The Synthesis And Properties Of Cyanide And Fluoride Ion Sensor Based On Hydroxyl Group Of Recognition Site

Anion recognition and detection is an important part of the anion sensor research, it is also the main content in supramolecular chemistry. Attention has been focused on anion sensors for its convenience, high efficiency, and quick detection. However, current research in anionic sensor mainly focuses on the design and synthesis of receptor molecules and their corresponding performance analysis, the practical application for real samples is rarely reported.In this paper, we designed and synthesized two anion receptors4-((E)-2-[(4-hydroxyl phenyl) ethenyl-1-allylpyridinium bromide (HPEAP) and (E)-l-allyl-4-(4-hydroxy phenyl) vinyl) quinolinium bromide (AHPEQB). We also prepared a series of cross-linked polymers using AHPEQB as the functional monomer, and Trimethylolpropane triacrylate (TRIM) as the cross-linker. The selectivity of the prepared anionic sensors in different solvents was investigated. The detailed contents are described as follows:Chapter1:The progresses in anion recognition, the types of anion sensors, and anion recognition mechanism and research methods have been reviewed.Chapter2:A novel colorimetric sensor HPEAP for CN-was designed and synthesized, and its chemical structure was confirmed using1H-NMR,13C-NMR. HPEAP displayed good selectivity among other competing anions in ethanol. A color change from yellow to red was simultaneously observed upon the addition of CN-. The limit of detection (LOD) and binding constant were measured to be3.46×10-6mol/L and1.69×104by UV-Vis. The recognition mechanism was discussed by UV-Vis,’H-NMR, and a comparison study.Chapter3:A novel colorimetric sensor AHPEQB for CN-was designed and synthesized, and its chemical structure was confirmed using1H-NMR,13C-NMR. AHPEQB displayed good selectivity among other competing anions in ethanol. A color change from yellow to blue was simultaneously observed upon the addition of CN-. The LOD and binding constant were measured to be1.70×10-6mol/L and3.21×104by UV-Vis. AHPEQB also showed good reversibility in CN-sensing. The recognition mechanism was discussed by UV-Vis,1H-NMR, and a comparison study. AHPEQB was applied for the determination of CN-in four real water samples (Tap water, River water, Domestic sewage, industrial wastewater).Chapter4:A series of cross-linked polymers for CN-sensing was prepared via free radical polymerization using AHPEQB as the functional monomer, and TRIM as the cross-linker. CpAiT3(The molar ratios:AHPEQB/TRIM=1/3) displayed good selectivity among other competing anions in ethanol. A color change from green to blue was observed upon the addition of CN-. The LOD and binding constant were measured to be1.66×10-5mol/L and5.32×104by UV-Vis. CpAiT3also showed good reversibility in CN-sensing. The morphology and structure of CpA1T3were characterized using SEM, TG, and BET. CpA1T3was applied for the determination of CN-in four real water samples(Tap water, River water, Domestic sewage, industrial wastewater).Chapter5:A series of cross-linked polymers for F-sensing was prepared via free radical polymerization using AHPEQB as the functional monomer, and TRIM as the cross-linker. CpAiT5(The molar ratios:AHPEQB/TRIM=1/5) displayed good selectivity among other competing anions in water. A color change from gray to yellow was observed upon the addition of F-. The LOD and binding constant were measured to be1.00×10-7mol/Land8.99×104by fluorescence spectrum. CpA1T5also showed good reversibility in F-sensing. The morphology and structure of CpAiTs were characterized using SEM, TG, and BET. CpAiTs was applied for the determination of F-in two mouth wash.