Chin Kae-Zheng, Chang Sue-Min
Institute of Environmental Engineering, National Yang Ming Chiao Tung University, 1001 University Road, Hsinchu 300093, Taiwan.
Graduate Institute of Environmental Engineering, National Taiwan University, No. 1, Section 4, Roosevelt Road, Da'an District, Taipei 10617, Taiwan.
ACS Appl Mater Interfaces. 2025 May 14;17(19):28568-28584. doi: 10.1021/acsami.5c03038. Epub 2025 Apr 30.
This study investigates the factors influencing the imprinting performance of molecularly imprinted hybrids (MIHs) with various template/monomer associations and their corresponding adsorption ability for three bisphenol analogues, bisphenol A (BPA), 2,2'-bisphenol F (2BPF), and 4,4'-bisphenol F (4BPF). Styrene (St) and methacrylic acid (MAA) were selected as the primary functional monomers for template complexation. Compared with hydrophilic MAA monomers, hydrophobic St monomers were more favorable for BPA imprinting, despite the lower binding energy of π-π interactions compared to hydrogen bonds. However, St monomers were unsuitable for 4BPF imprinting, while 2BPF exhibited limited complexation with MAA monomers. Among the bisphenols, BPA demonstrated the strongest imprinting capability, leading MIHs to exhibit the highest imprinting factor (IF = 14-18), adsorption capacity ( = 43.7-47.6 mg/g), binding affinity ( = 4.52-6.74 L/mg, Δ = -35.2 to -38.9 kJ/mol, and Δ = -40.5 to -50.6 J mol K), and selectivity over 2BPF and 4BPF (2.0-3.5). In contrast, 2BPF- and 4BPF-imprinted hybrids exhibited significantly lower adsorption capacities ( = 19.4-26.7 mg/g) and binding affinities ( = 1.22-4.35 L/mg) for their respective templates. In competitive adsorption systems, bisphenol rebinding followed the trend BPA > 2BPF > 4BPF, regardless of which template was used for imprinting. Based on NMR analysis, the superior structure-directing and competitive rebinding abilities of BPA are attributed to the restricted rotation of its two phenyl groups, -OH groups, and additional -CH groups on the bridged carbon, which enhance π-π stacking, H-bond, CH-π, and hydrophobic interactions within the imprinted cavities. In contrast, the -OH groups of 2BPF and the rotational phenyl groups of 4BPF hinder their imprinting and rebinding via H-bond and π-π interactions, respectively.
本研究考察了具有不同模板/单体组合的分子印迹杂化材料（MIHs）的印迹性能影响因素，以及它们对三种双酚类似物双酚A（BPA）、2,2'-双酚F（2BPF）和4,4'-双酚F（4BPF）的相应吸附能力。选择苯乙烯（St）和甲基丙烯酸（MAA）作为用于模板络合的主要功能单体。与亲水性MAA单体相比，疏水性St单体更有利于BPA印迹，尽管与氢键相比，π-π相互作用的结合能较低。然而，St单体不适用于4BPF印迹，而2BPF与MAA单体的络合作用有限。在双酚中，BPA表现出最强的印迹能力，使得MIHs表现出最高的印迹因子（IF = 14 - 18）、吸附容量（ = 43.7 - 47.6 mg/g）、结合亲和力（ = 4.52 - 6.74 L/mg，Δ = -35.2至-38.9 kJ/mol，且Δ = -40.5至-50.6 J mol K）以及对2BPF和4BPF的选择性（2.0 - 3.5）。相比之下，2BPF和4BPF印迹的杂化材料对其各自模板的吸附容量（ = 19.4 - 26.7 mg/g）和结合亲和力（ = 1.22 - 4.35 L/mg）显著较低。在竞争性吸附体系中，无论使用哪种模板进行印迹，双酚的再结合趋势均为BPA > 2BPF > 4BPF。基于核磁共振分析，BPA优异的结构导向和竞争性再结合能力归因于其两个苯基、-OH基团以及桥连碳上额外的-CH基团的受限旋转，这增强了印迹腔内的π-π堆积、氢键、CH-π和疏水相互作用。相比之下，2BPF的-OH基团和4BPF的旋转苯基分别通过氢键和π-π相互作用阻碍了它们的印迹和再结合。
