硫氫化物化學選擇性探針的開發與應用

Abstract

本篇論文分為兩部分，第一部分為對稱雙硫探針對芳香族硫醇的選擇性探討；苯硫酚是一種被廣泛應用的化合物，在工業、農業、藥品以及食品香料製程中皆有參與，然而苯硫酚也是毒性極強的環境汙染物，因此需要對工廠的製程以及汙水排放進行嚴格的管控。由於本探針中的螢光團以酯鍵連接，因此能夠透過分子內電荷轉移的形式消除其螢光，避免背景值的干擾，如此一來，在最佳條件下的放光倍率最高能達到84倍。另外，經測試發現該探針能夠區分芳香族硫醇與脂肪族硫醇，亦不會與其它硫化物鹽類有明顯的反應性。而本探針異於常見的苯硫酚探針有著酸性環境穩定性，開創了其在酸性環境下應用的可能性。 第二部分為本實驗室設計之一系列疊氮亞胺探針，此探針為硫化氫之專一性探針；由於硫化氫屬於強效的神經毒素，為避免殘留硫化氫的工業廢水造成環境汙染，本實驗室針對此情況設計了一款疊氮亞胺探針，此結構以3-(benzothiazolyl)-coumarin imine (BTCI) 作為螢光團，直接連接疊氮基作為硫化氫的專一性反應位點，經過一系列的優化過程，此探針最終具有不錯的反應速度與螢光增長倍率，並擁有可觀的選擇性及有機相溶解度。未來本實驗室將再度優化該探針進一步提高其水溶性，期望將其應用於生物體中的硫化氫內源訊號偵測。

This thesis is divided into two parts. The first part describes a symmetric dithiol probe developed by our laboratory. Thiophenol is a compound widely used in industrial, agricultural, pharmaceutical, and food flavoring processes. However, thiophenol is also a highly toxic environmental pollutant, necessitating strict control over factory processes and wastewater discharge. Our probe can differentiate between aromatic and aliphatic thiols, allowing for selective detection of aromatic thiols. Furthermore, the fluorescence groups of probe are connected by ester bonds, which enables the quenching of fluorescence through intramolecular charge transfer, thus minimizing background interference. Additionally, the structure with dual fluorescence groups means that one thiol molecule can produce two fluorescence groups, achieving a signal amplification effect. Under optimal conditions, the luminous efficiency can reach up to 84 times. The second part focuses on a series of AzBTCI probes designed by our laboratory. These probes are specifically designed for hydrogen sulfide detection, as hydrogen sulfide is a potent neurotoxin. To prevent environmental pollution caused by industrial wastewater containing residual hydrogen sulfide, we have developed an AzBTCI probe tailored for this purpose. The structure of the probe uses 3-(benzothiazolyl)-coumarin imine (BTCI) as the fluorophore, directly linked to an azide group that serves as a specific reaction site for hydrogen sulfide. After a series of optimizations, the probe demonstrated a favorable raactivity, a significant increase in fluorescence intensity, and satisfactory selectivity and solubility. In the future, we aim to further optimize the probe to enhance its water solubility, with the hope of applying it to detect endogenous hydrogen sulfide signals in biological systems.