Synthesis And Characterization Of Compounds And Water-Soluble Fluorescent Polymers Containing Perylene Diimide Units

Recently,conjugated polymers have been wildly applied in light-emitting diodes,nonlinear optics,solar cells because of its particular optoelectronic properties and electronic properties.Specifically,conjugated polymers have generated extensive study owing to its potential application in ultrasensitive chemo-and biosensors.Real-time and reversible measurement of chemical and biological information with high sensitivity and selectivity is one of the frontiers in sensor research.In this thesis,we have synthesized five compounds containing perylene diimide(PDI)unit and four water-soluble fluorescent polymers containing PDI unit,they have been characterized and measured by many modern analytical instrumental methods.M4 containing PDI conjugated unit and acrylate group as terminal groups was synthesized using Suzuki-couping reaction,P1 with trithioester was prepared via reversible addition-fragmentation chain transfer(RAFT)polymerization.Boc-protected amino groups and regular structure fluorescent polymer containing PDI conjugated unit P2 was prepared by one-pot method(in the same reaction bottle,both the reduction reaction of trithioester bond of P1 to thiol and the Click reaction of thiol with the carbon-carbon double bond of M4 was occurred at the same time).Water-soluble fluorescent polymer P3 containing PDI conjugated unit was obtained by the deprotection of the resulting Boc-protected polymer P2 with aqueous HCl.M4,P1,P2 and P3 have been characterized and measured by many modern analytical instrumental methods.These results showed that P3 in aqueous solution has similar optical properties to M4 and P2 in trichloromethane solution;in the research of live cell imaging and flow cytometry analysis,P3 has shown few cytotoxicity(concentration below 0.500 mg/m L),and fluorescence intensity has increased with the increase of concentration.P3 have great water-solubility and into cells normally,thereby making it a very good prospect in the biomedical field.Three compounds(M4-C2,M4-C4 and M4-C6)containing PDI conjugated unit and acrylate group as terminal groups was synthesized using Suzuki-couping reaction,P2-C2,P2-C4 and P2-C6 Boc-protected amino groups and regular structure fluorescent polymer containing PDI conjugated unit was prepared from by one-pot method P1 with M4-C2,M4-C4 and M4-C6,respectively.Water-soluble fluorescent polymer P3-C2,P3-C4 and P3-C6 containing PDI conjugated unit was obtained by the deprotection of Boc-protected polymer P2-C2,P2-C4 and P2-C6 with aqueous HCl.They have been characterized and measured by many modern analytical instrumental methods.These results have shown P3-C2,P3-C4 and P3-C6 have great water-solubility and good optical properties.The study found that no changes in the absorption spectra for P3-C2,P3-C4 and P3-C6 at different p H.For different p H,fluorescence emission spectra have its different changing rule with repulsive force between the ions and solvation effcet.Fluorescent intensity of P3-C2 and P3-C4 were decreased with the increase p H,but when p H?13,fluorescent intensity have a slight increase.M4 containing PDI conjugated unit and epoxy group as terminal groups was synthesized by N,N'-di(3-amyl)-1,7-dibromoperylene-3,4:9,10-tetracarboxylic diimide(M3)as a kind of starting material using Suzuki-couping reaction.M9 has been characterized and measured by many modern analytical instrumental methods.These results shown M9 has excellent thermal property and good optical properties and fluorescence quantum yield is 0.33.These works lay the experimental foundations for synthesizing hyperbranched polymer by ring opening polymerization.