Preparation Of Microporous Organic Polymers And Their Application In N-Glycopeptides Enrichment And Copper Ion Adsorption

Microporous organic polymers(MOPs)have attracted much attention in the fields of catalysis and gas adsorption.These kind of materials with large surface could provide enough binding sites for target compound.The devisable pore structure and uniform pore size distribution are benefit for selectivity enrichment and adsorption.However,due to the limited variety of MOPs and the difficulty of functional modification,it is not conducive to the wide application of MOPs in separation analysis,including proteomics and metal ion adsorption.In views of these problems,this paper designed and developed new functional MOPs,which has a strong affinity for different types of analytes.Thus,it greatly enriched the types and applications of MOPs.The detailed contents are as follows:1.Macroporous adsorption resin(MAR)with?10?m diameter was synthesized by seed-swelling polymerization and further modified with a layer of microporous organic polymers(MOP)by“one-pot”solvothermal reaction.The synthesized MAR@MOP exhibited high specific surface area of 131.3 m~2/g,which was higher than that of pristine MAR(57.8 m~2/g).The water contact angle also decreased from 58.8?(MAR)to 24?(MAR@MOP),indicating that the MOP was successfully grafted onto the surface of MAR.The enrichment efficiency of MAR@MOP to glycopeptides was demonstrated by enriching N-linked glycopeptides from tryptic digests of human immunoglobulin G(IgG)using hydrophilic interaction chromatography(HILIC),up to 17 N-glycopeptides were identified from IgG digest.Furthermore,879 unique N-glycosylation sites in 811 unique glycopeptides sequence were identified in three replicate analyses of proteins extracted from mouse liver.Therefore,this hydrophilic MOP-coated adsorbent has potential application in the enrichment and identification of low-abundance N-linked glycopeptides in complicated biological samples.The modification method not only simplifies the synthesis process,but also provides a new idea for the synthesis of microspheres with different functions.2.In order to further certified the influence of chemical structure of the monomer on the pore structure and surface properties of MOPs,CH-pPAL and CH-mPAL were synthesized through the highly density nitrogen element carbohydrazide(CH)reactions with p-benzaldehyde(pPAL)and m-benzaldehyde(mPAL).The surface chemical structure was characterized by FT-IR and NMR.The water contact angle of CH-pPAL and CH-mPAL is35.4?and 28.8?.Finally,due to better hydrophilicity,CH-pPAL was applied to the enrichment of glycopeptides in complex biological samples.For CH-pPAL and CH-mPAL,up to 22 and25 N-glycopeptides were identified from IgG digest,570 and 597 N-glycopeptides sequence,552 and 600 N-glycosylation sites were identified from human serum digest,respectively.3.COFs,as a kind of MOP,have larger specific surface area and more regular pore structure than other kinds of MOPs.The proof-of-concept design was demonstrated by synthesizing a novel COF material(TpODH)using 1,3,5-triformylphloroglucinol(Tp)and oxalyldihydrazide(ODH)as precursors,in which the different organic building units are combined through hydrazone bonds to form 2D porous frameworks.It should be pointed that irreversible enol-to-keto tautomerism and intramolecular N-H···O=C hydrogen bonding of TpODH enhanced the crystallinity and chemical stability,leading to large specific surface area of 835 m~2/g.However,TFBODH building from 1,3,5-triformylbenzene(TFB)and ODH exhibited less crystallinity and low special surface area(94 m~2/g).Representatively,TpODH afforded Cu(II)capacity of 324 mg/g,while TFBODH afforded only 23 mg/g.It shows that the method of constructing COF materials with flexible moleculars as building block provides a new way for designing and preparing new COF materials.4.In order to further explore the formation mechanism of COF material with flexible monomer,functionalized COFs were synthesized.Flexible formic hydrazide(FH)was reacted with 1,3,5-triformylphloroglucinal(Tp)or 1,3,5-triformylbenzene(TFB)via formation of Schiff base.Two synthesized COFs(TpFH and TFBFH)exhibited the expected aldehyde-group decoration and the uniform hollow tubular morphology.Remarkable stability and high density of N,O elements aligned in periodic arrays on the walls of COFs,facilitating their cooperation interaction and high affinities toward copper ions and gas adsorbent.Given the structure of hollow microtubules formed by the materials and the large amount of nitrogen and oxygen on the skeleton,TpFH was applied to the adsorption of Cu(II)with the adsorption capacity of 162 mg/g.