| Since bipyridinium and its derivatives were introduced into the field of supramolecular chemistry,numerous supramolecular motifs were designed and synthesized which employing those bipyridinium derivatives as functional components.In particularly,the bipyridinium derivatives were utilized to construct ?-electrondeficient amphiphiles,cyclophanes,polymeric structures,and more complicated architectures such as rotaxanes and catenanes.In this thesis,a diazapyrenium-based linear amphiphile was designed and synthesized for the purpose of fabricating a semiconductor molecular device.In previous work,the crystal structure of a bipyridinium-based linear amphiphile MJTT5 was found to have more compact molecular alignment than other reported structures and its conversion from gel to crystal can be performed through rather easily.Thus,as a derivative of bipyridinium amphiphile,the diazapyrenium-based linear amphiphile was assumed to exhibit similar features of crystal alignment and gel-crystal conversion,which can both satisfy the requirement of fabricating molecular semiconductors.For now,the synthesis and characterization of the diazapyrenium-based linear amphiphile has been completed,and further work regarding semiconductor preparation is on-going by our collaborators.The second part of my work employs bipyridinium-based amphiphiles as ?-electron-deficient functional units to prepare and process polymeric materials for use in water-treatment.Water treatment and remediation materials have been investigated,however the current commonly-used materials for water treatment for example active carbon,still suffer from poor efficiency and highly-regeneration-cost.In recent years,supramolecular host molecules such as b-cyclodextrin,calix[n]arenes,and pillar[n]arenes were chosen as functional units to fabricate polymeric materials for water remediation.Inspired by those works,we intended to develop processable polymeric material via a facile approach,which would be capable of sequestering organic contaminants from water.Supramolecular motifs based on bipyridinium or its derivatives have been demonstrated to interact with nemerous electron rich aromatic hydrocarbons,such that the bipyridinium derivatives were considered to be used as the functional group which form a complex with organic pollutants.Aiming at obtaining a readily-synthesized and processable poly-backbone,poly-disulfides were considered as the candidates.The ring-opening polymerization of disulfide-containing five/six member rings has been widely reported,among those cases,the lipoic acid evoked our interest due to its ability to undergo thermal-initiated bulk polymerization.Herein,the poly-lipoic ester was firstly synthesized through a thermal initiation approach,and then functionalized with mono-alkylated bipyridine to obtain the target polymer biprydinium-functionalized poly-lipoic ester BPLE.Then a series of adsorption experiments were set up to test the pollutant removal capability.Upon ultrasonic solution processing,the BPLE can form simple coacervates and showed excellent removal efficiencies(>90 %)for the uptake of highly concentrated solution of typical pollutants bisphenol A,valsartan,and carbamazepine.The material can be regenerated via a simple approach and reused for at least four cycles for each of three pollutants.The adsorption rates of BPLE to the pollutants were all acceptable,the time to reach the equilibrium was around forty minutes.Solution processing of this material facilitated the development of a pollutant sponge,which operates via a dip-removesqueeze action,with an adsorption rate constant for BPA ?85 times greater than its progenitor and achieving 80% removal efficiency in 30 seconds.This approach is particularly promising for quick point-of-use treatment of wastewater with high chemical oxygen demand. |
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