| Ultrasensitive response is an important discovery for effective detection of ions and molecules by chemosensor.Up to now,ultrasensitive response has been widely used in the fields of biological medicine,chemical sensing,surface science,environmental detection,among others.Therefore,to explore new mechanisms for realizing ultrasensitive response and synthesize sensor molecules with ultrasensitive response properties has become very important.Supramolecular polymer with ultrasensitive response is a new research field in the process of ultrasensitive response studies.In 2008,Ogoshi and co-work reported a pillar-like macrocyclic supramolecular host,which was named“Pillararene”.Pillararene has unique symmetric and rigid structure,and its cavity edge is easy to be modified by functionalization.So far,ultrasensitive response of supramolecular systems based on pillararenes to different ions and molecules has aroused wide attention of scientific research workers.In this thesis,we first summarized the research status of ultrasensitive response in ion and molecular detection in recent years,secondly,we summarized the stimulus response of sensor molecules based on pillararene to ions and molecules combined the research of pillararene in our group,and construction and properties of ultrasensitive responsive supramolecular polymer gel with host-guest tuned aggregation-induced emission were investigated carefully.This thesis is divided into four parts:In the first part,we summarized the research results of ultrasensitive response in different fields in recent years,and emphasize the application of ultrasensitive response in ion sensing,small molecule recognition and biomolecule detection.In addition,combined with the research direction of our group,we summarized the selective detection of pillararene-based supramolecular sensors for different guests,and put forward my own research subject.In the second part,in order to study ultrasensitive response of supramolecular polymer gels formed by interaction between small molecules to different ions,we prepared two kinds of small molecules?TH and TA?based on benzenetriformamide.TH and TA could form a supramolecular polymer gel THTA-G by hydrogen bonds interactions in a mixed solution of DMSO/H2O?3.33:6.67,v/v?.THTA-G could carry out sequential ultrasensitive detection of Th4+and Hg2+.Based on the mechanism study,we first proposed a new mechanism to realize ultrasensitive detection of Th4+and Hg2+by“rare earth metal ion tuned aggregation induced emission”.In addition,the xerogel of THTA-G and THTA-GTh could efficiently adsorb Th4+and Hg2+from aqueous solution with nice adsorption property,respectively.Meanwhile,the gel film based on THTA-G could act as a writable smart light-emitting material.In the third part,we designed and synthesized a naphthalimide-functionalized pillar[5]arene P5N,P5N could self-assemble to a stable supramolecular polymer gel P5N-OG in cyclohexanol with strong aggregation induced emission?AIE?via exo-wall?-?interactions.P5N-OG could carry out sequential ultrasensitive detection of Fe3+and H2PO4-.Based on the mechanism study,we first proposed a new method to realize ultrasensitive response by“competition between cation-?and exo-wall?-?interactions”.The xerogel of P5N-OG could effectively adsorb and separate Fe3+from aqueous solution.Meanwhile,the gel film based on P5N-OG could act as a smart fluorescent display material for detecting Fe3+and H2PO4-.The above results illustrated that P5N-OG has good potential for practical application in ion detection and separation,fluorescent display materials as well as ultrasensitive logic gates.In the fourth part,in order to further study and prove the influence of“competition between cation-?and exo-wall?-?interactions”for ultrasensitive response,we designed and synthesized two kinds of functionalized-pillar[5]arene PM and DP.PM and DP could construct a stable supramolecular AIE gel PMDP-G via exo-wall?-?interactions and host-guest interactions in cyclohexanol solution.PMDP-G could carry out ultrasensitive detection of Fe3+,Hg2+and Ag+.By rationally introducing Fe3+and Hg2+into PMDP-G,the obtained metallogels PMDP-GFe and PMDP-GHg could ultrasensitive fluorescently sense F-and Br-,respectively.Mechanism studies confirmed that ultrasensitive response of PMDP-G to different ions is also realized by“competition between cation-?and exo-wall?-?interactions”.Additionally,the xerogel of PMDP-G could effectively adsorb Fe3+,Hg2+,and Ag+from aqueous solution.At the same time,the gel film based on PMDP-G could act as a stimuli-responsive smart fluorescent display material. |
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