Graduate School of Engineering, Kobe University, 1-1, Rokkodai-cho, Nada-ku, Kobe 657-8501, Japan.
Center for Advanced Medical Engineering Research & Development (CAMED), Kobe University, 1-5-1 Minatojimaminami-machi, Chuo-ku, Kobe 650-0047, Japan.
J Mater Chem B. 2022 Sep 15;10(35):6682-6687. doi: 10.1039/d2tb00145d.
In this study, we aimed to create synthetic polymer receptors with the fluorescence signalling ability, using molecular imprinting, precisely designed template molecules, and site-specific post-imprinting modifications, which can mimic conjugated proteins and are capable of specific molecular recognition, and wherein successful binding can be indicated by a change in fluorescence. A molecularly imprinted APO-type nanocavity with a reconstructable domain was prepared by co-polymerisation of a template molecule containing cephalexin conjugated to polymerisable groups a Schiff base, a disulphide bond, and a cross-linker, followed by hydrolysis of the Schiff base and a disulphide exchange reaction. Fluorescence-based indication of binding was devised by the Schiff base formation reaction with 4-formylsalicylic acid, and the interacting site was introduced a disulphide exchange reaction with 4-mercaptobenzoic acid, yielding a multifunctional mature (HOLO)-type molecularly imprinted nanocavity. The ability to indicate binding events using changes in the fluorescence of the HOLO polymer was investigated, and it was revealed that the target antibiotic cephalexin can be selectively detected in aqueous media with high affinity ( = 1.1 × 10 M). Furthermore, the proposed sensor exhibited the potential to detect spiked cephalexin in chicken extracts with a limit of detection of 18 μM (1.3 ppm). The proposed fluorescence-sensing system based on molecular imprinting and post-imprinting modification is expected to enable the development of advanced materials for the specific detection of trace antibiotics in complex samples.
在这项研究中,我们旨在使用分子印迹、精确设计的模板分子和特定位置的后印迹修饰,创建具有荧光信号能力的合成聚合物受体,这些受体可以模拟共轭蛋白,并具有特定的分子识别能力,成功的结合可以通过荧光变化来指示。通过共聚含有聚合物化基团的头孢氨苄的模板分子、席夫碱、二硫键和交联剂,制备了具有可重构结构域的分子印迹 APO 型纳米腔,然后水解席夫碱和进行二硫键交换反应。通过与 4-甲酰基水杨酸的席夫碱形成反应设计了基于荧光的结合指示,并通过与 4-巯基苯甲酸的二硫键交换反应引入了相互作用位点,生成了多功能成熟(HOLO)-型分子印迹纳米腔。研究了使用 HOLO 聚合物的荧光变化指示结合事件的能力,结果表明,目标抗生素头孢氨苄可以在水相中以高亲和力(= 1.1×10^5 M)进行选择性检测。此外,所提出的传感器具有在鸡提取物中检测加标头孢氨苄的潜力,检测限为 18 μM(1.3 ppm)。基于分子印迹和后印迹修饰的拟议荧光传感系统有望开发用于特定检测复杂样品中痕量抗生素的先进材料。