Construction And Application Of Sensors Based On Pillar[5]arene

Since 2015,the State Council has pointed out that there is still a big gap between the development of“blue disciplines”and“green disciplines”in China and that of developed countries.Therefore,it is proposed to give priority to the development of the field of“new functional materials and devices”,encourage the cross-integration of various disciplines,and develop new functional materials that are more scientific frontier and more in line with the needs of the country and the people.As a new interdisciplinary subject,supramolecular chemistry combines units with different structures and functions through non-covalent interactions to build up dynamic and reversible intelligent materials.The progress of supramolecular chemistry is related to the design and synthesis of macrocyclic molecules.Pillararene is a new macrocyclic host designed and synthesized for the first time in 2008.Since it was reported,it has been widely used in intelligent response,sensing and detection,drug delivery and catalytic reaction due to their electron-rich and rigid cavity,regular structure and host-guest property.In recent years,a large number of wastes generated by the emerging chemical manufacturing industries enter the environment on which human beings depend for survival,which is fatally dangerous to the ecosystem and health of mankind.Compared with covalent polymers,supramolecular polymers show great advantages in the application of stimulus-responsive smart materials by virtue of the dynamic reversibility of non-covalent bonds.Therefore,taking advantage of the characteristics of pillararenes,the design and development of supramolecular polymer smart materials on the ground of pillararenes are expected to be used in the control and prevention of pollutants.Based on the above analytical content as the research background,in this paper,two supramolecular polymers were constructed by self-assembly using pillar[5]arene as supramolecular macrocycle,which achieved effective detection of organic pollutants in the form of fluorescence sensing and free radical sensing,respectively,and had certain practicality,they are expected to become sensing materials for detecting environmental pollution in the future.The experimental research content of this thesis is divided into the following two parts:1.By functionalizing pillar[5]arene,we synthesized the pillar[5]arene-based fluorescence macrocycle,which was functionalized by 1,8-naphthalimide,we explored its properties and the application in sensing detection of nitroaromatic contaminants（NACs）.First,we confirmed the successful synthesis of the compound by ¹H NMR,¹³C NMR spectroscopy and LC-MS.Then,we proved that fluorescence macrocycle were constructed into the fluorescent supramolecular polymer driven by intermolecular interactions through 2D NOESY and SEM experiments.In addition,we analyzed the fluorescence properties of the supramolecular polymer in solid state and liquid under different solvents and concentrations.Compared the fluorescence properties with those of the control monomer without the structure of pillar[5]arene,it was found that the emission wavelength of the supramolecular polymer was redshifted,and the fluorescence lifetime,luminescence intensity and luminescence stability were improved.Finally,we studied the fluorescence supramolecular polymer for NACs sensing detection experiment by fluorescence emission spectrum and UV-vis absorption spectrum.For the detection of NACs,the results indicated that the polymer had a good detection limit and sensitivity.2.We prepared a supramolecular polymer with pillar[5]arene as macrocyclic host using host-guest properties,and studied its properties and the application of volatile amines detection.First of all,we synthesized the pillar[5]arene functionalized quaternary ammonium salts as the host material and alkyl-linked viologen derivatives as the guest material,we confirmed the synthesis of target products through the test experiments of ¹H NMR,¹³C NMR spectroscopy and LC-MS.Next,we proved that the supramolecular polymer was successfully constructed by using ¹H NMR spectroscopy.We succeeded in constructing the supramolecular polymer gel by adjusting conditions such as temperature and concentration using the flexible characteristics of polymers.Considering that the bonding strength of the polymer host was different from that of different guests,we studied the stimulus-response of the supramolecular polymer gel with common organic solvents as the competitive guests,the result displayed that the gel had a certain stimulus-response and had the potential to be molecular recognition.Finally,we prepared supramolecular polymers into functional test paper for the steam chromism experiment.The experimental result showed that our supramolecular polymer could effectively perform visual discoloration detection on ammonia and organic amines vapor,which provides a research reference for polymer materials in terms of organic pollutant detection in the environment.