Prusti Banchhanidhi, Tripathi Shivani, Jain Akshita, Chakravarty Manab
Department of Chemistry, Birla Institute of Technology and Science-Pilani, Hyderabad Campus, Hyderabad 500078, India.
ACS Appl Mater Interfaces. 2023 Apr 5;15(13):16492-16504. doi: 10.1021/acsami.3c00791. Epub 2023 Mar 21.
Intermolecular amine-phenol interactions are largely recognized as unique models with diverse supramolecular interactions. However, fluorescence (FL) variations originating from such interactions are rare. Herein, FL changes are well realized from amine-phenol interactions to identify an important biomarker, biogenic amines (BAs). A simple, inexpensive, and thermally stable anthracenylphosphonate is linked with 2,2'-biphenol to design a functional dual-state emitter. Among the various amines tested, this emitter displays superior sensitivity with the lowest possible limit of detection as 5.8-9.7 ppb with aliphatic polyamines such as 1,3-, 1,4-, 1,5-, and 1,6- diamines and spermidine in the solution phase. Fast, on-spot detection of the BA vapors was visually conducted through a notable high-contrast change from blue to yellow emission in the solid state. FT-IR, H/P NMR, and mass spectroscopic studies identify the ground-state amine-phenol interactions. The failure in BA detection with the 2,2'-dimethoxy-biphenyl-linked analog verifies the role of amine-phenol interactions. Mechanistic studies determine amine-phenol interactions in the ground and excited states. The molecular structure and packing of the doubly twisted probe are documented with a substantial void space facilitating close contact of the BAs with the strong amine-phenol interactions desired for efficient detection. Finally, this probe governs the freshness of a piece of fish and prawn. Further, a remarkable concentration-controlled diverse emission with a red shift difference of 141 nm is detected with 1,3-diaminopropane (1,3-DAP) vapor (from 29 to 319 mg/L) for the first time. Thus, a cost-effective device is developed to detect 1,3-DAP at a precise concentration, visible through the naked eye.
分子间胺 - 酚相互作用在很大程度上被认为是具有多种超分子相互作用的独特模型。然而，源自此类相互作用的荧光（FL）变化却很少见。在此，通过胺 - 酚相互作用很好地实现了FL变化，以识别一种重要的生物标志物——生物胺（BAs）。一种简单、廉价且热稳定的蒽基膦酸酯与2,2'-联苯酚相连，设计出一种功能性双态发射体。在测试的各种胺中，该发射体表现出卓越的灵敏度，在溶液相中，对于脂肪族多胺如1,3 -、1,4 -、1,5 -和1,6 -二胺以及亚精胺，其最低检测限可达5.8 - 9.7 ppb。通过固态下从蓝色到黄色发射的显著高对比度变化，对BA蒸气进行了快速、现场的视觉检测。傅里叶变换红外光谱（FT - IR）、氢/磷核磁共振（H/P NMR）和质谱研究确定了基态胺 - 酚相互作用。用2,2'-二甲氧基 - 联苯连接的类似物检测BA失败，证实了胺 - 酚相互作用的作用。机理研究确定了基态和激发态下的胺 - 酚相互作用。记录了双扭曲探针的分子结构和堆积情况，其具有大量的空隙空间，有利于BA与有效检测所需的强胺 - 酚相互作用紧密接触。最后，该探针可用于判断一片鱼和虾的新鲜度。此外，首次用1,3 -二氨基丙烷（l,3 - DAP）蒸气（浓度从29到319 mg/L）检测到了显著的浓度控制的不同发射，红移差异为141 nm。因此，开发了一种经济高效的装置，可精确检测1,3 - DAP的浓度，肉眼可见。
