CN108287187A - A kind of electrochemical luminescence sensor - Google Patents
A kind of electrochemical luminescence sensor Download PDFInfo
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- CN108287187A CN108287187A CN201810294706.1A CN201810294706A CN108287187A CN 108287187 A CN108287187 A CN 108287187A CN 201810294706 A CN201810294706 A CN 201810294706A CN 108287187 A CN108287187 A CN 108287187A
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Abstract
The invention discloses a kind of electrochemical luminescence sensors.The electrochemical luminescence sensor is the metal organic frame thin layer electrode modified by luminophor, and the metal organic frame thin layer modified by electrode and positioned at the luminophor of the electrode surface forms.The electrode is glass-carbon electrode, carbon paste electrode, carbon electrode, carbon fiber electrode or ITO electro-conductive glass.The luminophor can be tris (bipyridine) ruthenium.Present invention combination electrochemical deposition technique, so that luminophor is fixed in metal organic frame thin layer and modifies in electrode surface, co-reactant or determinand, which can be directly entered in thin layer, to be detected, in conjunction with immune response, the structure of the luminous sensing interface of novel electrochemical and its super quick immunoassay are realized.The method of the present invention is simple, at low cost, and will detect the acute myocardial infarction AMI marker of extremely low concentration, can be used for, based on the affine single goal analysis analyte detection of biology and multiobjective analysis object multi-channel detection, having huge application prospect.
Description
Technical field
The invention belongs to sensor fields, are related to a kind of electrochemical luminescence sensor.
Background technology
Acute myocardial infarction AMI is one of current disease death reason most common in the world.It is dead for high incidence and height
Active demand of the rate acute myocardial infarction AMI to quick, sensitive, inexpensive vitro diagnostic techniques is badly in need of carrying out unmarked nanochemistry
Shine a new generation's vitro diagnostic techniques and its application study in acute myocardial infarction AMI quick diagnosis, development hypersensitivity, height
The acute myocardial infarction AMI quick diagnosis new method of specificity.For it is specified immune to immunoassay, because immune system has
Excellent specific recognition characteristic and the sensitivity that shows fabulous selectivity, therefore improve immunoassay has become immune point of innovation
The crucial point of penetration of analysis method.Because immune detection object (such as protein) is mostly without the direct output of notable signal Analysis, nanometer
The application of material has become the Critical policies in immunoassay.So far, the metal nano materials such as nano material such as gold, silver,
The quantum dots (QDs) such as metal sulfide (or metal selenide, metal telluride), metal oxide nano-material, nano-silicon and
Nano-sized carbon has unique optics, electricity, electrochemistry, catalysis and mechanical property, can also be obtained for Electrogenerated chemiluminescent immunoassay
Immune signal to Gao Min exports.And metal organic frame (MOFs) material is by central metallic ions and organic ligand voluntarily group
A kind of novel class zeolite porous material made of dress, therefore the organic ligand for designing specific structure and different centers can be passed through
Metal ion is coordinated, to construct the novel functional compounds of various structures.It is easy to set as a kind of environmentally protective, structure
Control, functional diversities, the novel porous materials derived from a wealth of sources are counted, since it is with unique light, electricity, magnetic, catalysis and absorption
Etc. performances, make that show tempting application prospects, and practical application is obtained in Electrogenerated chemiluminescent immunoassay.For example,
Yuan etc. synthesized N- (4- aminobutyls)-N- ethyl different luminols modification MOFs as electrochemical luminescence tracer-labelling in
On secondary antibody, the immunosensor of interlayer type is constructed on glassy carbon electrode, realizes the super of mucoprotein in human breast cancer cell
Sensitive Detection.Similarly, ruthenium compound modification MOFs can be not only used for internal external labeling, bio-light analysis and Photobiology at
Picture also can be used for Electrogenerated chemiluminescent immunoassay.For example, Yin etc. mixes the MOFs of ruthenium compound functionalization with graphene oxide
Drop coating is closed in glassy carbon electrode surface, carries out electrochemistry and electrochemical luminescence detection.However, utilizing these luminescence reagents to close in the past
At MOFs modification biosensor generally use elder generation complex functionality MOFs markers modify again in electrode surface carry out
The strategy of electrochemiluminescence analysis, in this way, inevitably complex operations limit Electrogenerated chemiluminescent immunoassay in the acute heart
The replacement of active demand of the flesh infarct to quick, sensitive vitro diagnostic techniques, solution also increases the complicated property of experimental implementation.
Invention content
The object of the present invention is to provide a kind of electrochemical luminescence sensors.
A kind of claimed electrochemical luminescence sensor, namely the metal modified by luminophor have machine frame
Frame thin layer electrode, the metal organic frame thin layer modified by electrode and positioned at the luminophor of the electrode surface form.
In the metal organic frame thin layer electrode of above-mentioned luminophor modification, the electrode is glass-carbon electrode, carbon paste electricity
Pole, carbon electrode, carbon fiber electrode or ITO electro-conductive glass.
The luminophor is at least one of tris (bipyridine) ruthenium and terpyridyl ruthenium derivative；
The metal organic frame thin layer is made by metal salt and the electrodeposited method of trimesic acid；
The metal salt is specially zinc salt or mantoquita；The zinc salt is more specifically zinc nitrate, zinc acetate or zinc chloride.
The metal organic frame thin layer electrode of the luminophor modification can be made by following methods provided by the invention.
The method of the metal organic frame thin layer electrode provided by the invention for preparing the tris (bipyridine) ruthenium modification, including such as
Lower step：
Electro-deposition is carried out to working electrode using electrodeposition process in situ, the metal for obtaining the tris (bipyridine) ruthenium modification is organic
Frame thin layer electrode；
Working electrode used is glass-carbon electrode, carbon paste electrode, carbon electrode, carbon fiber electrode or ITO electro-conductive glass；
Ligand, supporting electrolyte and water containing luminophor, formation metal organic frame thin layer in reaction solution used；
The luminophor is specially at least one of tris (bipyridine) ruthenium and terpyridyl ruthenium derivative；
The ligand for forming metal organic frame is zinc salt and trimesic acid；The zinc salt is specially zinc nitrate, acetic acid
Zinc or zinc chloride；
The supporting electrolyte is selected from least one of potassium nitrate, sodium nitrate, sodium chloride and potassium sulfate.
In the above method, the reaction solution is by the aqueous solution of zinc salt, the ethyl alcohol of the aqueous solution of tris (bipyridine) ruthenium, trimesic acid
Solution and potassium nitrate composition；The reaction solution can comprise the following steps：After each substance mixing of anabolic reaction liquid, at room temperature
It is vigorously stirred；The concretely 2.5-3.5 hours time of the stirring more specifically can be 3 hours；
The electrode radius of the working electrode is 1-5mm, specially 3mm.
A concentration of 0.1mg/mL~1.8g/mL of the aqueous solution of the zinc salt, specially 0.089g/mL；
A concentration of 1mmol/L~0.1mol/L of the aqueous solution of the tris (bipyridine) ruthenium；
A concentration of 1mg/mL~3.5g/mL of the ethanol solution of the trimesic acid, specially 0.035g/mL；
The dosage of the aqueous solution of the zinc salt, the aqueous solution of tris (bipyridine) ruthenium, the ethanol solution of trimesic acid and potassium nitrate
Than for 3mL：100μL：3mL：0.0303g.
Electrolytic cell used is two electrodes or three-electrode system；
Specifically, in the three-electrode system, used is platinum plate electrode to electrode；Reference electrode used is saturation calomel electricity
Pole.
In the electrodeposition step, negative potential is 0V (vs.SCE)~-2.0V (vs.SCE)；" vs.SCE " mean relative to
The current potential of saturated calomel electrode；
Electrodeposition time is 1-10800s, specially 1500s.
The method may also include the steps of：
Before the electrochemical-deposition step, metal organic frame thin layer electrode is conventionally cleaned；
Concretely cleaned as follows：By metal organic frame thin layer electrode successively in 0.5 and 0.05 μm of aluminium oxide
Sanding and polishing is handled in suspension, then fully rinses electrode surface with ultra-pure water, next respectively in ultra-pure water, ethyl alcohol, super
Each ultrasound 5min is to remove the remaining alumina powder of electrode surface in pure water；Then, dense H is added dropwise in electrode surface2SO4Washing lotion
And 15s is kept, use ultrapure water；Finally with electrochemical cleaning thoroughly to remove pollutant, then with after a large amount of ultrapure waters,
Nitrogen dries up.
In addition, the metal organic frame thin layer electrode of the tris (bipyridine) ruthenium modification is in Electrogenerated chemiluminescent immunoassay or light
Application in electro-catalysis and the application in detecting acute myocardial infarction AMI marker, also belong to protection scope of the present invention.
Wherein, the acute myocardial infarction AMI marker concretely cardic fatty acid binding protein；
In the detecting step, electrode used therein system is three-electrode system；
Working electrode is the metal organic frame thin layer electrode that the tris (bipyridine) ruthenium of the immune modification is modified；It is immune
The method of modification is conventional method.
It is platinum filament to electrode；
Reference electrode is Ag/AgCl electrodes；
Electrolyte is the 0.1mol/L phosphate buffers containing 0.1mol/L triethanolamines, pH value 7.0；
Sweep interval is 0V~1.35V (vs.Ag/AgCl), and photomultiplier PMT is set as 800V.
The present invention is constructed a kind of novel as tris (bipyridine) ruthenium luminophor is modified using electrochemical deposition method
Metal organic frame thin layer electrode.The present invention uses three-electrode system, required reaction solution is added in electrolytic cell, in working electrode
Electrochemical reaction just occurs for upper application negative potential, electrolytic cell, is electrically generated hydroxide ion in situ in electrode surface, activation neutrality is matched
Body deprotonation regulates and controls the growth of metal organic frame thin crystal layer.Due to electronegative trimesic acid ligand and positively charged
Terpyridyl ruthenium ion electrostatic attraction effect, the luminophors molecule such as tris (bipyridine) ruthenium is brought into metal organic frame
Crystal in, to a step original position electrodeposition process obtain tris (bipyridine) ruthenium modify metal organic frame thin layer electrode.It will
This modified electrode is used for unmarked Electrogenerated chemiluminescent immunoassay, indirect realize target analytes in sample quantitative point
Analysis so that electrochemical luminescence method can detect the protein down to fg/mL levels.Compared with prior art, the method for the present invention
Simply, at low cost, and the acute myocardial infarction AMI marker (cardic fatty acid binding protein, FABP) of extremely low concentration can be detected,
It can be used for based on the affine single goal analysis analyte detection of biology and multiobjective analysis object multi-channel detection.It is based on three pyrroles in research
Electrochemical luminescence and photoelectrocatalysis of pyridine ruthenium etc. have huge application prospect.
Description of the drawings
Fig. 1, which is the metal that (routine) electrochemical deposition method of embodiment 1 builds novel tris (bipyridine) ruthenium modification, machine frame
Frame lamellar means schematic diagram, wherein 1- electrochemical workstations, 2- solution, 3- working electrodes, 4- is to electrode, 5- reference electrodes, 6-
The metal organic frame thin layer electrode of tris (bipyridine) ruthenium modification.
Fig. 2 is the immune response schematic diagram of embodiment 1.Research system is cardic fatty acid binding protein on modified electrode
Immune response.
Fig. 3 is the electrochemical luminescence signals figure of embodiment 1.
Fig. 4 is the canonical plotting of embodiment 1.
Specific implementation mode
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following embodiments.Institute
It is conventional method to state method unless otherwise instructed.The raw material can obtain unless otherwise instructed from open commercial sources.
Embodiment 1,
(1) preparation of electrodeposit liquid：The zinc nitrate of 0.266g is dissolved in 3mL water, the potassium nitrate for adding 0.0303g is made
For supporting electrolyte.0.105g trimesic acids are dissolved in 3mL ethyl alcohol, are added in zinc nitrate aqueous solution, are added after mixing
The tris (bipyridine) ruthenium aqueous solution for entering 100 μ L 0.1M, is vigorously stirred 3 hours at room temperature.
(2) preparation of modified electrode：Glass-carbon electrode (GCE) is successively polished in 0.5 and 0.05 μm of aluminium oxide suspension
Polishing treatment, then electrode surface is fully rinsed with ultra-pure water, next each ultrasound in ultra-pure water, ethyl alcohol, ultra-pure water respectively
5min is to remove the remaining alumina powder of electrode surface；Then, dense H is added dropwise in electrode surface2SO4Washing lotion simultaneously keeps 15s, uses
Ultrapure water；Finally with electrochemical cleaning thoroughly to remove pollutant, then with after the flushing of a large amount of water, nitrogen dries up.
Electrochemical cleaning step is：In 10mL 0.50mol/L H2SO4In followed with the speed of sweeping of 0.1V/s with -1.0V to 1.0V
Ring voltammetric scan is to stabilization.The glass-carbon electrode handled well is rinsed with a large amount of water, is then dried up with nitrogen.
Electrode is placed in the electrodeposit liquid in above-mentioned (1), electro-deposition 1500s (vs.SCE (the saturation calomel at -1.3V
Electrode)).Then it is cleaned with secondary water, obtains the metal organic frame thin layer electrode (Ru-MOFs/ of tris (bipyridine) ruthenium modification
GCE)。
(3) unmarked immunoelectrode is prepared.The chitosan (CS) of 3.0 μ L 0.5% is dripped to the vitreous carbon modified in MOFs
On electrode (Ru-MOFs/GCE), glutaraldehyde (GA) the reaction 2h of 6 μ L 2.5% is added dropwise after dry, is then added dropwise 6.0 μ L rapidly
Contain 1.0mg/mL primary antibodies (Ab1) PBS solution drop on GA-CS/Ru-MOFs/GCE electrodes, (4 DEG C) of refrigerator preserves, overnight,
To ensure that antibody is adsorbed in the saturation of electrode surface, Ab is obtained1/ GA-CS/Ru-MOFs/GCE modified electrodes.Electrode is used successively
After PBS solution cleaning, drying, the 6.0 μ L PBS solutions for containing 3%BSA are dropped on electrode, 4 DEG C keep 1h non-specific to close
Property adsorption site, obtains BSA/Ab1/ GA-CS/Ru-MOFs/GCE modified electrodes.When being not used, electrode is stored in 4 DEG C of PBS
In.
The BSA/Ab that will be prepared1/ GA-CS/Ru-MOFs/GCE modified electrodes, be added dropwise 6.0 μ L contain 150fg/mL,
15fg/mL, 1.5fg/mL, 1.5pg/mL, 15pg/mL, 150pg/mL, 1.5ng/mL, 15ng/mL or 150ng/mL various concentration
The PBS of antigen (FABP, hFABP), incubates 1h at 37 DEG C, then uses PBS solution cleaning electrode table
Face obtains FABP/BSA/Ab1/ GA-CS/Ru-MOFs/GCE modified electrodes.(Ab1、Ab2For anti-human cardioid aliphatic acid combination egg
In vain).
(4) electrochemical luminescence detection process.Use three-electrode system (working electrode for above-mentioned (3) in prepare it is immune
Electrode, is platinum filament to electrode, and reference electrode is silver/silver chlorate (Ag/AgCl)), 500 μ L are contained into 0.1mol/L triethanolamines
0.1mol/L phosphate buffers (pH=7.0) add to electrolytic cell.Testing conditions are：Sweep interval is 0V~1.35V (vs.Ag/
AgCl), photomultiplier PMT is set as 800V.The electrochemical luminescence signals on the working electrode are obtained, to realize sample indirectly
The quantitative analysis of target analytes FABP in product.
Above-mentioned electrochemical depositer is as shown in Figure 1, immunoreaction process is as shown in Figure 2.Gained electrochemical luminescence signals
As shown in figure 3, as seen from the figure, as antigen concentration increases, electrochemical luminescence response also decreases；Electrochemistry is sent out in the present invention
Luminous intensity is 150fg/mL~150ng/mL with the antigen concentration range of linearity, and detection is limited to 2.6fg/mL (signal-to-noise ratio 3).This hair
The bright method range of linearity is wide, and detection limit is low.
Claims (10)
1. the metal organic frame thin layer electrode of luminophor modification, by electrode and positioned at the light emitting compound of the electrode surface
The metal organic frame thin layer composition of object modification.
2. the metal organic frame thin layer electrode of luminophor modification according to claim 1, it is characterised in that：It is described
Electrode is glass-carbon electrode, carbon paste electrode, carbon electrode, carbon fiber electrode or ITO electro-conductive glass；
The luminophor is at least one of tris (bipyridine) ruthenium and terpyridyl ruthenium derivative；
The metal organic frame thin layer is made by metal salt and the electrodeposited method of trimesic acid；
The metal salt is specially zinc salt or mantoquita；The zinc salt is more specifically zinc nitrate, zinc acetate or zinc chloride.
3. the metal organic frame thin layer electrode of luminophor modification according to claim 1 or 2, it is characterised in that：
The metal organic frame thin layer electrode of the luminophor modification is made by any the methods of claim 4-7.
4. a kind of method preparing the metal organic frame thin layer electrode that luminophor described in claims 1 or 2 is modified, including
Following steps：
Electro-deposition is carried out to working electrode using electrodeposition process in situ, obtains the metal organic frame of the luminophor modification
Thin layer electrode；
Working electrode used is glass-carbon electrode, carbon paste electrode, carbon electrode, carbon fiber electrode or ITO electro-conductive glass；
Ligand, supporting electrolyte and water containing luminophor, formation metal organic frame thin layer in reaction solution used.
5. according to the method described in claim 4, it is characterized in that：The luminophor is tris (bipyridine) ruthenium and terpyridyl
At least one of ruthenium derivative；
The ligand for forming metal organic frame is zinc salt and trimesic acid；The zinc salt be specially zinc nitrate, zinc acetate or
Zinc chloride；
The supporting electrolyte is selected from least one of potassium nitrate, sodium nitrate, sodium chloride and potassium sulfate；
The reaction solution is by the aqueous solution of zinc salt, the aqueous solution of tris (bipyridine) ruthenium, the ethanol solution of trimesic acid and potassium nitrate group
At；
The radius of the working electrode is 1-5mm or 3mm.
6. according to the method described in claim 5, it is characterized in that：A concentration of 0.1mg/mL of the aqueous solution of the zinc salt~
1.8g/mL or 0.089g/mL；
A concentration of 1mmol/L~0.1mol/L of the aqueous solution of the tris (bipyridine) ruthenium；
A concentration of 1mg/mL~the 3.5g/mL or 0.035g/mL of the ethanol solution of the trimesic acid；
The aqueous solution of the zinc salt, the aqueous solution of tris (bipyridine) ruthenium, the ethanol solution of trimesic acid and potassium nitrate amount ratio be
3mL：100μL：3mL：0.0303g.
7. according to any method in claim 4-6, it is characterised in that：Electrolytic cell used is two electrodes or three electrode systems
System；
Specifically, in the three-electrode system, used is platinum plate electrode to electrode；Reference electrode used is saturated calomel electrode；
In the electrodeposition step, negative potential is 0V~-2.0V；
Electrodeposition time is 1-10800s or 1500s.
8. the metal organic frame thin layer electrode of any luminophor modification of claims 1 or 2 is exempted from electrochemical luminescence
Application in epidemic disease analysis or photoelectrocatalysis.
9. the metal organic frame thin layer electrode of any luminophor modification of claims 1 or 2 is in detection Acute myocardial
Application in infarct marker.
10. application according to claim 9, it is characterised in that：The acute myocardial infarction AMI marker is cardioid aliphatic acid
Binding protein；
Specifically, in the detecting step, electrode used therein system is three-electrode system；
Working electrode is the metal organic frame that any luminophor is modified in the claim 1-3 of the immune modification
Thin layer electrode；
It is platinum filament to electrode；
Reference electrode is Ag/AgCl electrodes；
Electrolyte is the 0.1mol/L phosphate buffers containing 0.1mol/L triethanolamines, pH value 7.0；
Sweep interval is 0V~1.35V, and photomultiplier PMT is set as 800V.
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