| Nowadays,the detections of metal ions and halogen ions have gained more attention due to the great significance in human health and the ecological environment.Lots of methods have been adopted for the detection of ions,while among them,the fluorescence detection has gradually become a hot research objects,because of the advantages of low-cost,rapid detection,operational simplicity,high selectivity and sensitivity.Besides,small fluorescent molecule takes advantages of clear structure and high purity,are increasing favored by researches.According to the F-fluorescence detection mechanism,fluorescent method can be divided into two parts: On the one hand,sensors based on the interactions between F-and Lewis Acids: fluoride-promoted Si-O and Si-C cleavage,or react with borates forming fluoroborate anions,then cause changes in the fluorescence intensity;On the other hand,sensors utilizing Hydrogen-Bond interactions,then affect the fluorescence intensity.As well,a series of nitrogen-containing heterocylic materials have been applied in the F-detection,for example,the derivatives of amides,sulfonamides,imidazole,indole and et.al.However,one of the drawbacks reported in most of F-sensors is that the sensing materials are using as solution,which is irreversible and one-times usages to detect F-,hence,the practical applications are restricted.Thus,developing a fluorescent sensor with a recyclable thin film has become one of the current research directions of Fsensing.As for Fe3+ fluorescent detection,it is mainly divided into fluorescence quenching and fluorescence enhancement.And phenothiazine groups,rhodamine groups,BODIPY groups and other nitrogen-containing heterocylic groups have been introduced to the Fe3+ fluorescent detection.While,many fluorescent sensors cannot rule out the interference of Cu2+ and Zn2+,in addition,the sensors are with higher detection limit.Then,it is of significant research implications to develop a rapid method to detect Fe3+ with high selectivity,simplicity and lower detection limit.Based on the above statements,many nitrogen-containing heterocylic groups have been applied in the fluorescent detection of F-/Fe3+.The related F-/Fe3+ fluorescence detectors were designed and synthesized separately targeting solve the drawbacks of non-reversibility in F-detection and higher detection limit,poor selectivity in Fe3+ detection.The paper will focus on the following two parts:1.Design and synthesis of small fluorescence materials that containing nitrogen heterocylic,DPP,and its electropolymerization(EP)films for the fluorescent detection of F-.In order to improve the non-reversibility and expand its application range of F-fluorescent materials,we designed a sensor that containing nitrogen heterocylic,DPP,and introduced carbazole as electro-active group,then EP was utilized to prepare DPP-DWCZ fluorescent films to detect F-in organic solution.The electrochemical parameters were optimized to achieve great sensing performance.The DPP-DWCZ EP films were excellent fluorescent probes for F-with high sensitivity,remarkable anti-interference and prominent reusability.And the quenching rate was 67%,when the concentration of 1×10-4 M,with the detection limit was 4.1×10-8 M.2.Design and synthesis of small fluorescence materials that containing nitrogen heterocylic,TAZ,and their fluorescent response for Fe3+.From the point of increasing the selectivity and reducing its detection limit of Fe3+ sensing molecules,we synthesized two fluorescent molecules based on TAZ.Both of them showed high selectivity and sensitivity toward Fe3+,and the properties can exclude interference from other metal ions and surrounding environments.In addition,when the concentration of Fe3+ was 1×10-5 M,the quenching rate of NC-TAZ and CC-TAZ was up to 84% and 80%,respectively.The fluorescent detection limits of NC-TAZ and CC-TAZ for Fe3+ were calculated to be 3.3×10-8 M and 3.4×10-8 M,respectively,which are competitive detection limit compared with other fluorescence sensors containing nitrogen heterocylic. |
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