CN105510309B - A kind of water solubility electrochemical luminescence reagent and method that it is quantitatively detected - Google Patents
A kind of water solubility electrochemical luminescence reagent and method that it is quantitatively detected Download PDFInfo
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Abstract
The invention discloses a kind of water-soluble electrochemical luminescence reagents -- four (4- sulfonic groups phenyl) porphyrins（TSPP）, with K2S2O8When coexisting, there is good electrochemical luminescence performance.The applicant utilizes a kind of method of quantitative determination tetrasulfonic acid base phenyl porphyrin of the performance study.This method is with good stability and specificity, 1.13 × 10−6mol·L‑1To 3.39 × 10−5mol·L‑1The range of linearity in, the concentration of electrochemical luminescence intensity and TSPP is limited to 4.03 × 10 at good linear relationship, detection− 7mol·L‑1。
Description
Technical field
The invention belongs to Electroanalytical Chemistry technical fields, and in particular to a kind of water solubility electrochemical luminescence reagent and fixed to it
The method for measuring detection.
Background technology
Electrochemical luminescence is also known as electrogenerated chemiluminescence, abbreviation ECL.It refers to some intermediates, mainly free radical from
Son results from electrode surface under the excitation of electricity, then carries out high energy electron transport reaction, one generated to form excitation state
Kind luminescence phenomenon.Electrochemical luminescence be combine electrochemistry and chemiluminescent analysis and testing technology, electrochemiluminescence analysis in addition to
Other than some features for having fluorescence analysis and chemiluminescence analysis, while the also characteristic with some electrochemistry.Mainly have with
Lower feature：
1, the range of linearity is wide, high sensitivity.
2, reaction controllability is strong, is conducive to the research of luminescence-producing reaction mechanism.
3, analyze speed is fast, and experimental provision is simple.
4, in situ detection can be carried out, reagent circulation uses.
5, analysis has a wide range of application, and is combined with multiple technologies.
So far, many electrochemiluminescsystem systems are found, many reagents can generate electrochemical luminescence, but only
The electrochemical luminescence reaction of several types can be applied in practice, mainly there is following five class.The first kind is hydrazides chemical combination
The electrochemical luminescence of object.Hydrazide kind compound is a kind of typical electrochemical luminescence substance, and electrochemical luminescence behavior has hair
Light efficiency is high.The advantages that stable reagent, reaction carry out in water phase.The chemiluminescence of most of hydrazide kind compounds observed
There are hydrogen peroxide participation or pilot process to generate Peroxide compound.Second class is the electrochemistry hair of acridine compound
Light.The glossy essence of typical acridine electrochemical luminescence compound（lucigein）System and acridinium ester（AE）System, this kind of hair
Photo etching does not need the presence of catalyst, can shine in the dilute alkaline soln of hydrogen peroxide.Third class is polycyclic aromatic hydrocarbons electricity
Chemiluminescence.Most study is aromatic hydrocarbons in organic matter electrochemical luminescence substance, especially polycyclic aromatic hydrocarbon（PAH）.Polycyclic fragrance
Hydrocarbon is also known as condensed-nuclei aromatics, its electrochemical luminescence reaction has been widely studied.Typical polycyclic aromatic hydrocarbons (PAH) organic matter electrochemistry hair
Just carried out based on high-energy electron transfer reaction mechanism.4th class is peroxyoxalate electrochemical luminescence.Peroxidating grass
Acid esters（PO）Chemiluminescence reaction be considered as current most effective abiochemistry luminescence-producing reaction, the maximum quantum of the reaction
Yield is up to 34%.Since with very high chemiluminescence efficiency, peroxyoxalate class compound in analytical chemistry in addition to leading
Other than domain is widely studied and applied, also more development portable light source.5th class is metal complex electrochemical luminescence.
Many metal complexs and cluster class compound can generate electrochemical luminescence.There is no with four (4- sulfonic groups in the prior art
Phenyl) porphyrin（Meso-tetra (4-sulfonatophenyl) porphyrin, TSPP is synthesized by having document）
Report as electrochemical luminescence reagent.
Invention content
In order to solve the problems in the existing technology, the present invention provides a kind of water-soluble electrochemical luminescence reagent,
I.e. four (4- sulfonic groups phenyl) porphyrins（TSPP）；The present invention also provides the methods quantitatively detected to it.
It is to reach goal of the invention technical solution provided by the invention：
The present invention provides a kind of water-soluble electrochemical luminescence reagent, and the electrochemical luminescence reagent is four (4- sulfonic benzos
Base) porphyrin.
Preferably, the electrochemistry reagent is with K2S2O8For coreagent.
The present invention also provides the methods for carrying out quantitative detection to electrochemical luminescence reagent described in claim 1, in three electricity
In polar body system, to contain K2S2O8, TSPP phosphate buffer be solution, carry out electrochemical luminescence scanning, and tracer signal；
Result is substituted into linear equation：I=422.95+38.54C obtains the concentration of electrochemical luminescence reagent.
Preferably, in the three-electrode system, working electrode is naked glass-carbon electrode.
Preferably, -1.5V is arrived in current potential setting ranging from -0.3.
Preferably, the K2S2O8A concentration of 0.1mol/L-0.5mol/L；
It is highly preferred that the K2S2O8A concentration of 0.5mol/L.
Preferably, a concentration of 10mmol/L of the phosphate buffer.
Preferably, the pH value of the phosphate buffer is 7.4.
Preferably, the sweep speed of the electrochemical luminescence scanning is 0.05-0.5V/s.
It is highly preferred that the sweep speed of the electrochemical luminescence scanning is 0.1V/s.
The invention discloses a kind of new type water-solubility electrochemical luminescence material, i.e., four (4- sulfonic groups phenyl) porphyrins
（TSPP）, with K2S2O8When coexisting, there is good electrochemical luminescence performance.The applicant utilizes the performance study one
The method of kind four (4- sulfonic groups phenyl) porphyrins of quantitative determination.This method is with good stability and specificity, 1.13 ×
10−6mol·L-1To 3.39 × 10−5mol·L-1The range of linearity in, the concentration of electrochemical luminescence intensity and TSPP are at good
Linear relationship, detection are limited to 4.03 × 10−7mol·L-1。
Description of the drawings
Attached drawing is used to provide further understanding of the present invention, and a part for constitution instruction, the reality with the present invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.In the accompanying drawings：
Fig. 1 is cyclic voltammogram of the different solutions on naked glass-carbon electrode；Wherein, a is TSPP buffer solutions, b K2S2O8
Buffer solution, c are TSPP+ K2S2O8Mixed solution；
Fig. 2 is electrochemical luminescence figure of the different solutions on naked glass-carbon electrode；Wherein, a is TSPP buffer solutions, and b is
K2S2O8Buffer solution, c are TSPP+ K2S2O8Mixed solution；
Fig. 3 is the K of various concentration2S2O8Electrochemical luminescence figure on naked glass-carbon electrode；In figure, a's is a concentration of
A concentration of 0.25mol/L of a concentration of 0.2mol/L of a concentration of 0.15mol/L of 0.1mol/L, b, c, d, e's is a concentration of
A concentration of 0.5mol/L of a concentration of 0.4mol/L of 0.3mol/L, f, g；
Fig. 4 is naked glass-carbon electrode in TSPP/K2S2O8System, 0.1 molL-1PBS buffer solutions（Containing 0.1 mol
L-1KCl）In, sweep the electrochemical luminescence figure under speed in difference；
Fig. 5 is naked glass-carbon electrode in TSPP/K2S2O8System, 0.1 molL-1PBS buffer solutions（Containing 0.1 mol
L-1KCl）In, the electrochemical luminescence figure of the circle of continuous scanning 20；
Fig. 6 is the electrochemical luminescence scanning figure and TSPP linear equations of various concentration TSPP solution；Wherein, a-g's is dense
Degree is respectively：1.13×10-6 mol·L-1, 5.56 × 10-6 mol·L-1, 1.13 × 10-5 mol·L-1, 1.7 × 10-5
mol·L-1, 2.26 × 10-5 mol·L-1, 2.83 × 10-5 mol·L-1, 3.39 × 10-5 mol·L-1 。
Specific implementation mode
Embodiment below facilitates a better understanding of the present invention, but does not limit the present invention.Experiment in following embodiments
Method is unless otherwise specified conventional method.Test material as used in the following examples is unless otherwise specified city
It sells.The water used in experimentation is redistilled water, and it is that analysis is pure to test reagent used.Experiment at room temperature into
Row.
Embodiment 1
a）The polishing treatment of electrode：Before the experiments were performed, by glass-carbon electrode successively with 0.3 μm, 0.05 μm of three oxidations
Then two aluminium suspension sanding and polishings on chamois leather use volume fraction to rinse for several times for ethyl alcohol, the redistilled water of 95 ﹪, then put
It is spare after being dried up with nitrogen to being cleaned in ultrasonic cleaner.It is handled through above step and then electrode is placed in 5mL concentration
For 1mmol L-1The potassium ferricyanide in, wherein contain 0.1 mol L-1Potassium chloride electrolyte, using three-electrode system,
Wherein glass-carbon electrode is working electrode, and platinum filament is to be carried out at multiple channel operation station using Ag/AgCl electrodes as reference electrode to electrode
Cyclic voltammetry scan characterizes glass-carbon electrode；
b）Prepare TSPP buffer solutions：A certain amount of TSPP storing solutions are pipetted in the plastic centrifuge tube of 1.5 mL, then are moved into
0.1 molL that pH is 7.4-1PBS buffer solutions (contain 0.1 mol L-1KCl it) is diluted to 1mL, is shaken up；It prepares
A concentration of the 2 × 10 of TSPP in TSPP buffer solutions−5 mol·L-1；KCl is the supporting electrolyte of buffer solution；
Prepare K2S2O8Buffer solution：A certain amount of storing solution is pipetted in the plastic centrifuge tube of 1.5 mL, then moves into pH and is
7.4 0.1 molL-1PBS buffer solutions (contain 0.1 mol L-1KCl it) is diluted to 1mL, is shaken up；The K of preparation2S2O8It is slow
K in fliud flushing2S2O8A concentration of 0.1 molL-1；
Prepare TSPP+K2S2O8Mixed solution：Pipette a certain amount of TSPP storing solutions, storing solution in 1.5 mL plastics from
In heart pipe, then move into 0.1 molL that pH is 7.4-1PBS buffer solutions (contain 0.1 mol L-1KCl it) is diluted to 1mL,
It shakes up；A concentration of the 2 × 10 of TSPP in obtained mixed solution−5 mol·L-1, K2S2O8A concentration of 0.1 molL-1；
c）600 μ L steps b are pipetted respectively）In various solution in different sample cells, stand 2min, wait for stable system it
Afterwards, using glass-carbon electrode as working electrode, Ag/AgCl electrodes, platinum filament are respectively reference electrode and to electrode, and -1.5V is arrived in -0.3V
Between carry out cyclic voltammetry scan, as a result referring to Fig. 1.
Fig. 1 is cyclic voltammogram of the different solutions on naked glass-carbon electrode；Wherein, a is TSPP buffer solutions, b K2S2O8
Buffer solution, c are TSPP+ K2S2O8Mixed solution；As can be seen from Figure 1 curve a is the cyclic voltammetry curve of TSPP ,-
There is a reduction peak in 0.7V, and peak current is weaker；Curve b is K2S2O8Cyclic voltammetry curve, -1.1V or so occur
One reduction peak, this reaction are irreversible procedure；Curve c is TSPP and K2S2O8Cyclic voltammetry curve under existing simultaneously, mixing
There are two reduction peaks simultaneously in -0.7V and -1.3V in liquid, corresponds respectively to TSPP and K2S2O8Reduction peak, the peak of TSPP
Current potential is constant, K2S2O8Spike potential but bear and moved 0.2, reason may be that the presence of TSPP restores it and produces influence.
Embodiment 2
a）The polishing treatment of electrode is the same as embodiment 1；
b）The preparation of three kinds of solution is the same as embodiment 1；
c）The 600 above-mentioned mixed solutions of μ L are pipetted in sample cell, 2min are stood, after waiting for stable system, with glass-carbon electrode
For working electrode, Ag/AgCl electrodes, platinum filament are respectively reference electrode and to electrode, and electrification is carried out between -0.3V to -1.5V
Illumination scan is learned, as a result referring to Fig. 2.
Fig. 2 is electrochemical luminescence figure of the different solutions on naked glass-carbon electrode；Wherein, a is TSPP buffer solutions, and b is
K2S2O8Buffer solution, c are TSPP+ K2S2O8Mixed solution；As can be seen from Figure 2 in TSPP and K2S2O8When individualism not
There is luminous signal, and there are very strong electrochemical luminescence signals when the two coexists in a system.
Embodiment 3
a）The polishing treatment of electrode is the same as embodiment 1；
b）In the TSPP solution to 1.5 mL centrifuge tubes for pipetting 100 μ L, then move into the K of 100 μ L various concentrations2S2O8（1×
10−1mol·L-1-5×10−1 mol·L-1）To centrifuge tube, it is eventually adding 0.1 molL that 800 μ L pH are 7.4-1PBS is slow
Rush solution（Containing 0.1 molL-1KCl）It is 1mL to make total volume, shakes up and stands 2min；The concentration of TSPP in buffer solution
It is 2 × 10−5 mol·L-1；
c）The 600 above-mentioned mixed solutions of μ L are pipetted respectively in sample cell, using glass-carbon electrode as working electrode, Ag/AgCl electricity
Pole, platinum filament are respectively reference electrode and to electrode, and cyclic voltammetry scan and electrochemical luminescence are carried out between -0.3V to -1.5V
Scanning, as a result referring to Fig. 3.
Fig. 3 is the K of various concentration2S2O8Electrochemical luminescence figure, it can be seen that when various concentration, to its electrochemical luminescence
Intensity has a certain impact.In figure, a concentration of 0.2mol/L of a concentration of 0.15mol/L of a concentration of 0.1mol/L of a, b, c,
A concentration of 0.5mol/L of a concentration of 0.4mol/L of a concentration of 0.3mol/L of a concentration of 0.25mol/L of d, e, f, g.
Embodiment 4
a）The polishing treatment of electrode is the same as embodiment 2；
b）In the TSPP solution to 1.5 mL centrifuge tubes for pipetting 100 μ L, then move into the K of 100 μ L2S2O8To centrifuge tube, add
Enter 0.1 molL that 800 μ L pH are 7.4-1PBS buffer solutions（Containing 0.1 molL-1KCl）It is 1mL to make total volume, is shaken
It is even and stand 2min；A concentration of the 2 × 10 of TSPP in obtained buffer solution−5 mol·L-1, K2S2O8A concentration of 0.5
mol· L-1；
c）The 600 above-mentioned mixed solutions of μ L are pipetted in sample cell, using glass-carbon electrode as working electrode, Ag/AgCl electrodes, platinum
Silk is respectively reference electrode and to electrode, is arranged between -0.3V to -1.5V and different sweeps speed（0.05 V·s-1-0.8 V·
s-1）Electrochemical luminescence scanning is carried out, as a result referring to Fig. 4.
Fig. 4 is the different electrochemical luminescence figures swept under speed.
Embodiment 5
a）The polishing treatment of electrode is the same as embodiment 1；
b）In the TSPP solution to 1.5 mL centrifuge tubes for pipetting 100 μ L with liquid-transfering gun, the K of 100 μ L is then moved into2S2O8It arrives
Centrifuge tube, then move into 0.1 molL that pH is 7.4-1PBS buffer solutions（Containing 0.1 molL-1KCl）The total volume is set to be
1mL shakes up and stands 2min；A concentration of the 2 × 10 of TSPP in obtained buffer solution−5 mol·L-1, K2S2O8Concentration
For 0.5 mol L-1；
c）The 600 above-mentioned mixed solutions of μ L are pipetted in sample cell, using glass-carbon electrode as working electrode, Ag/AgCl electrodes, platinum
Silk is respectively reference electrode and to electrode, electrochemical luminescence scanning is carried out between -0.3V to -1.5V, as a result referring to Fig. 5.
Fig. 5 is naked glass-carbon electrode in TSPP/K2S2O8System, 0.1 molL-1PBS buffer solutions（Containing 0.1 mol
L-1KCl）In electrochemical luminescence figure, as seen from Figure 5, system continuous scanning 20 enclose after, electrochemical luminescence intensity has
Preferable stability does not carry out presentation unsure state with scanning.
Embodiment 6
a）The polishing treatment of electrode is the same as embodiment 1；
b）Various concentration is pipetted with liquid-transfering gun（Known to concentration）100 μ L TSPP solution to 1.5 mL centrifuge tubes in,
Then the K of 100 μ L is moved into2S2O8To centrifuge tube, then move into 0.1 molL that pH is 7.4-1PBS buffer solutions make the total volume be
1mL shakes up and stands 2min；K in obtained buffer solution2S2O8A concentration of 0.5 mol L-1；
c）The 600 above-mentioned mixed solutions of μ L are pipetted in sample cell, using glass-carbon electrode as working electrode, Ag/AgCl electrodes,
Platinum filament is respectively reference electrode and to electrode, electrochemical luminescence scanning is carried out, as a result referring to Fig. 6.
Fig. 6 is the electrochemical luminescence scanning figure and TSPP linear equations of various concentration TSPP solution；Wherein, uppermost
Curve is not in the range of linearity, and second curve of number to the 8th curve is respectively a-g from top to bottom；The concentration of a-g is respectively：
1.13×10-6 mol·L-1, 5.56 × 10-6 mol·L-1, 1.13 × 10-5 mol·L-1, 1.7 × 10-5 mol·L-1,
2.26×10-5 mol·L-1, 2.83 × 10-5 mol·L-1, 3.39 × 10-5 mol·L-1 。
As shown in Figure 6：1.13 × 10−6mol·L-1To 3.39 × 10−5mol·L-1The range of linearity in, electrochemistry hair
At good linear relationship, detection is limited to 4.03 × 10 for luminous intensity and the concentration of TSPP−7mol·L-1；It is obtained linearly according to Fig. 6
Equation：
I=422.95+38.54C, R2=0.998；Wherein, C represents the concentration of TSPP, and I represents electrochemical luminescence intensity.
Embodiment 7
The method that Concentration Testing is carried out to the TSPP solution of unknown concentration is as follows：TSPP solution is subjected to a series of 10 multiple proportions
Dilution, is tested according to the method for embodiment 6, dilution of the luminous intensity within the scope of 0-1800 is selected, by the dilution
Experimental result substitute into equation, be multiplied by the extension rate, obtain the concentration of TSPP solution.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be used
With technical scheme described in the above embodiments is modified or equivalent replacement of some of the technical features.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention's
Within protection domain.
Claims (11)
1. application of four (the 4- sulfonic groups phenyl) porphyrins in preparing water-soluble electrochemical luminescence reagent.
2. application according to claim 1, it is characterised in that：When preparing the water-soluble electrochemical luminescence reagent, with
K2S2O8For coreagent.
3. the method that pair four (4- sulfonic groups phenyl) porphyrins carry out quantitative detection, it is characterised in that：In three-electrode system, to contain
There is K2S2O8, TSPP phosphate buffer be solution, carry out electrochemical luminescence scanning, and tracer signal；Result is substituted into linear
Equation：I=422.95+38.54C obtains the concentration of electrochemical luminescence reagent.
4. according to the method described in claim 3, it is characterized in that：In the three-electrode system, working electrode is naked glass carbon
Electrode.
5. according to the method described in claim 3, it is characterized in that：- 1.5V is arrived in current potential setting ranging from -0.3.
6. according to the method described in claim 3, it is characterized in that：The K2S2O8A concentration of 0.1mol/L-0.5 mol/L.
7. according to the method described in claim 3, it is characterized in that：The K2S2O8A concentration of 0.5mol/L.
8. according to the method described in claim 3, it is characterized in that：A concentration of 10mmol/L of the phosphate buffer.
9. according to the method described in claim 3, it is characterized in that：The pH value of the phosphate buffer is 7.4.
10. according to the method described in claim 3, it is characterized in that：The sweep speed of the electrochemical luminescence scanning is 0.05-
0.5V/s。
11. according to the method described in claim 10, it is characterized in that：The sweep speed of electrochemical luminescence scanning is
0.1V/s。
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