Preparation And Appplication Of Molecularly Imprinted-Chemiluminescence Sensors In Analysis

In this thesis, molecularly imprinted polymer was synthesized by magnetic grapheneoxide as carrier has high selectivity. Combined with flow injection chemiluminescencetechnology, kinds of new molecularly imprinted-chemiluminescence sensors were designedand build to realize the on-line analysis of actual samples with high selectivity, highsensitivity and simple operation control.A novel flow injection chemiluminescence （FI-CL） sensor for determination of quercetinusing the system of luminol-NaOH-H2O2based on molecularly imprinted polymericmicrospheres （MIPm） as recognition element is established. The quercetin MIPm wassynthesized by precipitation polymerization using acetone as solvent, acrylamide （AM） asfunctional monomer, ethylene glycol dimethacrylate （EGDMA） as cross-linker and2,2-azobisisobutyronitrile （AIBN） as initiator. And the polymers’ properties werecharacterized. The FI-CL optimized experimental were obtained and the possible mechanismwas discussed. The CL intensity responded linearly to the concentration of quercetin rangedfrom1.4×10^-6to1.6×10^-4mol/L with a detection limit of9.3×10^-7mol/L. The relative standarddeviation （RSD） for determination was ranged from2.72to3.31%. On the basis of speedinessand sensitivity，the sensor is reusable and has a great improvement in selectivity. As a result,the new sensor had been successfully applied to the determination of quercetin in drugsamples.A new sensor for determination of L-Tryptophan based on flow injectionchemiluminescence using molecularly imprinted membrane as recognition element wasreported. The molecularly imprinted membrane was synthesized by precipitationpolymerization in acetone using Nylon membrane for support, and acrylamide as functionalmonomer and ethylene glycol dimethacrylate as cross-linker in the L-Tryptophan templatemolecule. And the possible schematic diagram of polymerization was studied. Then thesynthesized molecularly imprinted membrane was employed as recognition element, whichpacked into a lab-made “H” shape tube, which connected in flow injectionchemiluminescence analyzer. Under the optimal CL reaction conditions, the chemiluminescence intensity was correlated linear with the concentration of L-Tryptophanover the range of2.04×10^-7to7.06×10^-4mol/L and the detection limit was2.10×10^-8mol/L.The relative standard deviation （RSD） for determination of3.0×10^-5mol/L L-Tryptophan was2.4%（n=11）. The sensor was reusable and had a great improvement in sensitivity andselectivity in chemiluminescence analysis. As a result, the new method had been applied tothe determination of L-Tryptophan in real samples with satisfactory results.A chemiluminescence （CL） sensor for determination of epinephrine using the system ofluminol-Sodium hydroxide-Hydrogen peroxide based on graphene-magnetite-molecularlyimprinted polymer （GM-MIP） as recognition element is established. The epinephrineGM-MIP was synthesized using graphene which improving the adsorption capacity, magnetiteNPs makes the polymers easier to separate and fasten in the sensor. The adsorptionperformance and properties were characterized. And then, GM-MIP was used in CL analysisfor improving the selectivity. The CL optimized experimental were obtained and the possiblemechanism was also discussed. The CL sensor responded linearly to the concentration ofepinephrine ranged from1.04×10^-7to7.06×10^-3mol/L with a detection limit of1.09×10^-9mol/L. The relative standard deviation for determination was3.87%. On the basis ofspeediness and sensitivity，the sensor is reusable and has a great improvement in selectivityand adsorption capacity. As a result, the sensor had been applied to the determination ofepinephrine in drug samples.A chemiluminescence （CL） array sensor for determination of benzenediol isomerssimultaneously using the system of luminol-NaOH-H2O2based on a graphene-magnetite-molecularly imprinted polymer （GM-MIP） is described. Use of graphene in the GM-MIP thusprepared is helpful to improve the adsorption capacity, while use of magnetite nanoparticlescan facilitate the isolation of GM-MIP at end of their synthesis, and rendering easier the useof the polymers in the array sensor. The adsorption performance and properties werecharacterized. The GM-MIP was used to increase the selectivity in CL analysis. In addition,the sensor was reusable and of good selectivity and adsorption capacity. The array sensor wasfinally used for the determination of hydroquinone, resorcinol and catechol in waste watersamples simultaneously.A novel flow injection chemiluminescence （FI-CL） sensor for the determination of sulfamethoxazole （SMZ） was established which using chitosan/graphene oxide-molecularlyimprinted polymers （CG-MIP） as recognition element. The SMZ-CG-MIP was synthesized inacetone as solvent and chitosan/graphene oxide for support, using acrylamide as functionalmonomer, ethylene glycol dimethacrylate as cross-linker and2,2-azobisisobutyronitrile asinitiator. The CG-MIP showed satisfactory recognition capacity for the SMZ. Then thesynthesized CG-MIP was employed as recognition by packing into a lab-made tube connectedin FI-CL analyzer to establish a novel CL sensor respectively. The CL intensity respondedlinearly to the concentration of SMZ in the range1.0×10^-7mol/L-2.3×10^-3mol/L with adetection limit of2.9×10^-8mol/L, which is lower. The relative standard deviation for thedetermination of4.0×10^-4mol/L of SMZ was1.92%（n=11）. The sensor is reusable and has agreat improvement in sensitivity and selectivity for CL analysis which applied to thedetermination of SMZ in drug samples.A microflow chemiluminescence （CL） sensor for determination of dibutyl phthalate（DBP） based on magnetic molecularly imprinted polymer （MMIP） as recognition element wasfabricated. Briefly, a hydrophilic molecularly imprinted polymer layer was produced at thesurface of Fe3O4magnetic nanoparticles （MNPs） via combination of molecular imprinting andreversible stimuli responsive hydrogel. In this protocol, the initial step involvedco-precipitation of Fe²⁺and Fe³⁺in an ammonia solution. Silica was then coated on the Fe₃O₄nanoparticles using a sol-gel method to obtain silica shell magnetic nanoparticles. The MMIPwas synthesized using methacrylic acid （MAA） as functional monomer and ethylene glycoldimethacrylate （EGDMA） as cross-linker and2,2-azobisisobutyronitrile （AIBN） as initiator inchloroform. Then the synthesized MMIP and magnetic non-molecular imprinted polymers（MNIP） were employed as recognition by packing into lab-made straight shape tubes,connected in CL analyzer for establishing the novel sensor with a single channel syringepump. And a mixer for hydrolyzing of DBP was followed. Based on this experiment principle,DBP was determined indirectly. And the MMIP showed satisfactory recognition capacity toDBP, resulting to the wide linear range of3.84×10^-8-2.08×10^-5mol/L and the low detectionlimit of2.09×10^-9mol/L for DBP. The relative standard deviation （RSD） for DBP(3.20×10^-6mol/L) was1.40%（n=11）. Besides improving sensitivity and selectivity, the sensorwas reusable. The proposed DBP-MMIP-CL sensor has been successfully applied to determine DBP in drink samples.A biosensor for determination of bovine serum albumin （BSA） based on grapheneoxide-magnetite-molecularly imprinted polymer （GM-MIP） and luminol-CdTe is described.In this work, luminol was modified on the CdTe quantum dots （QDs） as chemiluminescence（CL） materials, which has a higher luminous efficiency. And recognition materials （BSAGM-MIP） was synthesized using graphene oxide （GO） and magnetite nanoparticles as carrier,the adsorption capacity and operation simplicity was improved respectively. Theperformances of GM-MIP and luminol-CdTe were characterized. The GM-MIP was used inCL analysis system before the process of BSA determination for increasing the selectivity.The chemiluminescence intensity of this biosensor responded linearly to the concentration ofBSA over the range from4.970×10^-10g/mL to2.510×10^-6g/mL with a detection limit of1.190×10^-10g/mL. The relative standard deviation （RSD） for the determination of5.0×10^-8g/mL BSA was2.59%（n=11）. On the basis of speediness, reusability and sensitivity, thebiosensor achieves the real-time online monitoring of BSA in milk samples.A microflow chip for determination of glucose using the chemiluminescence （CL）system of luminol-NaOH-H₂O₂based on core-shell magnetite molecularly imprinted polymer（MMIP） is described. The glucose-MMIP was synthesized using magnetite nanoparticles assupporter which made the chip changeful variegated and reusable. The adsorptionperformance and selective properties were characterized. The MMIP in chip was used in CLanalysis to increase selectivity and sensitivity. The MMIP-CL chip responded linearly to theconcentration of glucose over the range2.89×10^-8to3.16×10^-4mol/L with a detection limit of3.09×10^-10mol/L. On the basis of speediness and sensitivity，the microflow chip is reusableand shows a great improvement in selectivity and controllability and had been used for thedetermination of glucose in drug samples.