| Photoresponsive surface molecularly imprinted polymer（PSMIP） refers to a novel type of material obtained through combining stimuli-responsive polymer with the surface imprinting technique. Compared to traditional photoresponsive molecularly imprinted polymers, PSMIP has more excellent performance including more accessible binding sites, rapid transfer rate of target substance, higher separation efficiency and effectively reducing the chances of azobenzene monomer to be "embedded", which can increase the rotation space of azobenzene chromophore. PSMIP has a wide range of applications in chemical sensors, intelligent separation and extraction, artificial antibodies and drug release and so on. Traditional PSMIPs are prepared via free radical polymerization. In order to address the shortcomings in free radical polymerization such as slow initiation, rapid chain growth, uncontrollable chain termination and chain transfer. We introduced atom transfer radical polymerization（ATRP）. ATRP polymerization can achieve good controllability in the process of polymerization, a wider range of options for the monomer, easily available raw materials, and mild conditions for implementation, etc., which opens up a new way in PSMIP designation.In this paper, three water-soluble photoresponsive azobenzene monomer with different structures were designed and synthesized. PSMIPs on the surface of SiO2 and Zn O were prepared through ATRP. Subsequently, the influence of photoisomerization rate caused by steric hindrance of azobenzene was studied These PSMIPs were characterized in detail. Specific contents are as follows:1. In Chapter One, the research progress, influence factors of materials, preparation methods of PSMIP, the mechanism and research progress of ATRP, and the research purpose in the detection of triamterene and phthalates have been reviewed. The purpose and significance of this work were raised.2. In Chapter Two, a rapid detection method for triamterene was established. The PSMIP was prepared by ATRP on SiO2 surface using MAPADSA, triamterene, and EGDMA as functional monomer, template molecule, and cross-linker, respectively. The effect of the mole ratio of monomer and cross-linker on the morphology and the photoisomerization rate of the SiO2-MIP was investigated and optimized. The influence of triamterene concentrations on the isomerization rate of the materials was investigated. A new method for the detection of trace triamterene was developed. This method was applied for detection of triamterene in biological samples with the davantages ofrapidness, simplicity, avoiding large instruments, and high limit of detection（0.1 ppm）.3. In Chapter Three, the SiO2-MIP was successfully prepared on the surface of SiO2 by ATRP, after removal of the sacrificial SiO2 coer w by HF ethanol solution, a photoresponsive hollow MIP（PHMIP） was obtained. The effect of concentration and amount of HF on the morphology and photoisomerization rate of PHMIP was studied and optimized. Compared with SiO2-MIP, PHMIP had better performance. And the PHMIP was used for the detection of triamterene in biological samples.4. In Chapter Four, a rapid detection method for phthalates was established. Using three azobenzene derivatives（MAPASA, MAPADSA, MADPADSA） with different substitutents as the functional monomers, two kinds of phthalates（DBP, DCHP） as the template, TEAMA as a crosslinker, Zn O-MIPs were prepared on the surface of Zn O by ATRP. The influence of steric hindrance of the functional monomer on photoresponsive and adsorption properties were investigated. These results demonstrate that adsorption capacity increases as the steric hindrance of the functional monomer decreases. At the same time, The influence of phthalates concentration on the photoisomerization rate of Zn O-MIPs were studied. A new method for detection of plasticizers was established, and the phthalates in plastic cups and plastic toy samples were tested. This method is quick, simple, averting large instruments, and conducive to detection the content of phthalates in daily life.5. In the last chapter, the resuls and conclusions were summarized, and some recommendations for future work were given. |
