MIP films on the structured silica surface and nano-scale local gold surface were investigated by measuring the resonant frequency change (∆f) in QCM sensors. The ∆f values for the p-MIP (MIP on gold pinholes) and s-MIP films (MIP on silica skeleton surface) were obtained with the ∆f value of −199 ± 4.9 Hz and −376 ± 19.1 Hz, respectively, whereas for p-/s-NIP films, the ∆f values were observed to be −115 ± 19.2 Hz and −174 ± 5.8 Hz by the influence of non-specific adsorption on the surface of the films. Additionally, the imprinting factor (IF) appeared to be 1.72 for p-MIP film and 2.15 for s-MIP film, and the limits of quantitation (LOQ) and detection (LOD) were 54.924 and 18.125 nM (p-MIP film) and 38.419 and 12.678 nM (s-MIP film), respectively. Using the Freundlich isotherm model, the binding affinity of the BPA-imprinted films was evaluated. This was measured in an aqueous solution of BPA whose concentration ranged between 45 and 225 nM. It was found that the p-MIP film (m = 0.39) was relatively more heterogeneous than the s-MIP film (m = 0.33), both of which were obtained from the slope of the linear regressions. Finally, the selectivity of the MIP-QCM sensors for BPA detection was determined by measuring the effect of other analogous chemicals, such as bisphenol F (BPF), bisphenol AP (BPAP), and bisphenol B (BPB), in aqueous solutions. The selectivity coefficients (k*) of the two MIP films had ~1.9 for the p-MIP and ~2.3 for the s-MIP films, respectively. The results reveal that, with respect to signal amplification of the QCM sensors, the s-MIP film has better sensing features and faster detection responses than the p-MIP film.

Role of Functional Monomers upon the Properties of Bisphenol A Molecularly Imprinted Silica Films

“…The higher values of the imprinting factor and of the binding capacity registered for BPA-MIP MPTES , compared to BPA-MIP DAMOT were in agreement with the conclusions drawn from the morpho-structural evaluation of films. According to other reported values for the imprinting factor, such as the one reported for nylon nanofibers (3.4 [32]) and the one reported by Yang and Park (2.15 [31]), the maximum F value of 3.03 found in this study is quite adequate.…”

“…These results highlighted the impact of the film thickness and the discrete porous structure of BPA-MIP DAMOT film upon the rebinding performance. Chang et al [2] reported a maximum BPA adsorption of silica MIPs nanospheres of 444.6 µmol g −1 and Yang and Park [31] reported a Qmax of 170 mg g −1 . Hence, in this case, it seems like thinner films are more efficient for rebinding BPA and the maximum capacities are in good agreement with other reported values.…”

“…This work implied the use of expensive nanomaterials and the minimal characterization of the sol-gel film hampers the assessment of efficiency. A recent study of Yang and Park [31] used the surface-initiated atom transfer radical polymerization (SI-ATRP) for the synthesis of BPA-imprinted poly(4-vinyl pyridine-coethylene glycol dimethacrylate) films on a specific surface of silica inverse opal-formed quartz crystals (QCs). It is also worth mentioning the paper of Ardekani et al, who prepared molecularly imprinted nanofibers based on 3-aminopropyltriethoxysilane (APTES) as functional monomer and nylon 6 as the matrix, using the sol-gel and the electrospinning techniques, which can absorb BPA in water samples [32].…”

Recent Advances in Sensing Applications of Molecularly Imprinted Photonic Crystals

“…The diffraction wavelength of the sensor red shifted evidently as the structure color changed. Moreover, the MIPC sensor detection for chlorotoxin (Wang et al, 2012), bisphenol A (Guo et al, 2012;Oh et al, 2020;Yang and Park, 2020), diethylstilbestrol (Sai et al, 2013), hormone, (Kalecki et al, 2020) and other molecules (Hong et al, 2020) have also been reported as shown in Table 1.…”

“…Antibiotics Oxytetracycline (Wang et al, 2019a), clindamycin hydrochloride (Wang et al, 2019b), chloramphenicol (Sai et al, 2016(Sai et al, , 2019, sulfonamides (Zhang F. et al, 2018;Zhang Y. H. et al, 2018;Li et al, 2019;Lin et al, 2020) Organophosphates Parathion , methane phosphonic acid (Huang C. et al, 2018), monocrotophos (Hong et al, 2020) Explosives TNT (Lu et al, 2016(Lu et al, , 2017Fan et al, 2020), 2,6-DNT, 2,4-DNT (Dai et al, 2017b;Lu et al, 2017) and 4-MNT (Lu et al, 2017), RDX (Fan et al, 2020), HMX (Fan et al, 2020), CL-20 (Fan et al, 2020) Drug Dropropizine , drug delivery (Deng et al, 2018), sulpiride Proteins and amino acids Fibrinopeptide B (Resende et al, 2020), avidin (Jinn et al, 2019), S-layer proteins (Pan et al, 2019), glycoprotein , L-kynurenine (Rizvi et al, 2020), L-histidine (Chen et al, 2018), hormone (Dabrowski et al, 2019;Kalecki et al, 2020) Others Bisphenol A (Shin and Shin, 2019;Hong et al, 2020;Oh et al, 2020;Yang and Park, 2020;Zeng et al, 2020), 2,4-dichlorophenol (Qin et al, 2020), 2-butoxyethanol (Dai et al, 2017a), α-amanitin (Qiu et al, 2020), ethyl anthranilate (Zhang et al, 2019), benzocaine (Chen S. et al, 2019), testosterone (Kadhem et al, 2018), phthalate est...…”