Electrochemiluminescence Properties And Biosensing Application Of Perylene Imide Derivatives

Electrochemiluminescence（ECL）is a kind of chemiluminescence phenomenon caused by electrochemical reaction on the electrode surface based on electrochemistry.Combined with electrochemical and chemiluminescence processes,the quantitative analysis of specific substances is carried out.With the rapid development of nanotechnology and biotechnology,electrochemiluminescence technology is also changing with each passing day,because of its sensitive and efficient detection and analysis.Technology has attracted much attention in the fields of life analysis,such as environmental testing,clinical testing,food safety and industrial analysis.Sensitive highly electroluminescent sensors require excellent properties such as good chemical stability and high luminescence quantum yield.Researchers have also been working to develop excellent luminophores.At present,the commonly used luminescent bodies are quantum dots,bipyridine ruthenium and luminol.In recent years,perylenetetracarboxylic acid molecules withπconjugated systems have been used to construct sensitive electroluminescence sensors due to their excellent electroluminescence properties.However,perylenetetracarboxylic acid molecules only have strong electroluminescence intensity at higher luminescence potential（-1.8 V）.It is necessary to design a good electrochemiluminescence sensor to consider some properties of the luminophor.This paper is based on the design,synthesis and biological sensor of the low-potential electrochromic luminophor of the cathode,including the following four parts:1.Perylene diimide as cathodic single electrochemiluminescence luminophore for immunoassay at low potentialA new electrochemiluminescent N,N’-Dimethyl-3,4,9,10-perylenedicarboximide was prepared.The luminophore produces a strong electrochemiluminescence signal at-0.47 V in the presence of co-reactor K₂S₂O₈and produces an electroluminescence wavelength of689 nm,which is emitted by the H-type N,N’-Dimethyl-3,4,9,10-perylenedicarboximide excited back to the ground state during the electroluminescent process.The electrochemiluminescence was further used to construct a biosensor with low potential electrochemiluminescence for the detection of tumor markers.We assemble the luminous body N,N’-Dimethyl-3,4,9,10-perylenedicarboximide on graphene oxide sheet byπ-πconjugated action,then the gold nanoparticles were fixed to N,N’-Dimethyl-3,4,9,10-perylenedicarboximide/graphene oxide composite,and finally adsorbed on the gold nanoparticles/N,N’-Dimethyl-3,4,9,10-perylenedicarboximide/graphene oxide composite,and made into a second antibody electrochemiluminescence material to construct sandwich immunosensor,which detect tumor marker carcinoembryonic antigen.The results showed that the prepared electrochemiluminescence biosensor showed a sensitive electrochemiluminescence response at-0.47 V for carcinoembryonic antigen,which has a high sensitivity and the detection limit was lowed to 0.29 fg m L^-1.And the sensor has a satisfact recovery rate in the serum detection of the cancer patient,and has proved that the sensor has good clinical practical value.2.Perylene diimide and luminol as potential-resolved electrochemiluminescence nanoprobes for dual targets immunoassay at low potentialOn the basis of study content 1,we synthesized a novel luminophore N,N-bis-（3-dimethyl aminopropyl）-3,4,9,10-perylene tetracarboxylic acid diimide,which emitters produce two strong electrochemiluminescence signal,and the electrochemiluminescence wavelength is 718 nm,which is light emitted by J-type N,N-bis-（3-dimethyl aminopropyl）-3,4,9,10-perylene tetracarboxylic acid diimide when the excited state returns to the ground state during the electrochemiluminescence.Under the catalysis of 0.6 V and silver nanoparticles,luminol can produce a strong electrochemiluminescence signal with hydrogen peroxide.Therefore,using N,N-bis-（3-dimethyl aminopropyl）-3,4,9,10-perylene tetracarboxylic acid diimide and luminol as potential-resolved emitters,we constructed two-component biosensors with potential resolution to detect different tumor markers at the same time.N,N-bis-（3-dimethyl aminopropyl）-3,4,9,10-perylene tetracarboxylic acid diimide combined with graphene oxide and second antibody,luminol and gold and silver composite particles,graphene oxide,second antibody.Electrochemiluminescence nanomaterials modified by two antibodies were formed by combining with the formation of potential resolved electrochemiluminescence nanomaterials.These two potential-resolved electrochemiluminescence nanomaterials are further used to construct potential-resolved sandwich biosensors.For simultaneous detection of carcinoembryonic antigen and alpha-fetoprotein,the linear scanning potential range is-0.6 V to 0.6 V.The sensor showed a sensitive electrochemiluminescence response to carcinoembryonic antigen at-0.6 V and a sensitive electrochemiluminescence response to alpha-fetoprotein at 0.6 V.The sensor had a good recovery rate in serum detection of cancer patients.These results suggest that the fabricated two-component simultaneous detection sensor has good practical value in clinical applications.3.Based on two different cathodic electrochemiluminescence luminophore to construct the ratio sensorA new electrochemiluminescence 1,6,7,12-tetrachloroperylene tetracarboxylic acid hydroxide（PTCDA-Cl₄）was prepared,exhibiting strong emission in-1.2 V in the S₂O₈^2-water system,is the emission of excited-state PTCDA-Cl₄dimers due to the synergistic reaction of PTCDA-Cl₄with S₂O₈^2-.The peak emission wavelength of electrochemiluminescence at 640 nm.We use this electrochemiluminescence body and the dual emission electrochemiluminescence body PDI used in study content 2 to construct a ratio immunosensor.Graphene oxide（GO）loaded with PDI binds to an antibody to form an electrochemiluminescent hybrid material labeled antibody.PTCDA-Cl₄was dripped on the glassy carbon electrode（GCE）,then dried and immersed in the electrodeposition Au NPs,then the antibody（Ab₁）was fixed.Next,the tumor markerα-fetoprotein（AFP）was used as the target analyte.Finally,the PDI electroluminescent hybridization conjugated to the antibody were added to the GCE/PTCDA-Cl₄/Au/Ab₁to form a proportional ECL immunosensor with PDI of-0.48 V and PTCDA-Cl₄of-1.2 V as the detection signal was formed.The immunosensor can sensitively detect AFP,from 0.01 pg m L^-1to 100 pg m L^-1has a good linear relationship and the detection limit low down 3.33 fg m L^-1.The self-calibration of the two emission signals to eliminate most interference and uncertainty,which shows the profound significance of self-calibration and can be used for accurate quantification.4.Construction of label-free immunosensor by multi-color electrochemiluminescent materials of tetramethylenedic anhydride-anilineWe have prepared a new polychromatic ECL nanomaterials in the aqueous phase to produce polychromatic emissions in the same potential range.The polychromatic ECL nanomaterials were prepared by assembling a single-emitting luminescent body3,4,9,10-perylenetetracarboxylic anhydride（PTCDA）with the co-reactant aniline（An）.The emission of PTCDA-An nanomaterials at 692 nm and 760 nm with K₂S₂O₈as the co-reactant,and at 486 nm is stronger than a single PTCDA at 483 nm.This highly efficient ECL nanomaterial PTCDA-An was further used to construct a label-free immunosensor to detect tumor markers.On the principle that the effective covering of the protein on the luminescent PTCDA-An hinders the effective collision between the luminescent body and the solution co-reaction agent,and then causes the sensitive change of the electroluminescent intensity.Gold nanoparticles were electrodeposited on the PTCDA-An surface and the primary antibody（Ab₁）was fixed to capture the target.Produced a potential-resolved polychromatic ECL,which greatly promoted the development of polychromatic ECL.