Preparation And Performance Research Of Metalloporphyrin-functionalized Polymer And Molecular Imprinted Polymers Based On Metalloporphyrin Functional Monomer

Porphyrins are an important large class of macrocycle compounds, and existextensively in nature and living bodies. The unique chemical structure of porphyrinsendows them with superior physical, chemical and optical characteristics, so they arebroadly applied in many fields. However, the free porphyrins have the inherent defects,such as lacking chemical stability, reusability, processability, and so on. These defectslimit their applications greatly. By means of bonding the Porphyrin andmetalloporphyrin to different polymer carrier, not only can keep the characteristics ofthe porphyrin and metalloporphyrin, but also can improve the chemical stability, and italso makes the porphyrin and metalloporphyrin had good processability at the sametime, thus it can greatly expand the application scope of porphyrin compounds,andsignificantly improve its application efficiency. In addition to, prepare molecularimprinted polymer using the Zn porphyrins as functional monomer, and use it tofluorescent chemical sensors to detect the contents of triazine compounds in water, cangreatly improve its molecular recognition function. In this work, we initially preparedtwo kind of Zn porphyrin-functionalized polymer materials. Furthermore, the spectralproperties of ZnTPP-PS and the effect of terbuthylazine as axial ligands was researchedin depth. And the molecularly imprinted polymers of terbuthylazine using Zinc porphyrinas functional monomer was prepared，and mainly stydied recognition selectivity and finebinding affinity for terbuthylazine molecule. This study will be helpful in providing agreater understanding of design and preparation of more superior performancephotochemical sensorsFunctional monomer, which has high affinity and selectivity for a certain template, plays important role for synthesis of molecularly imprinted polymers（MIPs）. In thisthesis, vinyl-substituted zinc porphyrin was employed as a functional to synthesize theMIPs with the templates of terbuthylazine. In this work,Firstlly, in this work, the benzylporphyrin （PP）-functionalized polyglycerylmethacrylate （PGMA） and the hydroxylbenzylporphyrin（HPP）-functionalizedPGMA, i.e. PP-PGMA and HPP-PGMA, were coordinated with Zn2+ion respectively,resulting in the Zn porphyrin-functionalized PGMA, i.e. ZnPP-PGMA andZnHPP-PGMA. The chemical structures of ZnPP-PGMA and ZnHPP-PGMA werecharacterized by nuclear magnetic resonance （1H-NMR） spectroscopy. Thespectroscopic properties were studied between two kinds of Zn porphyrin-functionalizedPGMA and terbuthylazine by means of UV-vis spectroscopy and fluorescencespectroscopy. The results showed that ZnPP-PGMA and ZnHPP-PGMA had bothpossessed strong spectral characteristics. As compared with PP-PGMA and HPP-PGMA,the Soret absorption bands of ZnPP-PGMA and ZnHPP-PGMA exhibited obvious redshift, and the blue shift occurred for Q emission bands of them. In addition, as thecoordination reaction between ZnPP-PGMA and terbuthylazine, both the Soret and Qabsorption bands of ZnPP-PGMA exhibited red shift in the electronic absorption spectraof it. Also the fluorescence quenching was exhibited in the system of coordinationreaction between ZnPP-PGMA, or ZnHPP-PGMA, and terbuthylazine. And thefluorescence quenching of ZnHPP-PGMA was strengthed with the increasingconcentration of terbuthylazine.Then，Zinc tetraphenyl porphyrin （ZnTPP） was bond on the side chains of linearchloromethylated polystyrene（CMPS）via Friedel-Crafts alkylation reaction, leading tothe soluble metalloporphyrin-functionalized ZnTPP-PS. The above target product wascharacterized using spectroscopy methods, such as infrared spectrum （IR）, electronicabsorption spectrum and fluorescence emission spectrum. And the effects of variousfactors on the bonding reaction of ZnTPP were studied in detail. The spectroscopicproperties of Zn porphyrin-functionalized PS and the coordination compound between itsand terbuthylazine were studied by means of UV-vis spectroscopy and fluorescencespectroscopy. The research results show that via Friedel-Crafts alkylation reaction could bond ZnTPP to the linear polystyrene successfully, and under the condition of thetemperature25℃, the dosage of catalyst0.1mL, the degree of bond of ZnTPP can beattain7%. ZnTPP-PS had possessed strong spectral characteristics. In the certainconcentration range, the fluorescence emission spectrum of ZnTPP-PS appeared theconcentration quenching effect; As the coordination reaction between ZnTPP-PS andterbuthylazine, the Q absorption bands of ZnTPP-PS exhibited red shift in the electronicabsorption spectra of it, And the fluorescence quenching of ZnTPP-PS was strengthedwith the increasing concentration of terbuthylazine.The coordination reaction betweenZnTPP-PS and terbuthylazine rearched equilibrium after9h, and the fluorescenceintensity no longer drop. The Stern–Volmer plot indicates the combined dynamic andstatic quenching of ZnPP/PS by TBA.Last，MIPs based on zinc poprhyrin were prepaerd for imidoazole derivativesreognition when terbuthylazine was used as the template with the methacrylic acid asmonomer, ethyene glycol dimethacrylate as crossing reagent and AIBN as initiator inimprinting reaction. In this work, with pirimicarb as contrast substances, static methodswere adopted to study the binding properties and recognition character of molecularlyimprinted polymers of terbuthylazine for terbuthylazine. The experiment results showthat molecularly imprinted polymers of terbuthylazine have the binding properties andrecognition character for terbuthylazine. In relation to pirimicarb, the selectivitycoefficient of molecularly imprinted polymers for pirimicarb is5.66, showing highselectivity of molecular recognition. The MIPs showed a high affinity and differentialselectivity for closely related imidazole derivatives when the competitive bound methodwas usd.The main factors that will influence the synthesis of MIPs are cooperation effectof coordinate and geometry-matching.