Three-dimensional (3D) printing technology has attracted great attention for prototyping different electrochemical sensor devices. However, chiral recognition remains a crucial challenge for electrochemical sensors with similar physicochemical properties such as enantiomers. In this work, a magnetic covalent organic framework (COF) and bovine serum albumin (BSA) (as the chiral surface) functionalized 3D-printed electrochemical chiral sensor is reported for the first time. The characterization of the chiral biomolecule–COF 3D-printed constructure was performed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray spectroscopy (EDX). A tryptophan (Trp) enantiomer was chosen as the model chiral molecule to estimate the chiral recognition ability of the magnetic COF and BSA-based 3DE (Fe₃O₄@COF@BSA/3DE). We have demonstrated that the Fe₃O₄@COF@BSA/3DE exhibited excellent chiral recognition to l-Trp as compared to d-Trp. The chiral protein–COF sensing interface was used to determine the concentration of l-Trp in a racemic mixture of d-Trp and l-Trp. This strategy of on-demand fabrication of 3D-printed protein–COF-modified electrodes opens up new approaches for enantiomer recognition.

中文翻译：

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手性蛋白-共价有机框架3D打印结构作为手性生物传感器

三维（3D）打印技术在为不同的电化学传感器设备制作原型方面引起了极大的关注。然而，对于具有类似物理化学性质的电化学传感器，例如对映异构体，手性识别仍然是一个关键的挑战。在这项工作中，首次报道了磁性共价有机骨架（COF）和牛血清白蛋白（BSA）（作为手性表面）功能化的3D打印电化学手性传感器。通过扫描电子显微镜（SEM），X射线光电子能谱（XPS）和能量色散X射线能谱（EDX）对手性生物分子– COF 3D打印的结构进行了表征。选择色氨酸（Trp）对映体作为模型手性分子，以评估磁性COF和基于BSA的3DE（Fe₃ O ₄ @ COF @ BSA / 3DE）。我们已经证明，与d -Trp相比，Fe ₃ O ₄ @ COF @ BSA / 3DE对l -Trp表现出优异的手性识别。手性蛋白-COF传感界面用于确定d- Trp和1- Trp的外消旋混合物中1- Trp的浓度。这种按需制造3D打印蛋白质-COF修饰电极的策略为对映体识别开辟了新方法。