Synthesis And Properties Of The Long Alkyl Chain Based Copillar[5]Arenes

This paper includes five chapters:Chapter 1: This chapter mainly introduces the nature of a kind of novel macrocyclic molecule pillar[n]arenes Mainly from the synthesis of pillar[n]arenes including: several commonly synthesis method, cyclization reaction mechanism as well as the separation and purification. The functional group modification of pillar[n]arenes contain fully modification and partial modification two aspects. Host-guest chemistry properties of pillar[n]arenes including all alkoxy pillar[n]arenes, all hydroxylation pillar[n]arenes, hydrophilic pillar[n]arenes and amphiphilic pillar[n]arenes. Finally introduced the application of pillar[n]arenes in drug release, ion recognition, gel material, biological membrane channel and other aspects including catalytic applications.Chapter 2: This chapter mainly designed and synthesized with long alkyl chain of two kinds of pillar[5]arenes for COP5–12 and COP5–16. These two kinds of copillar[5]arenes can be formed supramolecular gel materials in acetonitrile solvent. By the driving force of C–H???π the copillar[5]arenes can form two kinds of phase state, eventually forming supramolecular framework structured organic gel. The phase A of the gels exhibit excellent self–healing properties and stretchability and the phase B of the gels show good hardness and moldability. The supramolecular polymer gels also showed reversible gel–sol phase transitions by heating and cooling.Chapter 3: This chapter mainly designed and synthesized with dodecyl long alkyl chains symmetry pillar[5]arenes DCP5–12. The monomer in acetonitrile solvent drivied by C–H???π force to form micelle, one dimensional linear supramolecular polymers, two–dimensional polymers and three dimensional organic framework change eventually forming supramolecular polymer gels. This gel showed good stretchability, moldability high transparency and fluorescence properties. The supramolecular polymer gels also showed reversible gel–sol phase transitions by heating and cooling. Finally, we prepared the application of the gel of DCP5–12 and tested its application in terms of acidalkali, the gel of DCP5–12 almost showed no destruction found it is good for corrosion resistance of inorganic acid and alkali.Chapter 4: This chapter mainly designed and synthesized with hexadecyl long alkyl chain symmetry pillar[5]arenes DCP5–16. We studied the formation conditions and performance of the gel in novel stimuli–responsive supramolecular materials. The supramolecular polymer was envisioned to be driven by C–H???π force to construct the other phase(phase B) of the supramolecular polymer gel–supramolecular organic framework in CD3 CN accompanied by aggregation–induced enhanced emission(AIEE) of fluorescence. They showed very good extension and exhibit properties at the first phase, and very good hardness properties and moldability at the second phase of the gel. Moreover, the supramolecular polymer gel showed reversible gel–sol phase transitions by heating and cooling. When adding surfactant bearing hexadecylpyridinium chloride into the gel, the electron-poor compound penetrated the rich–electron cavity of DCP5-16, forming the host-guest complex and causing fluorescence quenching for the electron transfer driven by C–H???π and cation???π interactions. The gelator DCP5–16 shows excellent sensitivity to hexadecylpyridinium chloride.Chapter 5: This chapter uses pillar[5]arene spatial dimensions based on the size of the part of chapter 4 as a fluorescent sensor. This sensor is found to be a highly selective colorimetric and “off–on” fluorescent chemosensor for the recognition of L–Trp. The detection limit of the sensor towards Trp is 1.33×10-7 M, and other L–amino acids including: Gly, Asp, Met, Pro, Thr, Leu, Val, Glu, Cys, Tys, Ala, Gln, Asn, Ser, Phe, Ile, Lys, Arg and His had nearly no significant influence on the probing behavior. In addition, test strips based on DCP5 were fabricated, which also exhibits a good selectivity to L–Trp as in aqueous media. We believe the test strips could act as a convenient and efficient L–Trp test kits.