| In recent years,new chemiluminescence(CL)materials,chemiluminescence reagents and chemiluminescence systems have been continuously discovered.CL functionalized materials,synthesized by using various catalysts and CL reagents,not only have the characteristics of nanomaterials,but also exhibit good CL signals response.Based on these CL materials,numerous CL analytical methods have been developed and are widely used in the fields of environmental monitoring,biological analysis,food safety,and clinical testing.However,CL functionalized materials still don't well meet the signal requirements for detection of various ultra-trace targets,and the development of CL functionalized materials faces many problems,such as complexly synthetic steps,long synthetic time,poor stability,and so on.Therefore,it is of great significance to design and synthesize novel materials with excellent CL property,and to develop new methods for further enhancing the CL signals.In this thesis,two kinds of CL functionalized materials were synthesized by microwave method and solvothermal method.The morphology and composition of the materials were characterized.The CL performance of the materials was studied in detail,and the related CL mechanism was discussed.In addition,metal ions catalysts were introduced into the CL systems for signal amplification.Based on the synthesized CL functionalized materials and metal ions enhanced CL systems,CL analytical methods for rapid and sensitive detection of hydrogen peroxide,ascorbic acid,and hydroquinone(HQ)were developed.The main research contents are as follows:1.Based on the synthetic methods and characteristics of cobalt disulfide nanowires(CoS2 NWs)and N-(aminobutyl)-N-(ethylisoluminol)(ABEI)functionalized gold nanoparticles(AuNPs)materials,we designed and developed a rapid synthesis method for preparing ABEI/AuNPs/CoS2 NWs hybrids with strong CL emission.We developed a facile one-step method to decorate AuNPs on CoS2 NWs with the reductant of ABEI by simply microwave assisted treatment of the reactant for 2 min.ABEI acts as a stabilizer,reducing agent and CL reagent.Transmission electron microscopy(TEM),Energy-dispersive X-ray spectroscopy(EDS),X-ray photoelectron spectroscopy(XPS)and other techniques were used to characterize the morphology and composition of the prepared ABEI/AuNPs/CoS2 NWs.The results show that the products have good water solubility and dispersibility,and ABEI-functionalized AuNPs are evenly distributed on CoS2 NWs.Under alkaline conditions,the reaction of ABEI/AuNPs/CoS2 NWs and H2O2 produces a strong CL signal.The CL mechanism of ABEI/AuNPs/CoS2 NWs was also proposed.The excellent CL activity was attributed to that AuNPs and Co2+could catalyze the decomposition of H2O2 to produce of ·OH and ·O2-free radicals.At the same time,a nano platform of ABEI/AuNPs/CoS2 NWs is formed,which can promote electron transfer,which further enhances the CL emission.Herein,the ABEI/AuNPs/CoS2 NWs were used for non-enzymatic CL detection of H2O2.The CL intensity is proportional to the concentration of H2O2 in the range from 1 to 100 ?M,with the detection limit of 0.3 ?M.The developed method was also successfully applied for the detection of H2O2 in actual sample.ABEI/AuNPs/CoS2 NWs with excellent CL performance may be further expanded for applications in bioassays,environmental monitoring and biosensors in the future.This work provides new guideline for the design and synthesis of CL nanomaterials based on transition metal compounds.2.Based on the characteristics of phloroglucinol with activated hydroxyl group and large electronic conjugated structure,a simple solvothermal method was developed to synthesize carbon dots(CDs)by using phloroglucinol as precursor.The prepared CDs exhibit irregular shape and graphite-like structures,and the surface was partially oxidized.CDs reacted with H2O2 in a strong alkaline solution to generate highly efficient CL emission.Cu2+ions was observed to dramatically enhance the CL intensity of CDs-H2O2 system by 7.5 times,which outperformed other metal ions,such as Cr3+,Fe3+,Co2+,Fe2+ Ba2+,Mn2+,Mg2+,Ni2+,Zn2+and Sn2+.The enhancing mechanism of the Cu2+on the CDs-H2O2/NaOH system is that Cu2+can catalyse H2O2 to produce ·OH and ·O2-similarly to Fenton reaction,which accelerates the production of reactive oxygen species.The produced free radicals can interact with each other and/or with CDs,resulting in CDs·+ and CDs·-radicals CDs·+react with CDs·-to release energy in the form of CL emission.Ascorbic acid is a common reductant,and is often used as a free radical scavenger to ·OH and ·O2-.The inhibition of ascorbic acid on the CL of Cu2+-CDs-H2O2/NaOH system verified the CL mechanism of the reaction once again.Based on this,we developed a simple and fast CL method for the detection of ascorbic acid.The change of CL intensity responds linearly to the logarithm of ascorbic acid concentration from 0.1 ?M to 100?M,with a detection limit of 0.03 ?M.This work provides new ideas for the design and synthesis of other carbon dots materials with CL emission.3.The reaction of hydroquinone with potassium persulfate(K2S2O8)under alkaline conditions was observed to produce a strong CL signal.In the HQ+K2S2O8/NaOH system,the peak of CL emission located in the range of 520 nm-720 nm.Cu2+significantly enhanced the CL signal of the HQ+K2S2O8/NaOH system.The CL mechanism of HQ+K2S2O8/NaOH system was studied by free radical scavengers and electron spin resonance instrument.Cu2+ promotes the production of reactive oxygen species,such as ·OH and 1O2,and catalyzes the oxidation of HQ.Based on this reaction,we developed a CL analytical method for HQ.The linear range of HQ detection is from 0.05 ?M to 100?M,and the limit of the detection is 0.025 ?M.This method is sensitive and simple,and catechol and resorcinol have less interference on the signal.In addition,this work provides new ideas for the study of CL of other phenol derivatives,which is very meaningful for discovering and enriching CL systems. |
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