School of Food Science and Engineering, Yangzhou University, Yangzhou, 225127, China.
School of Food Science and Engineering, Yangzhou University, Yangzhou, 225127, China.
Talanta. 2025 Jan 1;281:126827. doi: 10.1016/j.talanta.2024.126827. Epub 2024 Sep 7.
Bisphenol analogues are the typical class of endocrine disrupting chemicals (EDCs) that interfere with binding of endogenous hormones to androgen receptor (AR). With the expansion of industrial activities and the intensification of environmental pollution, an increasing array of bisphenol analogues is being released into the environment and food chain. This highlights the urgency to develop sensitive methods for the detection of bisphenol analogues. Here, we propose a biomimetic AR-based biosensor platform for detecting bisphenol analogues (BPF, TBBPA, and TBBPS) by binding with Aggregation-Induced Emission (AIE) probes. Following a comparison of the PROSS and ABACUS methods, biomimetic AR was designed using the ABACUS approach and subsequently expressed in vitro via the E. coli expression system. Through molecular docking and the observation of fluorescence changes upon binding with biomimetic AR, BS-46006 was selected as the AIE probe for the biosensor. The biomimetic AR-based biosensor showed sensitive detections of BPF, TBBPA, and TBBPS within a range of 0-50 mM. To further elucidate the multi-residue recognition mechanism, molecular orbitals, Electron Localization Function (ELF), and Localized Orbital Locator (LOL) were systematically calculated in this study. Lowest unoccupied molecular orbital and highest occupied molecular orbital indicated the energy gap of BPF, TBBPA, and TBBPS, which correspond to 0.12812, 0.19689, and 0.18711 eV, respectively. ELF and LOL offered clearer perspective through heat maps to visually represent the electron delocalization in BPF, TBBPA, and TBBPS. The matrix effect analysis suggested that the responses of bisphenol analogues in soil matrices could be effectively mitigated through sample pretreatment. The analysis of spiked soil samples showed the acceptable recoveries ranged from 91 % to 105 %. Additionally, the biomimetic AR-based AIE biosensor, which combines multi-residue detection with Tolerable Daily Intakes, shows great promise for the risk assessment of bisphenol analogues. This research may present a viable approach for the analysis of environmental pollutants.
双酚类似物是一类典型的内分泌干扰化学物质（EDCs），它们会干扰内源性激素与雄激素受体（AR）的结合。随着工业活动的扩展和环境污染的加剧，越来越多的双酚类似物被释放到环境和食物链中。这凸显了开发用于检测双酚类似物的敏感方法的紧迫性。在这里，我们提出了一种基于仿生 AR 的生物传感器平台，用于通过与聚集诱导发射（AIE）探针结合来检测双酚类似物（BPF、TBBPA 和 TBBPS）。在比较了 PROSS 和 ABACUS 方法之后，使用 ABACUS 方法设计了仿生 AR，并随后通过大肠杆菌表达系统在体外进行表达。通过分子对接和结合仿生 AR 时荧光变化的观察，选择 BS-46006 作为生物传感器的 AIE 探针。基于仿生 AR 的生物传感器对 BPF、TBBPA 和 TBBPS 的检测范围在 0-50 mM 内具有较高的灵敏度。为了进一步阐明多残留识别机制，本研究系统地计算了分子轨道、电子局域函数（ELF）和局域轨道定位器（LOL）。最低未占据分子轨道和最高占据分子轨道表明 BPF、TBBPA 和 TBBPS 的能隙分别为 0.12812、0.19689 和 0.18711 eV。ELF 和 LOL 通过热图提供了更清晰的视角，直观地表示了 BPF、TBBPA 和 TBBPS 中的电子离域。基质效应分析表明，通过样品预处理可以有效缓解土壤基质中双酚类似物的响应。对加标土壤样品的分析表明，回收率在 91%至 105%之间。此外，基于仿生 AR 的 AIE 生物传感器结合了多残留检测和可耐受日摄入量，为双酚类似物的风险评估提供了很大的前景。本研究可能为环境污染物的分析提供了一种可行的方法。
