Construction Of Perylene Derivatives Electrochemiluminescence Sensor Based On Coreaction Accelerator Signal Amplification Strategy

Electrochemiluminescence(ECL)analysis technology,with the advantages of rapid analysis process,low background signals,high sensitivity,and low cost,exihibits great application in the field of biomolecular determination.Comparing with the classic ECL reagents such as ruthenium bipyridine,quantum dots,and metal clusters,perylene and its derivatives,have became an potential ECL materials owing to the virtues of excellent film-forming property,easily preparation,and remarkable optical and electron characteristic.Signal amplification is crucial for improving the analytical sensitivity in fabricating ECL sensor.Therefore,study of signal enhancement strategy becomes the reaserch hotspot.Common signal amplification strategies such as enzyme-catalyzed signal enhancement and nucleric acid-assisted signal amplification suffer from the disadvantagies like high cost,complicated experiment process and harsh storage conditions.Coreaction accelerator signal amplification strategy has attracted widely attention owing to its advantages of simple preaparation process,low-cost and high signal enhancement efficiency.This article mainly based upon the utility of perylene derivatives as ECL illuminant,with application of novel coreaction accelerators as signal amplification strategy and synthesis of signal probes which combined ECL luminophore and coreaction accelerator through ?-? stacking effect,electrostatic absorption effect and coordination effect for fabricating three kinds of ECL sensor to realize sensitive detection of folic acid(FA)and methotrexate(MTX).Main research contents of this article are presented as follows:Part 1.Fabricating ECL folic acid sensor based on PBs-PrGO as coreaction accelerator of PTCA/S2O82-systemThe Prussian blue functionalized partial reduced graphene oxide(PBs-PrGO)is employed as the signal amplification strategy of perylenetetracarboxylic acid(PTCA).The nanocomposite PTCA-PBs-PrGO is synthesized through ?-? stacking effect between PTCA and PBs-PrGO.Comparing with PTCA,the nanocomposite PTCA-PBs-PrGO exhibits stronger ECL emitting(about 3-fold enhancement).The possible mechanism is that the electrochemical reversible Fe2+/Fe3+ active could accelerate the reduction of S2O82-to promote the generation of more SO4·-thus obviously enhance the ECL response of the fabricated sensor.Target determination substance folic acid(FA)could be oxidized by SO4·-to produce 2-amino-1,4-dihydro-4-oxypteridine-6-carboxylic acid(ADOCA)thus leading to consumption of SO4·-and evidently quenched ECL emitting.Under the optimum conditions,a linear range of the FA targeted ECL sensor from 1×10-3 mol·L-1 to 1×10-9 mol·L-1 with the detection limits low as 0.719 nmol·L-1 could be obtained.Meanwhile,the fabricated sensor successfully applied for analysis of FA in tablets and spiked human urine samples.It is worth noting that the proposed strategy further widening the application of prussian blue and its analogues in the field of ECL sensor.Part 2.Fabricating ECL Methotrexate sensor based on 3D flower-like MoS2 as coreaction promotor of PTC-PEI/S2O82-systemThe amino-functionalized perylene derivatives PTC-PEI was synthesized through crosslinking perylenetetracarboxylic acid(PTCA)and poly ethyl enimine(PEI).Under the effect of electrostatic absorption,PTC-PEI was coupled with 3D flower-like MoS2 nanomaterial(3D MoS2 NFs)to prepare the nanocomposite of PTC-PEI-MoS2,which combined ECL luminophore and coreaction.3D MoS2 NFs as the coreaction accelerator in ternary ECL system(PTC-PEI/K2S2O8/3D MoS2 NFs)could enhance the ECL response of PTC-PEI via catalyzing S2O82-to generate more SO4·-.Meanwhile,the reversible Mo6+/Mo4+active sites could regenerate in electrochemical reaction process,thus prominently improving the ECL signal amplification efficiency of 3D MoS2 NFs.As a result,the nanocomposite PTC-PEI-MoS2 presents 3-fold stronger ECL emitting compared with PTC-PEI,and the constructed sensor exhibits a linear range from 1×10-5 mol·L-1 to 1×10-12 mol·L-1 with the detection limits down to 0.15 pmol·L-1.The proposed strategy not only provides a novel analytical method for quantitation of MTX,but also avoids the defect that traditional amino coreaction accelerator could easily be consumed during electrochemical reaction process in ECL system using K2S2O8 as coreactant,greatly improving the signal enhancement effeciency of coreaction accelerator.Part 3.Fabricating ECL folic acid sensor based on CuO nanoneedles as coreaction accelerator of PTCA/S2O82-systemThe ECL signal probe CuO NNs functionalized PTCA(PTCA-CuO)was synthesized through the specific absorption effect between Cu2+of CuO nanoneedles(CuO NNs)and carboxyl group(-COOH)of perylenetetracarboxylic acid(PTCA).The CuO NNs acted as the coreaction accelerator of PTCA/S2O82-system exhibits excellent catalytic effect towards the electrochemical reduction process of S2O82-,thus resulting in generating of more SO4·-and evidently improving the ECL reaction efficiency between PTCA and S2O82-.Moreover,the electrochemical reversible Cu+/Cu2+active sites endow CuO NNs higher signal amplification efficiency.Comparing with PTCA,the ECL emitting of PTCA-CuO exhibits 3-fold enhancement.With the existence of targeted determination folic acid(FA),the ECL signal could prominently quenched through consumption of SO4·-to realize sensitive analysis of FA.Under the optimum condition,the constructed sensor used for FA quantitation exhibits a linear range from 1×10-3 mol·L-1 to 1×10-10 mol·L-1 with the detection limits down to 62.4 pmol·L-1.Also,an excellent analytical performance could be obtained when determination of FA in spiked human serum samples.