CN106872546B - Electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe - Google Patents
Electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe Download PDFInfo
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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 to carry out reduction treatment using functionalization gold nano cluster material as presoma using electrochemical process and obtain.Above-mentioned electrogenerated chemiluminescence gold nano cluster probe modification on the electrode, using over cure acid ion as coreagent, has good electrochemical luminescence performance.The present invention has the characteristics that preparation method is simple, reaction condition is mild, favorable reproducibility, probe electrochemiluminescence signal is strong and quantum yield is high.With the rapid development of Electrochemiluminescsensor sensor technology, it is contemplated that the probe will have greater significance in fields such as chemistry, biology, 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 systems
Preparation Method belongs to field of nanometer technology.
Background technique
In recent years, semiconductor nanocrystal or quantum dot are as a kind of new electrochemical luminescence nano luminous body, due to it
The advantages that stability is good, anti-light bleaching power is 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 it quickly grows.However the defects of strong toxicity and non-molecule power rate fluorescence intermittency, is in tracking and imaging especially organism
Using etc. researchs bring difficulty, therefore the marker of high sensitivity, good biocompatibility is selected to examine for bioanalysis and medicine
It surveys extremely urgent.
Gold nano cluster has small size, nontoxic, good water solubility, special photoelectric property etc. as novel nano illuminator
Feature, oneself is widely applied in fields 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, are based on gold nano
The electrogenerated chemiluminescence sensing Study of An of cluster is also considerably less.Therefore, there are strong electrochemical luminescence signals and high quantum to produce for preparation
The electrogenerated chemiluminescence gold nano cluster probe of rate is of great significance 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 simple process, reaction condition be mild, favorable reproducibility, and prepared gold nano cluster probe electrochemiluminescence signal is strong and steady
It is fixed, and quantum yield is high.
Summary of the invention
The purpose of the present invention is to provide a kind of electrochemical reducings to prepare high quantum production rate electrochemical luminescence gold nano group
Aggregate probe.
To achieve the goals above, the invention adopts the following technical scheme:
Electrochemical reducing of the present invention prepares high quantum production rate electrochemical luminescence gold nano cluster probe, feature
It is to be restored to obtain gold nano cluster probe to gold nano cluster material using constant potential reduction method, reduction potential is -0.2 V
~ -2.0 V, gold nano cluster probe have good electrochemical luminescence performance.
The gold nano cluster material is functional modification gold nano cluster, and the functional modification gold nano cluster is adopted
With N- acetylation-L-cysteine-gold nano cluster, glutathione-gold nano cluster or bovine serum albumin(BSA)-gold nano group
Cluster.
The electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that by golden
Nanocluster probe modification, using potassium peroxydisulfate as coreagent, carries out electrification on glass-carbon electrode, and as working electrode
The test that shines is learned, electrochemical luminescence signals can be generated.
N-acetyl-L-cysteine-gold nano cluster synthesis step is as follows: being 0.1 ~ 0.8 mol/ by concentration
The sodium hydroxide and concentration of L are the N- acetyl-that 0.01 ~ 0.1 g/L chlorauric acid solution is added to that concentration is 0.02 ~ 0.18 mol/L
In L-cysteine solution, mixing is placed on 20 ~ 70 DEG C of water bath with thermostatic control isothermal reactions 0.1 ~ 3.5 hour, to saturating after reaction
Purification process is analysed, N-acetyl-L-cysteine-gold nano cluster aqueous solution is obtained, N- acetyl-L- half can be obtained after freeze-drying
Cystine-gold nano cluster material powder, N-acetyl-L-cysteine-gold nano cluster aqueous solution carry out spectrofluorimetry,
Its maximum excitation wavelength and launch wavelength are respectively 355 nm and 650 nm.
The electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that electrochemical
Learn what luminous signal was acquired by following methods: by glass-carbon electrode Al2O3Powder is polished to smooth mirror surface, then is sequentially placed into HNO3
Aqueous solution, dehydrated alcohol are cleaned by ultrasonic in deionized water, N2Drying；By gold nano cluster probe modification in the glass carbon handled well
Electrode surface obtains gold nano cluster probe modification glass-carbon electrode；It is tested using three-electrode system, is visited with gold nano cluster
Needle modified glassy carbon electrode is working electrode, and platinum electrode is to electrode, and Ag/AgCl is reference electrode, and buffer solution is phosphate
Buffer or Tris-HCl buffer solution, electrolyte used are KCl or KNO3；Above-mentioned three electrode is inserted into and is total to containing potassium peroxydisulfate
In the buffer solution of reactant, apply certain voltage, working electrode surface generates electrochemical luminescence radiation.
The electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that continuously
24 sections of Electrochemical Scanning or more electrochemical luminescence signals remain unchanged.
The electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that electrochemical
It is related to reduction potential used in electrochemical luminescence gold nano cluster probe is prepared to learn luminous signal power.
The electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that electrochemical
The ratio for learning Au (0) in luminous signal power and electrochemical luminescence gold nano cluster probe is linear.
The electrochemical reducing prepares high quantum production rate electrochemical luminescence gold nano cluster probe, it is characterized in that using
Constant potential reduction method is restored to obtain to gold nano cluster material, and reduction potential is -2.0 V, obtained electrochemical luminescence gold
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 to electrode, and Ag/AgCl is reference electrode, in phosphoric acid
Apply -0.2 V of V ~ -2.0 voltage in salt buffer solution gold nano cluster material progress constant potential is restored to obtain.
Specifically, the invention adopts the following technical scheme:
(1) N-acetyl-L-cysteine-gold nano cluster preparation
N-acetyl-L-cysteine-gold nano cluster synthesis step is as follows: the hydrogen-oxygen for being 0.1 ~ 0.8 mol/L by concentration
Change sodium and concentration is half Guang of N- acetyl-L- that 0.01 ~ 0.1 g/L chlorauric acid solution is added to that concentration is 0.02 ~ 0.18 mol/L
In propylhomoserin solution, mixing is placed on 20 ~ 70 DEG C of water bath with thermostatic control isothermal reactions 0 ~ 3.5 hour.At dialysis purification after reaction
Reason, obtains N-acetyl-L-cysteine-gold nano cluster aqueous solution, N-acetyl-L-cysteine-can be obtained after freeze-drying
Gold nano cluster material powder.
(2) preparation of gold nano cluster modified electrode
By glass-carbon electrode with 1.0 μm, 0.3 μm and 0.05 μm of Al2O3Powder successively polishes, polishing, until smooth mirror surface,
It is sequentially placed into HNO again3Solution (1:1), dehydrated alcohol are cleaned by ultrasonic 3 minutes in deionized water, N2Drying.Take 5 μ L N- acetyl-
L-cysteine-gold nano cluster aqueous solution is added dropwise in the glassy carbon electrode surface handled well, and drying at room temperature is to get N- acetyl-L-
Cysteine-gold nano cluster modified glassy carbon electrode.
(3) electrochemical reduction handles gold nano cluster
It is restored using three-electrode system, using N-acetyl-L-cysteine-gold nano cluster modified glassy carbon electrode as work
Make electrode, platinum electrode is to electrode, and Ag/AgCl is reference electrode, and above-mentioned electrode is inserted into the phosphorus of 0.1 mol/L pH 7.4
In hydrochlorate buffer solution, apply different negative potential voltages (within the scope of -0.2 V of V ~ -2), carries out constant potential reduction treatment, obtain
To electrochemical luminescence gold nano cluster probe.
(4) generation and detection of gold nano cluster probe electrochemiluminescence signal
It is tested using three-electrode system, using gold nano cluster or gold nano cluster probe modification glass-carbon electrode as work
Electrode, platinum electrode are to electrode, and Ag/AgCl is reference electrode, and above-mentioned electrode is inserted into the buffer solution 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.
Photomultiplier tube high pressure is set as the V of 600 V ~ 800, and the electrochemiluminescence signal that detection working electrode surface generates uses
Its electrochemiluminescence signal of the gold nano cluster probe of electrochemical reducing preparation significantly increases.
The invention has the advantages that
(1) it is high to carry out reduction preparation using electrochemical method using functional modification gold nano cluster as presoma by the present invention
Performance electrochemical luminescence gold nano cluster probe, this method have environmentally protective, easy to operate, favorable reproducibility of preparation method etc. excellent
Point.
(2) the obtained electrochemical luminescence gold nano cluster probe luminous intensity of the present invention is big, and electrochemical luminescence quantum produces
Rate is high, and good biocompatibility has a good application prospect in Electrochemiluminescsensor sensor part and field of biomedicine.
Detailed description of the invention
Fig. 1 is N-acetyl-L-cysteine-gold nano cluster fluorescence spectra.
Fig. 2 is N-acetyl-L-cysteine-gold nano cluster modified glassy carbon electrode electrogenerated chemiluminescence-time graph
Figure.
Fig. 3 is electrogenerated chemiluminescence-time of the gold nano cluster probe modification glass-carbon electrode of electrochemical reducing preparation
Curve graph.
Fig. 4 is gold nano cluster probe modification glass-carbon electrode 24 sections of resulting electricity of continuous scanning of electrochemical reducing preparation
Chemiluminescence intensity figure.
Fig. 5 prepares current potential to the influence diagram of Au (0) ratio in gold nano cluster probe for gold nano cluster probe.
Fig. 6 prepares current potential to the influence diagram of 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 in the following with reference to the drawings and specific embodiments, and the present invention is not limited thereto.
Embodiment 1
It is 0.5 that 0.6 mL concentration is added into the N-acetyl-L-cysteine solution that 4 mL concentration are 0.08 mol/L
The sodium hydroxide of mol/L and 0.4 mL concentration are 20 mg/mL chlorauric acid solutions, and mixing, which is placed in 37 DEG C of thermostatic water baths, to be incubated for
3 hours.Reaction solution after reaction carries out dialysis purification processing with the bag filter that retention molecule is 3500, obtains N- acetyl-
L-cysteine-gold nano cluster aqueous solution obtains N-acetyl-L-cysteine-gold nano cluster powder after freeze-drying.It takes
Above-mentioned N-acetyl-L-cysteine-gold nano cluster aqueous solution carries out spectrofluorimetry, can obtain maximum excitation wavelength and transmitting
Wavelength is respectively that 355 nm and 650 nm(are shown in Fig. 1).
Embodiment 2
The glass-carbon electrode of 3 mm of diameter is successively used to 1.0 μm, 0.3 μm and 0.05 μm of Al2O3Powder is polished to smooth
Mirror surface, then it is sequentially placed into HNO3Solution (concentrated nitric acid and water volume ratio be 1:1), dehydrated alcohol are cleaned by ultrasonic 3 points 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 phosphate buffer solution of the 0.1 mol/L pH 7.4 of mol/L potassium peroxydisulfate and 0.1 mol/L KCl.Using step pulse
Method, initial potential are 0 V, and the burst length is 10 s, and termination current potential is -2 V, and the burst length is 1 s.Photomultiplier tube high pressure is set
Be set to 700 V, the electrochemiluminescence signal that detection working electrode surface generates, obtain weaker electrochemical luminescence signals (see
Fig. 2).
Embodiment 3
Electrochemical reduction is carried out using three-electrode system, with N-acetyl-L-cysteine-gold nano cluster modification glass carbon electricity
Extremely working electrode, platinum electrode are to electrode, and Ag/AgCl is reference electrode, and above-mentioned electrode is inserted into 0.1 mol/L pH
In 7.4 phosphate buffer solution, constant potential reduction is carried out, reduction potential is -2.0 V, and the recovery time is 5 minutes, is gone back
Former gold nano cluster probe modification glass-carbon electrode.The reduction gold nano cluster probe modification glass-carbon electrode insertion of preparation is contained
In the phosphate buffer solution of the 0.1 mol/L pH 7.4 of 0.1 mol/L potassium peroxydisulfate and 0.1 mol/L KCl.Using step
Impulse method, initial potential are 0 V, and the burst length is 10 s, and termination current potential is -2 V, and the burst length is 1 s.Photomultiplier tube is high
Pressure is set as 700 V, the electrochemiluminescence signal (see figure 3) that detection working electrode surface generates, and signal does not restore about
30 times of N-acetyl-L-cysteine-gold nano cluster of processing.
Embodiment 4
Electrochemical reduction is carried out using three-electrode system, with N-acetyl-L-cysteine-gold nano cluster modification glass carbon electricity
Extremely working electrode, platinum electrode are to electrode, and Ag/AgCl is reference electrode, and above-mentioned electrode is inserted into 0.1 mol/L pH
In 7.4 phosphate buffer solution, constant potential reduction is carried out, reduction potential is -2.0 V, and the recovery time is 5 minutes, obtains gold
Nanocluster probe modification glass-carbon electrode.The gold nano cluster probe modification glass-carbon electrode insertion of preparation is contained into 0.1 mol/L
In the phosphate buffer solution of the 0.1 M pH 7.4 of potassium peroxydisulfate and 0.1 mol/L KCl.Using step pulse method, initial electricity
Position 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 tube high pressure is set as 700
V, records electrochemiluminescence signal (see figure 4) by 24 sections of continuous scanning, and electrochemiluminescence signal remains unchanged.
Embodiment 5
Electrochemical reduction is carried out using three-electrode system, with N-acetyl-L-cysteine-gold nano cluster modification glass carbon electricity
Extremely working electrode, platinum electrode are to electrode, and Ag/AgCl is reference electrode, and above-mentioned electrode is inserted into 0.1 mol/L pH
In 7.4 phosphate buffer solutions, carry out constant potential reduction, reduction potential be 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 electricity of different reducing degrees
Pole.Again to the gold nano cluster probe modification of reduction treatment under the conditions of above-mentioned different reduction potentials removable glassy carbon electrode surface into
The detection of row x-ray photoelectron spectroscopy, obtains Au (0) content.As shown in figure 5, Au (0) content increases as reduction potential reduces
Greatly, when reduction potential is -1.5 V, Au (0) content shows that+1 valence Au is completely reduced as zeroth order Au close to 100%.
Embodiment 6
Electrochemical reduction is carried out using three-electrode system, with N-acetyl-L-cysteine-gold nano cluster modification glass carbon electricity
Extremely working electrode, platinum electrode are to electrode, and Ag/AgCl is reference electrode, and above-mentioned electrode is inserted into 0.1 M pH, 7.4 phosphorus
In hydrochlorate buffer solution, constant potential reduction is carried out, reduction potential is 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.
The reduction gold nano cluster probe modification glass-carbon electrode insertion of preparation is contained into 0.1 mol/L potassium peroxydisulfate and 0.1 mol/L
In 0.1 mol/L pH, 7.4 phosphate buffer solution of KCl.Using step pulse method, initial potential is 0 V, burst length
For 10 s, termination current potential is -2 V, and the burst length is 1 s.Photomultiplier tube high pressure is set as 700 V, and record is different also respectively
The electrochemiluminescence signal of the gold nano cluster modified electrode of former current potential processing.As shown in fig. 6, above-mentioned gold sodium rice cluster probe
Modified electrode electrochemiluminescence signal intensity is directly proportional to reduction potential, and reduction potential reaches maximum when being -1.5 V, and becomes
In stabilization.Meanwhile the gold nano cluster probe obtained to reduction treatment under the conditions of above-mentioned different reduction potentials carries out X-ray photoelectricity
Sub- power spectrum (XPS) test, obtains the content of corresponding Au (0).As shown in fig. 7, electrochemical luminescence intensity is with Au (0) content at good
Linear relationship.
Embodiment 7
Electrochemical reduction is carried out using three-electrode system, with N-acetyl-L-cysteine-gold nano cluster modification glass carbon electricity
Extremely working electrode, platinum electrode are to electrode, and Ag/AgCl is reference electrode, and above-mentioned electrode is inserted into 0.1 M pH, 7.4 phosphorus
In hydrochlorate buffer solution, constant potential reduction is carried out, reduction potential is -2.0 V, and the recovery time is 5 minutes, obtains reduction gold nano
Cluster probe modification glass-carbon electrode.The gold nano cluster probe modification glass-carbon electrode insertion of preparation is contained into 0.1 mol/L over cure
In 0.1 mol/L pH, 7.4 phosphate buffer solution of sour potassium and 0.1 mol/L KCl.Using cyclic voltammetry, apply 0 V
The linear ramp of ~ -2.0 V, scanning speed are 0.2 V/s, and photomultiplier tube high pressure is set as 700 V, detection work electricity
Pole surface generate electrochemiluminescence signal (I), the corresponding electricity generated is Q f .In addition, by the glass carbon electricity of 3 mm of diameter
1.0 μm, 0.3 μm and 0.05 μm of the Al in pole2O3Powder successively polishes, polishing, until smooth mirror surface, then it is sequentially placed into HNO3It is molten
Liquid (concentrated nitric acid and water volume ratio be 1:1), dehydrated alcohol are cleaned by ultrasonic 3 minutes in deionized water, N2Drying.Using three electrodes
System, using bare glassy carbon electrode as working electrode, platinum electrode is to electrode, and Ag/AgCl is reference electrode, and bare glassy carbon electrode is inserted
Enter containing 1.0 mmol/L [Ru (bpy)3]2+In the acetonitrile solution of 0.1 mol/L tetrabutylammonium perchlorate, apply -1.0 V
The linear ramp of ~ -1.8 V, scanning speed are 0.2 V/s, and photomultiplier tube high pressure is set as 700 V, detection work electricity
Pole surface generate electrochemiluminescence signal (I °) its generate corresponding electricity be Q° f .By formulaΦ ECL =Φ ° ECL (IQ° f / I ° Q f ) the electrochemical luminescence efficiency of gold nano cluster probe prepared by electrochemical reducing is calculatedΦ ECL It is 4.11%.
The foregoing is merely exemplary embodiments of the invention, are not intended to limit the invention, all in essence of the invention
Made any modification within mind and principle, equivalent replacement and improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
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 reduction method restores gold nano cluster material to obtain 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, the functional modification gold nano cluster is adopted
With N- acetylation-L-cysteine-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, it is anti-altogether with potassium peroxydisulfate
Agent is answered, electrochemical luminescence test is carried out, electrochemical luminescence signals can be generated.
4. electrochemical reducing according to claim 2 prepares high quantum production rate electrochemical luminescence gold nano cluster probe,
It is characterized in that N-acetyl-L-cysteine-gold nano cluster synthesis step is as follows: being 0.1 ~ 0.8 mol/ by concentration
The sodium hydroxide and concentration of L are the N- acetyl-that 0.01 ~ 0.1 g/L chlorauric acid solution is added to that concentration is 0.02 ~ 0.18 mol/L
In L-cysteine solution, mixing is placed on 20 ~ 70 DEG C of water bath with thermostatic control isothermal reactions 0.1 ~ 3.5 hour, to saturating after reaction
Purification process is analysed, N-acetyl-L-cysteine-gold nano cluster aqueous solution is obtained, N- acetyl-L- half can be obtained after freeze-drying
Cystine-gold nano cluster material powder, N-acetyl-L-cysteine-gold nano cluster aqueous solution carry 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 electrochemical luminescence signals were acquired by following methods: by glass-carbon electrode Al2O3Powder is polished to smooth mirror surface, then
It is sequentially placed into HNO3Aqueous solution, dehydrated alcohol are cleaned by ultrasonic in deionized water, N2Drying；Gold nano cluster probe modification is being located
The glassy carbon electrode surface managed obtains gold nano cluster probe modification glass-carbon electrode；It is tested using three-electrode system, with gold
Nanocluster probe modification glass-carbon electrode is working electrode, and platinum electrode is to electrode, and Ag/AgCl is reference electrode, is buffered molten
Liquid is phosphate buffer or Tris-HCl buffer solution, and electrolyte used is KCl or KNO3；The insertion of above-mentioned three electrode is contained
In the buffer solution of potassium peroxydisulfate coreagent, apply certain voltage, working electrode surface generates 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 electrochemical luminescence signals power is related to reduction potential used in electrochemical luminescence gold nano cluster probe is prepared.
7. electrochemical reducing according to claim 5 prepares high quantum production rate electrochemical luminescence gold nano cluster probe,
It is characterized in that the ratio of Au (0) is linear in electrochemical luminescence signals power and electrochemical luminescence gold nano cluster probe.
8. electrochemical reducing prepares the spy of high quantum production rate electrochemical luminescence gold nano cluster according to claim 1 or 5
Needle, it is characterized in that being restored to obtain to gold nano cluster material using constant potential reduction method, reduction potential is -2.0 V, is obtained
Electrochemical luminescence gold nano cluster probe relative electrochemical luminous efficiency be 4.11%.
9. 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
Material modified glassy carbon electrode is working electrode, and platinum electrode is to electrode, and Ag/AgCl is reference electrode, in phosphate buffer solution
- 0.2 V of V ~ -2.0 voltage of middle application carries out constant potential to gold nano cluster material and restores to obtain.
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| CN109142331A (en) * | 2018-08-08 | 2019-01-04 | 福建医科大学 | A kind of electrogenerated chemiluminescence method and its kit for carcinomebryonic antigen detection |
| CN108693172A (en) * | 2018-08-08 | 2018-10-23 | 福建医科大学 | Ascorbic acid electrogenerated chemiluminescence assay method |
| CN109142731A (en) * | 2018-08-08 | 2019-01-04 | 福建医科大学 | Human ovarian cancer antigen detection method and its kit |
| CN108872209A (en) * | 2018-08-08 | 2018-11-23 | 福建医科大学 | Alkaline phosphatase assay method based on nanogold cluster electrogenerated chemiluminescence probe |
| CN112461818B (en) * | 2020-11-13 | 2022-06-24 | 武汉纺织大学 | Gold nanocluster with multiple optical signal channels |
| CN112461819B (en) * | 2020-11-13 | 2022-06-21 | 武汉纺织大学 | Application of gold nanocluster with multiple optical signal channels |
| CN114384053B (en) * | 2022-01-13 | 2023-09-08 | 山东大学 | Flash and glow adjustable near infrared chemiluminescence system with nano gold clusters as luminophors |
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| CN104237185B (en) * | 2014-09-13 | 2017-02-22 | 福建医科大学 | PH value measurement method based on N-acetyl-L-cysteine-gold nanocluster |
| CN104330392B (en) * | 2014-11-04 | 2016-11-02 | 福建医科大学 | Hydrogen peroxide enzymatic fluorimetric assay based on gold nano cluster probe |
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