CN106872546A - Electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe - Google Patents
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Abstract
The present invention discloses a kind of electrochemical reducing and prepares high quantum production rate electrochemical luminescence gold nano cluster probe.Electrogenerated chemiluminescence gold nano cluster probe of the present invention is, with functionalization gold nano cluster material as presoma, to carry out reduction treatment using electrochemical process and obtain.Above-mentioned electrogenerated chemiluminescence gold nano cluster probe modification on electrode, with over cure acid ion as coreagent, with good electrochemical luminescence performance.The present invention has that preparation method is simple, reaction condition gentle, favorable reproducibility, strong probe electrochemiluminescence signal and the features such as quantum yield high.With developing rapidly for Electrochemiluminescsensor sensor technology, it is contemplated that the probe will be with greater significance in fields such as chemistry, biological, medicine and environment.
Description
Technical field
The present invention relates to a kind of high quantum production rate electrochemical luminescence gold nano cluster probe material and its electrochemical reduction system
Preparation Method, belongs to field of nanometer technology.
Background technology
In recent years, semiconductor nanocrystal or quantum dot be used as a kind of new electrochemical luminescence nano luminous body, due to it
The advantages of good stability, anti-light bleaching power are strong, excitation spectrum is wider has received significant attention.Semiconductor nanocrystal or quantum
Point electrochemical luminescence combines the advantages such as semiconductor, electrochemistry and chemiluminescence as the frontier in Electrochemiluminescprocess process
And quickly grow.But the defect such as strong toxicity and non-molecule power rate fluorescence intermittency is in tracking and imaging especially organism
Using etc. research bring difficulty, therefore selection sensitivity is high, good biocompatibility label is used for bioanalysis and medical science is examined
Survey extremely urgent.
Gold nano cluster as novel nano illuminator, with size is small, nontoxic, good water solubility, special photoelectric property etc.
Feature, oneself is in the field extensive use such as clinical analysis, biological medicine, bio-sensing and catalysis.Although the fluorescence of gold nano cluster
Performance and its application have been widely studied, but due to weak electrochemical luminescence intensity and unknown mechanism, based on gold nano
The electrogenerated chemiluminescence sensing Study of An of cluster is also considerably less.Therefore, preparing, there is strong electrochemical luminescence signals and quantum high to produce
The electrogenerated chemiluminescence gold nano cluster probe of rate is significant for building high-performance Electrochemiluminescsensor sensor.
The present invention prepares electrochemical luminescence gold nano cluster probe, side of the present invention using simple electrochemical reducing
Method process is simple, reaction condition are gentle, favorable reproducibility, and prepared gold nano cluster probe electrochemiluminescence signal is strong and steady
It is fixed, and quantum yield is high.
The content of the invention
High quantum production rate electrochemical luminescence gold nano group is prepared it is an object of the invention to provide a kind of electrochemical reducing
Aggregate probe.
To achieve these goals, the present invention uses following technical scheme：
Electrochemical reducing of the present invention prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that adopting
Gold nano cluster material reduce with constant potential reducing process and obtains gold nano cluster probe, reduction potential be -0.2 V ~ -
2.0 V, gold nano cluster probe has good electrochemical luminescence performance.
The gold nano cluster material is functional modification gold nano cluster, and described functional modification gold nano cluster is adopted
With N- acetylations-Cys-gold nano cluster, glutathione-gold nano cluster or bovine serum albumin(BSA)-gold nano group
Cluster.
Described electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that by gold
Nanocluster probe modification, with potassium peroxydisulfate as coreagent, carries out electrification on glass-carbon electrode, and as working electrode
Luminous test is learned, electrochemical luminescence signals can be produced.
The synthesis step of described N-acetyl-L-cysteine-gold nano cluster is as follows：It is 0.1 ~ 0.8 mol/ by concentration
The NaOH of L and concentration be 0.01 ~ 0.1 g/L chlorauric acid solutions be added to N- acetyl that concentration is 0.02 ~ 0.18 mol/L-
Be placed in 20 ~ 70 DEG C of water bath with thermostatic control isothermal reactions 0.1 ~ 3.5 hour in Cys solution, after mixing, question response terminate after thoroughly
Analysis purification process, obtains N-acetyl-L-cysteine-gold nano cluster aqueous solution, and N- acetyl-L- half is can obtain after freeze-drying
Cystine-gold nano cluster material powder, N-acetyl-L-cysteine-gold nano cluster aqueous solution carries out spectrofluorimetry,
Its maximum excitation wavelength and launch wavelength are respectively 355 nm and 650 nm.
Described electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that electrochemical
Learn what luminous signal was gathered by following methods：By glass-carbon electrode Al2O3Powder is polished to smooth mirror surface, then is sequentially placed into HNO3
The aqueous solution, absolute ethyl alcohol is cleaned by ultrasonic, N in deionized water2Drying；By gold nano cluster probe modification in the glass carbon handled well
Electrode surface, obtains gold nano cluster probe modification glass-carbon electrode；Tested using three-electrode system, visited with gold nano cluster
Pin modified glassy carbon electrode is working electrode, and platinum electrode is that, to electrode, Ag/AgCl is reference electrode, and cushioning liquid is phosphate
Buffer solution or Tris-HCl cushioning liquid, electrolyte used are KCl or KNO3；The insertion of above-mentioned three electrode is total to containing potassium peroxydisulfate
In the cushioning liquid of reactant, apply certain voltage, working electrode surface produces electrochemical luminescence radiation.
Described electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that continuously
More than 24 sections electrochemical luminescence signals of Electrochemical Scanning keep constant.
Described electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that electrochemical
Learn luminous signal strong and weak related to the reduction potential that electrochemical luminescence gold nano cluster probe used is prepared.
Described electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that electrochemical
Learn luminous signal strong and weak linear with the ratio of Au (0) in electrochemical luminescence gold nano cluster probe.
Described electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that using
Constant potential reducing process is reduced to gold nano cluster material, and reduction potential is -2.0 V, the electrochemical luminescence gold for obtaining
The relative electrochemical luminous efficiency of nanocluster probe is 4.11%.
The preparation method of high quantum production rate electrochemical luminescence gold nano cluster probe of the present invention, it is characterized in that with gold
Nanocluster material modified glassy carbon electrode is working electrode, and platinum electrode is that, to electrode, Ag/AgCl is reference electrode, in phosphoric acid
In salt buffer solution apply -0.2 V voltages of V ~ -2.0 gold nano cluster material is carried out constant potential reduction obtain.
Specifically, the present invention uses following technical scheme：
（One）The preparation of N-acetyl-L-cysteine-gold nano cluster
N-acetyl-L-cysteine-gold nano cluster synthesis step is as follows：It is the NaOH of 0.1 ~ 0.8 mol/L by concentration
It is the N-acetyl-L-cysteine that 0.01 ~ 0.1 g/L chlorauric acid solutions are added to that concentration is 0.02 ~ 0.18 mol/L with concentration
20 ~ 70 DEG C of water bath with thermostatic control isothermal reactions 0 ~ 3.5 hour are placed in solution, after mixing.Question response terminates rear dialysis purification treatment, obtains
To N-acetyl-L-cysteine-gold nano cluster aqueous solution, N-acetyl-L-cysteine-gold nano is can obtain after freeze-drying
Cluster powder.
（Two）The preparation of gold nano cluster modified electrode
By glass-carbon electrode with 1.0 μm, 0.3 μm and 0.05 μm of Al2O3Powder is polished successively, polishing, to smooth mirror surface, then
It is sequentially placed into HNO3Solution（1:1）, absolute ethyl alcohol, ultrasonic cleaning 3 minutes, N in deionized water2Drying.Take 5 μ L N- acetyl-L-
Cysteine-gold nano cluster aqueous solution is added dropwise in the glassy carbon electrode surface handled well, drying at room temperature, obtains final product N- acetyl-L- half
Cystine-gold nano cluster modified glassy carbon electrode.
（Three）Electrochemical reduction processes gold nano cluster
Reduced using three-electrode system, be work electricity with N-acetyl-L-cysteine-gold nano cluster modified glassy carbon electrode
Pole, platinum electrode is that, to electrode, Ag/AgCl is reference electrode, and above-mentioned electrode is inserted the phosphate of 0.1 mol/L pH 7.4
In cushioning liquid, apply different negative potential voltages（In the range of -0.2 V of V ~ -2）, constant potential reduction treatment is carried out, obtain electricity
Chemiluminescence gold nano cluster probe.
（Four）The generation and detection of gold nano cluster probe electrochemiluminescence signal
Tested using three-electrode system, be work electricity with gold nano cluster or gold nano cluster probe modification glass-carbon electrode
Pole, platinum electrode is that, to electrode, Ag/AgCl is reference electrode, by above-mentioned electrode insert the cushioning liquid containing coreagent in,
Using step pulse method, initial potential is 0 V, and the burst length is 10 s, and termination current potential is -2 V, and the burst length is 1 s.Photoelectricity
Multiplier tube high pressure is set to 600 V ~ 800 V, the electrochemiluminescence signal that detection working electrode surface is produced, using electrification
Gold nano cluster probe its electrochemiluminescence signal prepared by reducing process is learned to significantly increase.
It is an advantage of the invention that：
（1）The present invention carries out reduction and prepares high-performance with functional modification gold nano cluster as presoma, using electrochemical method
Electrochemical luminescence gold nano cluster probe, the method has preparation method environmental protection, easy to operate, high repeatability and other advantages.
（2）Electrochemical luminescence gold nano cluster probe luminous intensity obtained by the present invention is big, and electrochemical luminescence quantum is produced
Rate is high, good biocompatibility, is had a good application prospect in Electrochemiluminescsensor sensor part and biomedical sector.
Brief description of the drawings
Fig. 1 is the fluorescence spectra of N-acetyl-L-cysteine-gold nano cluster.
Fig. 2 is the electrogenerated chemiluminescence-time graph of N-acetyl-L-cysteine-gold nano cluster modified glassy carbon electrode
Figure.
Fig. 3 is the electrogenerated chemiluminescence-time of gold nano cluster probe modification glass-carbon electrode prepared by electrochemical reducing
Curve map.
Fig. 4 is that gold nano cluster probe modification glass-carbon electrode prepared by electrochemical reducing continuously scans 24 sections of electricity of gained
Chemiluminescence intensity figure.
Fig. 5 prepares influence figure of the current potential to Au (0) ratio in gold nano cluster probe for gold nano cluster probe.
Fig. 6 prepares influence figure of the current potential to gold nano cluster probe electrochemical luminescence intensity for gold nano cluster probe.
Fig. 7 is the linear pass of Au (0) ratio in gold nano cluster probe electrochemical luminescence intensity and gold nano cluster probe
System's figure.
Specific embodiment
The present invention is further elaborated with specific embodiment below in conjunction with the accompanying drawings, and the present invention is not limited thereto.
Embodiment 1
It is 0.5 mol/L that 0.6 mL concentration is added toward the N-acetyl-L-cysteine solution that 4 mL concentration are 0.08 mol/L
NaOH and 0.4 mL concentration be 20 mg/mL chlorauric acid solutions, be placed in after mixing in 37 DEG C of Water Tanks with Temp.-controlled be incubated it is 3 small
When.Reaction solution after reaction terminates carries out dialysis purification treatment with the bag filter that retention molecule is 3500, obtains N- acetyl-L- half
Cystine-gold nano cluster the aqueous solution, obtains N-acetyl-L-cysteine-gold nano cluster powder after freeze-drying.Take above-mentioned
N-acetyl-L-cysteine-gold nano cluster aqueous solution carries out spectrofluorimetry, can obtain maximum excitation wavelength and launch wavelength
Respectively 355 nm and 650 nm（See Fig. 1）.
Embodiment 2
By the glass-carbon electrode of the mm of diameter 3 successively with 1.0 μm, 0.3 μm and 0.05 μm of Al2O3Powder is polished to smooth mirror
Face, then it is sequentially placed into HNO3Solution（Concentrated nitric acid is 1 with water volume ratio:1）, absolute ethyl alcohol, 3 points of ultrasonic cleaning in deionized water
Clock, N2Drying.5 μ L N-acetyl-L-cysteines-gold nano cluster solution is taken to be added dropwise in the glassy carbon electrode surface handled well,
Drying at room temperature, obtains N-acetyl-L-cysteine-gold nano cluster modified glassy carbon electrode.The insertion of above-mentioned electrode is contained 0.1
In the PBS of the 0.1 mol/L pH 7.4 of mol/L potassium peroxydisulfates and 0.1 mol/L KCl.Using step pulse
Method, initial potential is 0 V, and the burst length is 10 s, and termination current potential is -2 V, and the burst length is 1 s.Photomultiplier high pressure sets
700 V are set to, the electrochemiluminescence signal that detection working electrode surface is produced obtains weaker electrochemical luminescence signals（See
Fig. 2）.
Embodiment 3
Electrochemical reduction is carried out using three-electrode system, is with N-acetyl-L-cysteine-gold nano cluster modified glassy carbon electrode
Working electrode, platinum electrode is that, to electrode, Ag/AgCl is reference electrode, and above-mentioned electrode is inserted into 0.1 mol/L pH's 7.4
In PBS, constant potential reduction is carried out, reduction potential is -2.0 V, and the recovery time is 5 minutes, obtains reducing Jenner
Rice cluster probe modification glass-carbon electrode.The reduction gold nano cluster probe modification glass-carbon electrode insertion that will be prepared contains 0.1 mol/
In the PBS of the 0.1 mol/L pH 7.4 of L potassium peroxydisulfates and 0.1 mol/L KCl.Using step pulse method,
Initial potential is 0 V, and the burst length is 10 s, and termination current potential is -2 V, and the burst length is 1 s.Photomultiplier high pressure is set
It is 700 V, the electrochemiluminescence signal that detection working electrode surface is produced（See Fig. 3）, its signal is about non-reduction treatment
30 times of N-acetyl-L-cysteine-gold nano cluster.
Embodiment 4
Electrochemical reduction is carried out using three-electrode system, is with N-acetyl-L-cysteine-gold nano cluster modified glassy carbon electrode
Working electrode, platinum electrode is that, to electrode, Ag/AgCl is reference electrode, and above-mentioned electrode is inserted into 0.1 mol/L pH's 7.4
In PBS, constant potential reduction is carried out, reduction potential is -2.0 V, and the recovery time is 5 minutes, obtains gold nano group
Aggregate probe modified glassy carbon electrode.The gold nano cluster probe modification glass-carbon electrode insertion that will be prepared contains 0.1 mol/L persulfuric acid
In the PBS of the 0.1 M pH 7.4 of potassium and 0.1 mol/L KCl.Using step pulse method, initial potential is 0
V, the burst length is 10 s, and termination current potential is -2 V, and the burst length is 1 s.Photomultiplier high pressure is set to 700 V, continuously
24 sections of scanning, records electrochemiluminescence signal（See Fig. 4）, its electrochemiluminescence signal keep it is constant.
Embodiment 5
Electrochemical reduction is carried out using three-electrode system, is with N-acetyl-L-cysteine-gold nano cluster modified glassy carbon electrode
Working electrode, platinum electrode is that, to electrode, Ag/AgCl is reference electrode, and above-mentioned electrode is inserted into the phosphorus of 0.1 mol/L pH 7.4
In hydrochlorate cushioning liquid, constant potential reduction is carried out, reduction potential is respectively -0.2V, -0.5 V, -0.8 V, -1.0 V, -1.2
V, -1.5 V, -1.7 V, -1.8 V and -2.0 V, obtain the gold nano cluster probe modification glass-carbon electrode of different reducing degrees.
The gold nano cluster probe modification to reduction treatment under the conditions of above-mentioned different reduction potentials carries out X in removable glassy carbon electrode surface again
X-ray photoelectron spectroscopy X detection, obtains Au (0) content.As shown in figure 5, Au (0) contents increase with reduction potential reduction, also
When former current potential is -1.5 V, close to 100%, it is zeroth order Au to show that+1 valency Au is completely reduced to Au (0) content.
Embodiment 6
Electrochemical reduction is carried out using three-electrode system, is with N-acetyl-L-cysteine-gold nano cluster modified glassy carbon electrode
Working electrode, platinum electrode is that, to electrode, Ag/AgCl is reference electrode, and above-mentioned electrode is inserted into the phosphate of 0.1 M pH 7.4
In cushioning liquid, carry out constant potential reduction, reduction potential be respectively -0.2 V, -0.5 V, -0.8 V, -1.0 V, -1.2 V, -
1.5 V, -1.7 V, -1.8 V and -2.0 V, obtain the gold nano cluster probe modification glass-carbon electrode of different reducing degrees.Will system
The insertion of standby reduction gold nano cluster probe modification glass-carbon electrode is containing 0.1 mol/L potassium peroxydisulfates and 0.1 mol/L KCl
In the PBSs of 0.1 mol/L pH 7.4.Using step pulse method, initial potential is 0 V, and the burst length is 10
S, termination current potential is -2 V, and the burst length is 1 s.Photomultiplier high pressure is set to 700 V, and different reduction potentials are recorded respectively
The electrochemiluminescence signal of the gold nano cluster modified electrode for the treatment of.As shown in fig. 6, above-mentioned golden sodium rice cluster probe modification electricity
Pole electrochemiluminescence signal intensity is directly proportional to reduction potential, and reduction potential reaches maximum when being -1.5 V, and tends towards stability.
Meanwhile, x-ray photoelectron power spectrum is carried out to the gold nano cluster probe that reduction treatment under the conditions of above-mentioned different reduction potentials is obtained
（XPS）Test, obtains the content of corresponding Au (0).As shown in fig. 7, electrochemical luminescence intensity and Au (0) contents are into good linear
Relation.
Embodiment 7
Electrochemical reduction is carried out using three-electrode system, is with N-acetyl-L-cysteine-gold nano cluster modified glassy carbon electrode
Working electrode, platinum electrode is that, to electrode, Ag/AgCl is reference electrode, and above-mentioned electrode is inserted into the phosphate of 0.1 M pH 7.4
In cushioning liquid, constant potential reduction is carried out, reduction potential is -2.0 V, and the recovery time is 5 minutes, obtains reducing gold nano cluster
Probe modification glass-carbon electrode.The gold nano cluster probe modification glass-carbon electrode insertion that will be prepared contains 0.1 mol/L potassium peroxydisulfates
In the PBSs of 0.1 mol/L pH 7.4 of 0.1 mol/L KCl.Using cyclic voltammetry, apply 0 V ~-
The linear ramp of 2.0 V, sweep speed is 0.2 V/s, and photomultiplier high pressure is set to 700 V, detects working electrode
The electrochemiluminescence signal that surface produces（I）, the corresponding electricity that it is produced is Q f .In addition, by the glass-carbon electrode of the mm of diameter 3
With 1.0 μm, 0.3 μm and 0.05 μm of Al2O3Powder is polished successively, polishing, to smooth mirror surface, then is sequentially placed into HNO3Solution
（Concentrated nitric acid is 1 with water volume ratio:1）, absolute ethyl alcohol, ultrasonic cleaning 3 minutes, N in deionized water2Drying.Using three electrode bodies
System, with bare glassy carbon electrode as working electrode, platinum electrode is that, to electrode, Ag/AgCl is reference electrode, and bare glassy carbon electrode is inserted
Contain 1.0 mmol/L [Ru (bpy)3]2+In the acetonitrile solution of 0.1 mol/L tetrabutylammonium perchlorates, -1.0 V of applying ~
The linear ramp of -1.8 V, sweep speed is 0.2 V/s, and photomultiplier high pressure is set to 700 V, detects working electrode
The electrochemiluminescence signal that surface produces（I °）The corresponding electricity that it is produced is Q° f .By formulaΦ ECL =Φ ° ECL (IQ° f / I ° Q f )
It is calculated the electrochemical luminescence efficiency of the gold nano cluster probe of electrochemical reducing preparationΦ ECL It is 4.11%.
Exemplary embodiments of the invention are the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification made within god and principle, equivalent and improvement etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that using permanent electricity
Position reducing process to gold nano cluster material reduce and obtains gold nano cluster probe, and reduction potential is -0.2 V of V ~ -2.0, gold
Nanocluster probe has good electrochemical luminescence performance.
2. electrochemical reducing according to claim 1 prepares high quantum production rate electrochemical luminescence gold nano cluster probe,
It is characterized in that the gold nano cluster material is functional modification gold nano cluster, described functional modification gold nano cluster is adopted
With N- acetylations-Cys-gold nano cluster, glutathione-gold nano cluster or bovine serum albumin(BSA)-gold nano group
Cluster.
3. electrochemical reducing according to claim 1 prepares high quantum production rate electrochemical luminescence gold nano cluster probe,
It is characterized in that by gold nano cluster probe modification on glass-carbon electrode, and as working electrode, with potassium peroxydisulfate as anti-altogether
Agent is answered, electrochemical luminescence test is carried out, electrochemical luminescence signals can be produced.
4. electrochemical reducing according to claim 2 prepares high quantum production rate electrochemical luminescence gold nano cluster probe,
It is characterized in that the synthesis step of described N-acetyl-L-cysteine-gold nano cluster is as follows：It is 0.1 ~ 0.8 mol/ by concentration
The NaOH of L and concentration be 0.01 ~ 0.1 g/L chlorauric acid solutions be added to N- acetyl that concentration is 0.02 ~ 0.18 mol/L-
Be placed in 20 ~ 70 DEG C of water bath with thermostatic control isothermal reactions 0.1 ~ 3.5 hour in Cys solution, after mixing, question response terminate after thoroughly
Analysis purification process, obtains N-acetyl-L-cysteine-gold nano cluster aqueous solution, and N- acetyl-L- half is can obtain after freeze-drying
Cystine-gold nano cluster material powder, N-acetyl-L-cysteine-gold nano cluster aqueous solution carries out spectrofluorimetry,
Its maximum excitation wavelength and launch wavelength are respectively 355 nm and 650 nm.
5. electrochemical reducing according to claim 3 prepares high quantum production rate electrochemical luminescence gold nano cluster probe,
It is characterized in that what electrochemical luminescence signals were gathered by following methods：By glass-carbon electrode Al2O3Powder is polished to smooth mirror surface, then
It is sequentially placed into HNO3The aqueous solution, absolute ethyl alcohol is cleaned by ultrasonic, N in deionized water2Drying；By gold nano cluster probe modification at place
The glassy carbon electrode surface managed, obtains gold nano cluster probe modification glass-carbon electrode；Tested using three-electrode system, with gold
Nanocluster probe modification glass-carbon electrode is working electrode, and platinum electrode is that, to electrode, Ag/AgCl is reference electrode, is buffered molten
Liquid is phosphate buffer or Tris-HCl cushioning liquid, and electrolyte used is KCl or KNO3；The insertion of above-mentioned three electrode is contained
In the cushioning liquid of potassium peroxydisulfate coreagent, apply certain voltage, working electrode surface produces electrochemical luminescence radiation.
6. electrochemical reducing according to claim 5 prepares high quantum production rate electrochemical luminescence gold nano cluster probe,
It is characterized in that continuous electrochemical scans more than 24 sections electrochemical luminescence signals keeps constant.
7. electrochemical reducing according to claim 5 prepares high quantum production rate electrochemical luminescence gold nano cluster probe,
It is characterized in that electrochemical luminescence signals are strong and weak related to the reduction potential that electrochemical luminescence gold nano cluster probe used is prepared.
8. electrochemical reducing according to claim 5 prepares high quantum production rate electrochemical luminescence gold nano cluster probe,
It is characterized in that electrochemical luminescence signals are strong and weak linear with the ratio of Au (0) in electrochemical luminescence gold nano cluster probe.
9. electrochemical reducing prepares the spy of high quantum production rate electrochemical luminescence gold nano cluster according to claim 1 or 5
Pin, it is characterized in that being reduced to gold nano cluster material using constant potential reducing process, reduction potential is -2.0 V, is obtained
Electrochemical luminescence gold nano cluster probe relative electrochemical luminous efficiency be 4.11%.
10. a kind of preparation method of high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that with gold nano cluster
Material modified glassy carbon electrode is working electrode, and platinum electrode is that, to electrode, Ag/AgCl is reference electrode, molten in phosphate-buffered
In liquid apply -0.2 V voltages of V ~ -2.0 gold nano cluster material is carried out constant potential reduction obtain.
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| CN108802139A (en) * | 2018-08-08 | 2018-11-13 | 福建医科大学 | A kind of electrogenerated chemiluminescence method of detection glutathione |
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