Preparation Of Functional Porous Organic Polymer And Its Application In The Detection Of Organic Contaminant Residues In Environment And Food

With the improvement of people’s living standard and quality,the safety of the environment and food has become an increasingly widespread concern.Therefore,efficient and sensitive methods for the detection of contaminant residues in the environment and food are of great importance and have become a major research focus in recent years.Due to the complex matrices present in the environment and food and low concentration of target analytes,sample pre-treatment is essential.Among the various sample pretreatment techniques developed to date,solid phase extraction(SPE)and magnetic solid phase extraction(MSPE)are widely used in food testing because of their simplicity,low solvent usage and high enrichment.For SPE/MSPE,developing efficient and selective sorbent is essential to achieve high extraction and enrichment efficiencies.In this paper,functional hyper-crosslinked polymer and porous organic polymer materials were designed and prepared as solid phase extraction sorbents/magnetic solid phase extraction sorbents.In combination with high performance liquid chromatography(HPLC),new methods for the detection of chlorophenols,phenylurea herbicides and endocrine disrupting chemicals in environmental water samples,beverages,honey,juice and mushroom samples were developed.The main studies were as follows:1.Three carbanyl-functionalized HCPs(HCP-TPS,HCP-TPA and HCP-TPP)were successfully fabricated through one-step Friedel-Crafts acylation reaction by copolymerizing paraphthaloyl chloride with triphenylsilane,triphenylamine and triphenylphosphine,respectively.The resultant HCPs contained a plenty of carbonyl functional groups.Among them,HCP-TPS displayed the best adsorption capability for chlorophenols(CPs),and thus it was employed as solid phase extraction(SPE)adsorbent for enrichment of chlorophenols from water,honey and white peach beverage before their determination by high-performance liquid chromatography.The structure and morphology of HCP-TPS were also characterised by Fourier transform infrared spectroscopy,scanning electron microscopy,thermogravimetric analysis,X-ray diffraction and contact angle testing.structure and morphology were characterised.Under the optimal conditions,the detection limits of the method(S/N=3)were 0.15-0.3 ng mL-1 for tap water and leak water,2.5-6.0 ng g-1 for honey sample and 0.4-0.6 ng mL-1 for white peach beverage sample.The recoveries of CPs in the spiked water,honey samples and white peach beverage were in the range of 89.0-108.4%,81.4-118.2%and 85.0-113.5%,respectively.This work provides a new strategy for constructing functionalized HCPs as efficient SPE adsorbents.2.Three aryl ketones-derived porous organic polymers(ATP-POPM,ATP-POPP and ATP-POPO)were fabricated through the aldol condensation reaction of acetylated triphenylsilane precursor(ATP)with different aromatic aldehydes for the first time.The ATP-POPM exhibited the best extraction capacity toward phenylurea herbicides(PUHs).A sensitive method for the simultaneous determination of six PUHs in water,tea drink and mushroom samples was developed with ATP-POPM as solid phase extraction adsorbent prior to high performance liquid chromatography ultraviolet detection.Under the optimized conditions,the linear response of six PUHs was 0.09-80.0 ng mL-1 for water,0.18-100.0 ng mL-1 for tea drinks and 4.50-200.0 ng g-1 for mushroom samples.The detection limits(S/N=3)of the method were 0.03-0.10 ng mL-1,0.06-0.18 ng mL-1,1.50-4.50 ng g-1 for water,tea drink and mushroom,respectively.The method recoveries for spiked samples were in the range of 80.7-116.0%,with relative standard deviations less than 10.3%.The results proved that the established method was sensitive and was suitable to detect PUHs with acceptable accuracy and precision.This work provides a powerful tool to synthesize promising adsorbent by aldol condensation reaction for detecting six PUHs simultaneously in real sample.3.The POP-PC and POP-BT were obtained through Friedel-Crafts acylation reaction of potassium tetraphenylborate with p-phthaloyl chloride(PC)and 1,3,5-benzenetricarbonyl trichloride(BT),respectively.And then POP-PC and POP-BT were modified with ethylenediamine(EDA)to prepare organic porous polymers rich in amine groups(EDAPOP-PC and EDA POP-BT).The EDA-POPs exhibited superior adsorption capacity for endocrine disrupting chemicals(EDCs).After magnetically functionalization,the obtained M-EDA-POP-PC was employed as a magnetic adsorbent for enrichment of EDCs from real samples prior to high performance liquid chromatography-ultraviolet detection.The current strategy showed the low detection limits(S/N=3)of 0.02-0.07,0.04-0.08 and 0.04-0.10 ng mL-1 for river water,peach juice and lychee juice samples,respectively.The method recoveries were 82.2-115%with relative standard deviations below 8.6%.The proposed strategy showed good practicality for sensitive determination of EDCs in real samples.