Research For The Enrichment And Separation Of New Pollutant And Mechanism Based On Functionalized Conjugated Microporous Polymers

In this study,according to the structural characteristics perfluoroalkyl substances and nonsteroidal anti-inflammatory drugs,as well as the functionalization modification of materials,two new covalent organic polymers were designed and synthesized.And extremely sensitive sample preparation methods for the pollutant residues in environmental samples coupled with instrumental analysis technology were established.The details are as follows:1.Fluorine-functionalized conjugated microporous polymer for solid-phase extraction of nine perfluoroalkyl acidsPerfluoroalkyl acids（PFAAs）,which are persistent,toxic,ubiquitously distributed,and bioaccumulated have attracted increasing concern.To investigate the environmental effects of PFAAs,it is urgent to develop sensitive,rapid,and efficient methods for detecting trace level PFAAs.In this study,a conjugated microporous polymer（CMP）with loading of fluorine,fabricated by Sonogashira–Hagihara cross-coupling,was exploited as a solid-phase extraction（SPE）adsorbent.The prepared fluorine-functionalized CMP（FCMP）,which showed a large surface area of 1089 m²·g^-1,high porosity,and good chemical stability,was applied to extracting PFAAs from water samples.The adsorption mechanism was investigated using a sorption isotherm model,and the main interactions were fluorous and hydrophobic affinity.The FCMP-based SPE method combined with high-performance liquid chromatography-tandem mass spectrometry was achieved with low limits of detection(0.19–0.97 ng·L^-1),wide linear range(2–1600 ng·L^-1),and good reproducibility（3.4%–12.9%）under the optimal conditions.Furthermore,the approach was utilized for the analysis of three water samples（snow,river water,and irrigation water）to evaluate its reliability,and satisfactory recoveries（70.5%–127.5%）were obtained.Therefore,FCMP was feasible SPE adsorbent for the selective extraction of PFAAs.2.Magnetically modified covalent organic polymers and application of separation and enrichment for NSAIDs in water samplesIn recent years,due to the advancement of medical standard and population growth,the demand for drugs has grown rapidly.Nonsteroidal anti-inflammatory drugs（NSAIDs）are a class of commonly used anti-inflammatory and analgesic drugs.And the effects of these compounds and their metabolites on the environment need to be studied.So,sensitive,rapid,and efficient detection methods for NSAIDs are the basic premises.In this work,a magnetic covalent organic polymer material（Fe₃O₄@COP-triazole）with magnetism and a large number of adsorption sites was synthesized via a one pot method and click chemistry theory.The extraction conditions were optimized by the response surface method,and the eluent condition was optimized by the single-factor method.Under optimal conditions,the MSPE-HPLC-MS/MS method based Fe₃O₄@COP-triazole was established for the quantitative analysis of NSAIDs residues in water samples.The recoveries of four NSAIDs showed a good linear relationship in the range of 0.25–25μg·L^-1,and the correlation coefficient are higher than 0.9928.The limits of detection and limits of quantification of the method were in 0.016–0.056μg·L^-1 and 0.055–0.189μg·L^-1,respectively.Three environmental water samples were used for the spiked recovery experiments to verify the practicability of method.The recovery of four NSAIDs are from76.3%to 119.4%.It can be illustrated that interaction forces between Fe₃O₄@COP-triazole and NSAIDs are hydrogen bonds,van der Waals forces andπ-πaccumulation forces according to the results of density functional theory（DFT）.This study provides an idea for the rapid construction of magnetic COP and its utilization of extraction for environmental pollutants.The established two methods of solid-phase extraction in this work can achieve satisfied recovery.And the adsorption mechanism in procedure of extraction was studied by adsorption experiments and DFT simulation calculations,which provide some new ideas for the future research.The synthesis and application of Fluorine-and magnetic functional conjugated organic polymers show the great potential in the field of sample pretreatment.