The Synthesis Of Acylhydrazone Containing Naphthalene Ring And Salphen And Properties In Cyanide Anion Fluorescence Recognition

Supramolecular chemistry is a new interdisciplinary subject that transforms molecular language into macroscopic information through reversible non-covalent interactions or dynamic covalent interactions.Anion recognition,which acts as a hot topic in this field,attracts more and more attention of chemical researchers.Among them,the qualitative and quantitative detection of cyanide anion is an important part of this segment.Although cyanide anion plays a very significant role in medical chemistry,biochemistry and catalysis,it also causes serious harm to human health and environmental problems.Therefore,it is urgent to develop numerous efficient and convenient methods to achieve the detection of cyanide anion.It is worth notice that fluorescent probes have many excellent properties,such as high detection sensitivity,short response time and colorimetric response to analyte.Fluorescent probes are very suitable for cyanide anion detection.In view of this,this thesis summarized current progress about fluorescent probes in selective and sensitive recognition of cyanide anion.On this basis,we designed and synthesized fluorescence probe based on 2-hydroxy-1-naphthaldehyde derivatives.Meanwhile,we constructed supramolecular gel materials and investigated their self-assembly performance and anion sensing properties.This thesis is divided into four sections to introduce.(1)We summarized literatures of cyanide anion recognition according to different chemical reaction mechanisms such as nucleophilic addition reaction,deprotonation interaction and hydrogen bonding interaction and other different photophysical mechanisms such as intramolecular charge transfer block and fluorescence resonance energy transfer.In addition,detection applications of cyanide anion in different phases such as liquid,gel and solid phase are described in detail.Based on the above research background and combined with our group’s study orientation in the field of ion recognition,we come up with our research topic.(2)We designed and synthesized fluorescence probe Zn(salphen)using 2-hydroxy-1-naphthaldehyde,benzene-1,2-diamine and diacetoxyzinc,which showed superb aggregation induced emission(AIE)performance in DMSO/H2O mixed solvent.In addition,it could selectivly detect CN-in the mixed solvent of DMSO/H2O(9:1,v/v),the minimum detection limit is 1.71×10-9 M.It is important that the sensing process is almost free from interference of other coexisting anions.This study provides an effective method for the design of low molecular weight(LMW)fluorescence probe used to ultrasensitive detection of cyanide anion.(3)And then,we designed and synthesized acylhydrazone derivatives HD by the condensation reaction of 2-hexadecyloxy-1-naphthaldehyde as well as 2-amino-1 H-benzo[de]isoquinoline-1,3-2H-dione.The compound HD could self-assemble to structure supramolecular gel HD-G in DMSO solution through π-π interaction.Importantly,it can show wonderful selectivity and ultrasensitive detection performance for CN-,and the lowest fluorescence detection limit of 1.82×10-10 M.In particular,the detection mechanism of this supramolecular gel was induced by anion-π interaction to generate optical response,which was different with the traditional mechanism of cyanide anion detection.This research not only supplied of the detection methods by anion-πinteraction for cyanide anion,but also expanded the development of LMW supramolecular gel in the aspect of anion recognition.(4)Finally,we designed and synthesized bis-acylhydrazone compound HT by the condensation reaction 2-hexadecyloxy-1-naphthaldehyde and terephthalohydrazide,which could self-assemble into a supramolecular gel HT-G in DMSO/H2O(9:1,v/v)mixed solvent.The self-assembly process of HT-G is certified that it mainly depended on π-π stacking interaction by mechanism research.Interestingly,this supramolecular gel was able to selectively recognize CN-as the result of fluorescence quenching,the lowest fluorescence detection limit was 5.01×10-10 M.At the same time,we prepared a HT-G-based thin film to used fluorescent display material for CN-detection.The study provided a convenient method for the real-time in situ detection of cyanide anion.