CN107290311A - A kind of fluorescent optical sensor " opening pass " detects ascorbic method - Google Patents
A kind of fluorescent optical sensor " opening pass " detects ascorbic method Download PDFInfo
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- CN107290311A CN107290311A CN201710430539.4A CN201710430539A CN107290311A CN 107290311 A CN107290311 A CN 107290311A CN 201710430539 A CN201710430539 A CN 201710430539A CN 107290311 A CN107290311 A CN 107290311A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention belongs to technical field of chemical detection, disclosing a kind of fluorescent optical sensor based on graphene quantum dot/manganese dioxide nano-plates is used for the ascorbic method of " opening pass " detection.The present invention is by the use of graphene quantum dot as fluorescence probe, and manganese dioxide nano-plates form a kind of graphene quantum dot/manganese dioxide nano-plates Quenching System as fluorescence quencher.Can occur redox mechanism with manganese dioxide nano-plates using vitamin C, promote graphene quantum dot fluorescence to recover, obtain the linear work curve of vitamin C concentration and system fluorescence intensity change, coefficient correlation is 0.996.The inventive method can be used for the vitamin C of analysis detection low concentration, have higher selectivity to vitamin C.Other this fluorescent optical sensor need not be expensive experimental facilities and complicated sample handling processes, with preparation method is simple and detection quickly and easily advantage.
Description
Technical field
The invention belongs to technical field of chemical detection graphene quantum dot/manganese dioxide nano-plates are based on there is provided one kind
Fluorescent optical sensor preparation method.
Background technology
Vitamin C was operated as the constituent of biological enzyme cofactor, reducing agent and neurotransmitter enzyme in the physiology of people
Journey plays key player.As essential amino acid, the vitamin C in human body can only be supplemented by diet.Life is tieed up simultaneously
Plain C is also a kind of antioxidant, is added in food, can practically extend the holding time of food.Therefore realization pair
Ascorbic effective analysis detection either still all has important actual meaning in medical diagnosis on disease in food security aspect
Justice.Traditional detection method has oxidimetric titration, AAS, chromatogram and Capillary Electrophoresis etc., and these methods have at operation
Reason process is cumbersome, the shortcomings of analysis time is long.Therefore a kind of sensitive quick, easy to operate and cost economy method of development is needed
To realize to ascorbic detection.
Fluorescence graphene quantum dot is a kind of zero dimensional nanometer materials of quantum size, and it, which inherits graphene, has many property
Matter, such as excellent optics, electronic property and big specific surface area, graphene quantum dot is also with the adjustable light of size dependence in addition
The advantages of photoluminescence, the photoluminescence stability of height, hypotoxicity and high biocompatibility, its preparation method is simple and low
It is with low cost, obtain extensive development in fields such as fluorescent optical sensor, cell imaging and insoluble drug releases.But ordinary circumstance
Under, single graphene quantum dot can not be realized to ascorbic analysis detection.
Manganese dioxide nano-plates have very high specific surface area, stability and excellent light absorpting ability, and it is in 201-
There is the absorption band of non-constant width at 600nm, be a kind of preferable graphene quantum dot fluorescence quenching.Other manganese dioxide nano
The material such as vitamin C of easy the being reduced property of piece is reduced into manganese ion, promotes the fluorescence of graphene quantum dot to recover.Based on so
Simple redox mechanism, which can build a kind of fluorescent optical sensor of unmarked " on/off " system, to be used to detect vitamin C.
The content of the invention
For problem above and technology, the invention provides one kind using based on graphene quantum dot/manganese dioxide nano
The fluorescent optical sensor " on/off " of piece detects ascorbic method, comprises the following steps：
(1) structure of graphene quantum dot/manganese dioxide nano-plates fluorescent quenching system：
After the manganese dioxide nano-plates solution mixing vibration of graphene quantum dot solution and various concentrations is shaken up, meter
The relation between mixed solution fluorescence intensity change and manganese dioxide concentration is calculated, it is determined that optimal quenching concentration.
(2) structure of graphene quantum dot/ascorbic linear relationship of manganese dioxide nano-plates fluoroscopic examination：
To certain volume than graphene quantum dot/manganese dioxide nano-plates solution and phosphate buffer solution in add not
With the vitamin c solution of concentration, after vibration shakes up, between survey calculation mixed solution fluorescence intensity change and vitamin C concentration
Relation, set up corresponding fluorescence and recover linear equation.
(3) graphene quantum dot/manganese dioxide nano-plates system is to ascorbic detection：
In containing ascorbic solution to be detected, a certain amount of graphene quantum dot/manganese dioxide nano-plates solution is added
And phosphate buffer solution, after vibration shakes up, measure its intensity level of its fluorescence and substitute into the linear equation of step (2) structure, from
And calculate and obtain ascorbic content.
In above-mentioned steps (1), the preparation method of described graphene quantum dot solution is：A certain amount of graphene oxide is complete
Full ultrasonic disperse prepares the graphene oxide solution that concentration is 1.0g/L, to 90.0mL graphene oxide solutions in water
Middle addition 1.0mL mass fractions are 28% ammonia spirit, and stir and evenly mix 10min, are then transferred to polytetrafluoroethylene (PTFE)
In reactor, 180 DEG C are heated to, the reaction time is 12h, reaction end is cooled to after room temperature, and obtained product is used into 0.22 μ
M mixed cellulose ester membrane is filtered, and obtained filtrate is transferred in 3500Da bag filter, is stirred in immersion deionized water
Dialysis 2 days, the fluorescence maximum excitation wavelength for finally obtaining graphene quantum dot solution is 324nm, and fluorescence maximum emission wavelength is
445nm。
In above-mentioned steps (1), described manganese dioxide nano-plates are layer structure, and its preparation method is：First will
14.0mL0.05mol/L neopelex solution, 1.5mL 0.1mol/L sulfuric acid solutions, 30.0mL ethanol and
220.0mL deionized waters are sufficiently mixed, and magnetic agitation is heated to 90 DEG C, then by 3.0mL 0.05mol/L potassium permanganate
Solution is by being added dropwise in the solution, and reaction 10min, which stops heating, simultaneously continues stirring, be cooled to after room temperature with a large amount of ethanol and go from
Sub- water cleaning removes unnecessary reactant, last 50 DEG C of drying of vacuum.
In above-mentioned steps (1), the preparation method of described manganese dioxide nano-plates dispersion liquid is：Manganese dioxide nano-plates are passed through
Ultrasonic disperse is in deionized water, and its concentration is 0-150.0 μ g/mL, and it has very broad at wavelength X=300-600nm
Absorption band, have characteristic absorption peak at ultraviolet wavelength λ=360nm.
In above-mentioned steps (1), in described graphene quantum dot and manganese dioxide nano-plates solution, both mixed volumes
Than for 1:3, duration of oscillation is 1-5min.
In above-mentioned steps (1), the optium concentration of described manganese dioxide nano-plates quenching graphene quantum dot is 100.0
μg/mL。
In above-mentioned steps (2), the concentration of described vitamin c solution is 0-175 μm of ol/L, its with graphene quantum dot/
Manganese dioxide nano-plates solution, the volume ratio of phosphate buffer solution are 5:4:16.
In above-mentioned steps (2), the concentration of described phosphate buffer solution is 0.01mol/L, pH between 5.5-8.5,
Optimal pH is 6.0, and solution mixing duration of oscillation is 3-5min.
In above-mentioned steps (2), described linear equation is Y=0.001566X+0.02494, R2=0.996, to vitamin
C detection is limited to 10.7 μm of ol/L.Wherein Y is graphene quantum dot and manganese dioxide nano-plates solution adds vitamin C and is not added with
The ratio of ascorbic fluorescence intensity, and X is ascorbic concentration, unit is μm ol/L.
In above-mentioned steps (3), described vitamin c solution and graphene quantum dot/manganese dioxide nano-plates solution, phosphoric acid
The volume ratio of salt buffer solution is 5:4:16.
In above-mentioned steps (3), the concentration of described phosphate buffer solution is 0.01mol/L, pH 5.5-8.5 it
Between, Optimal pH is 6.0, and solution mixing duration of oscillation is 3-5min, concretely 3min.
Compared with existing traditional sensing techniques, the graphene quantum dot/manganese dioxide that is based on prepared by the present invention is received
The fluorescent optical sensor of rice piece is used for " on/off " and detects that ascorbic method has advantages below：
(1) mechanism of redox reaction, graphene amount can be occurred with manganese dioxide nano-plates based on reducing agent vitamin C
Son point is combined into a kind of fluorescent optical sensor with " on/off " function with manganese dioxide nano-plates, has to vitamin C higher
Selectivity, can be used for the vitamin C of analysis detection low concentration.
(2) experimental facilities and complicated sample handling processes that this fluorescent optical sensor need not be expensive in addition, with system
Preparation Method is simple and detects quickly and easily advantage.
Brief description of the drawings：
The fluorescence excitation and emission spectrum for the graphene quantum dot that Fig. 1 synthesizes for the present invention.
The UV absorption visible spectrum for the manganese dioxide nano-plates that Fig. 2 synthesizes for the present invention.
Fig. 3 adds graphene quantum dot/manganese dioxide nano-plates for the vitamin C (0-175.00 μm of ol/L) of various concentrations
Fluorescence emission spectrum after system.
Fig. 4 is that graphene quantum dot/manganese dioxide nano-plates system detects ascorbic working curve.
Embodiment：
With reference to Figure of description and specific embodiment, the present invention is expanded on further, but protection scope of the present invention is simultaneously
Not limited to this.
Firstly the need of setting up working curve before implementation：Eight centrifuge tubes are taken, 100.0 μ L stones are all added thereto respectively
Black alkene quantum dot solution, the μ g/mL manganese dioxide nano-plates solution of 300.0 μ L 100.0 and 16.0mL pH are 6.0 0.01mol/
L phosphate buffer solutions, mixed solution, vibration shakes up 3min, graphene quantum dot and manganese dioxide nano-plates is fully contacted.
Then 500.0 μ L deionized waters, 20.0 μm of ol/L, 50.0 μm of ol/L, 75.0 μm of ol/L, 100.0 μm of ol/L, 125.0 μm of ol/L,
150.0 μm of ol/L, 175.0 μm of ol/L are separately added into above-mentioned eight centrifuge tubes, after vibration stirring 3min, its fluorescence are surveyed respectively strong
Degree.Contrasted with blank, obtain the linear equation Y=0.001566X+ of fluorescence intensity change value and vitamin C concentration
0.02494, R2=0.996,10.7 μm of ol/L are limited to ascorbic detection.Wherein Y is graphene quantum dot and manganese dioxide
Nanometer sheet solution adds vitamin C and is not added with the ratio of ascorbic fluorescence intensity, and X is ascorbic concentration, and unit is μ
mol/L。
Embodiment 1
(1) by 100.0 μ L graphene quantum dots solution, the μ g/mL manganese dioxide nano-plates solution of 300.0 μ L 100.0 and
16.0mL pH are well mixed it to vibrate 1min after 6.0 phosphate buffer solution mixing.
(2) orange beverage bought from supermarket is pre-processed：By a certain amount of fruit juice 10000r/min rotating speed
Lower centrifugation 10min, takes supernatant with 0.22 μm of mixed cellulose ester membrane suction filtration, obtained fruit juice filtrate is diluted with deionized water
5 times.
(3) fruit juice made from taking 500.0 μ L processes (2) is added in the mixed solution in process (1), oscillation treatment
3min, makes the vitamin C in orange juice fully be reacted with manganese dioxide nano-plates.Its fluorescence intensity level is measured, linear equation Y is substituted into
It is 614.3 μm of ol/L that=0.001566X+0.02494, which is calculated and obtained ascorbic content in orange juice,.10.0 μm of ol/L are configured,
15.0 μm of ol/L, 20.0 μm of ol/L vitamin C standard liquid tests the rate of recovery using standard addition method, and the rate of being recycled is
97-106%；As a result show that the fluorescent optical sensor for preparing of the present invention has good stability and the degree of accuracy.
Embodiment 2
(1) by 100.0 μ L graphene quantum dots solution, the μ g/mL manganese dioxide nano-plates solution of 300.0 μ L 100.0 and
16.0mL pH are well mixed it to vibrate 1min after 6.0 phosphate buffer solution mixing.
(2) grape juice beverage bought from supermarket is pre-processed：By a certain amount of fruit juice turning in 10000r/min
The lower centrifugation 10min of speed, takes supernatant with 0.22 μm of mixed cellulose ester membrane suction filtration, obtained fruit juice filtrate is dilute with deionized water
Release 5 times.
(3) fruit juice made from taking 500.0 μ L processes (2) is added in the mixed solution in process (1), oscillation treatment
3min, makes the vitamin C in orange juice fully be reacted with manganese dioxide nano-plates.Its fluorescence intensity level is measured, linear equation Y is substituted into
It is 572.2 μm of ol/L that=0.001566X+0.02494, which is calculated and obtained ascorbic content in orange juice,.10.0 μm of ol/L are configured,
15.0 μm of ol/L, 20.0 μm of ol/L vitamin C standard liquid tests the rate of recovery using standard addition method, and the rate of being recycled is
101-105%；As a result show that the fluorescent optical sensor for preparing of the present invention has good stability and the degree of accuracy.
Embodiment 3
(1) by 100.0 μ L graphene quantum dots solution, the μ g/mL manganese dioxide nano-plates solution of 300.0 μ L 100.0 and
16.0mL pH are well mixed it to vibrate 1min after 6.0 phosphate buffer solution mixing.
(2) the peach juice beverage bought from supermarket is pre-processed：By a certain amount of fruit juice 10000r/min's
10min is centrifuged under rotating speed, supernatant is taken with 0.22 μm of mixed cellulose ester membrane suction filtration, obtained fruit juice filtrate deionized water
5 times of dilution.
(3) fruit juice made from taking 500.0 μ L processes (2) is added in the mixed solution in process (1), oscillation treatment
3min, makes the vitamin C in peach juice fully be reacted with manganese dioxide nano-plates.Its fluorescence intensity level is measured, is substituted into linear
It is 730.15 μm of ol/L that equation Y=0.001566X+0.02494, which is calculated and obtained ascorbic content in orange juice,.Configure 10.0 μ
Mol/L, 15.0 μm of ol/L, 20.0 μm of ol/L vitamin C standard liquid are tested the rate of recovery using standard addition method, returned
Yield is 103-112%；As a result show that the fluorescent optical sensor for preparing of the present invention has good stability and the degree of accuracy.
The fluorescence excitation and emission spectrum for the graphene quantum dot that Fig. 1 synthesizes for the present invention, are drawn by Fig. 1, and its maximum swashs
Hair wavelength is 324nm, and maximum emission wavelength is 445nm.
Moreover, under uviol lamp wavelength X=365nm irradiation, graphene quantum dot sends visible blue-fluorescence.
The UV absorption visible spectrum for the manganese dioxide nano-plates that Fig. 2 synthesizes for the present invention, is drawn, it is in wavelength X by Fig. 2
There is very broad absorption band at=300-600nm, have characteristic absorption peak at ultraviolet wavelength λ=360nm.
Fig. 3 adds graphene quantum dot/manganese dioxide nano-plates for the vitamin C (0-175.00 μm of ol/L) of various concentrations
Fluorescence emission spectrum after system, is drawn by Fig. 3, and with the increase of vitamin solution concentration, fluorescence intensity is in enhancing.
Claims (10)
1. a kind of fluorescent optical sensor " on/off " detects ascorbic method, it is characterised in that comprise the following steps：
(1) structure of graphene quantum dot/manganese dioxide nano-plates fluorescent quenching system：
After graphene quantum dot solution and manganese dioxide nano-plates solution mixing vibration are shaken up, survey calculation mixed solution fluorescence
Relation between Strength Changes and manganese dioxide concentration, it is determined that optimal quenching concentration；
(2) structure of graphene quantum dot/ascorbic linear relationship of manganese dioxide nano-plates fluoroscopic examination：
To certain volume than graphene quantum dot/manganese dioxide nano-plates solution and phosphate buffer solution in add vitamin
C solution, after vibration shakes up, the relation between survey calculation mixed solution fluorescence intensity change and vitamin C concentration sets up corresponding
Fluorescence recover linear equation；
(3) graphene quantum dot/manganese dioxide nano-plates system is to ascorbic detection：
In containing ascorbic solution to be detected, a certain amount of graphene quantum dot/manganese dioxide nano-plates solution and phosphorus are added
Hydrochlorate cushioning liquid, after vibration shakes up, measures its intensity level of its fluorescence and substitutes into the linear equation of step (2) structure, so as to count
Calculation obtains ascorbic content.
2. a kind of fluorescent optical sensor " on/off " according to claim 1 detects ascorbic method, it is characterised in that step
Suddenly (1), the preparation method of described graphene quantum dot solution is：By the complete ultrasonic disperse of a certain amount of graphene oxide in water
In, the graphene oxide solution that concentration is 1.0g/L is prepared, 1.0mL mass is added into 90.0mL graphene oxide solutions
Fraction is 28% ammonia spirit, and stirs and evenly mixs 10min, is then transferred in ptfe autoclave, is heated to
180 DEG C, the reaction time is 12h, and reaction end is cooled to after room temperature, and obtained product is used to 0.22 μm of mixed cellulose ester
Film is filtered, and obtained filtrate is transferred in 3500Da bag filter, stirring dialysis 2 days in immersion deionized water, finally
Fluorescence maximum excitation wavelength to graphene quantum dot solution is 324nm, and fluorescence maximum emission wavelength is 445nm.
3. a kind of fluorescent optical sensor " on/off " according to claim 1 detects ascorbic method, it is characterised in that step
Suddenly in (1), described manganese dioxide nano-plates are layer structure, and its preparation method is：First by 14.0mL 0.05mol/L 12
Alkyl benzene sulphonate sodium solution, 1.5mL 0.1mol/L sulfuric acid solutions, 30.0mL ethanol and 220.0mL deionized waters are sufficiently mixed,
Magnetic agitation is heated to 90 DEG C, then reacts 3.0mL 0.05mol/L liquor potassic permanganates by being added dropwise in the solution
10min stops heating and continuing stirring, is cooled to after room temperature and the unnecessary reactant of removing is cleaned with a large amount of ethanol and deionized water,
Last 50 DEG C of drying of vacuum.
4. a kind of fluorescent optical sensor " on/off " according to claim 1 detects ascorbic method, it is characterised in that step
Suddenly in (1), the preparation method of described manganese dioxide nano-plates dispersion liquid is：Manganese dioxide nano-plates through ultrasonic disperse in go from
In sub- water, concentration is 0-150.0 μ g/mL.
5. a kind of fluorescent optical sensor " on/off " according to claim 1 detects ascorbic method, it is characterised in that step
Suddenly in (1), in described graphene quantum dot and manganese dioxide nano-plates solution, both mixed volume ratios are 1:3, during vibration
Between be 1-5min；The optium concentration of described manganese dioxide nano-plates quenching graphene quantum dot is 100.0 μ g/mL.
6. a kind of fluorescent optical sensor " on/off " according to claim 1 detects ascorbic method, it is characterised in that step
Suddenly in (2), the concentration of described vitamin c solution is 0-175 μm of ol/L, itself and graphene quantum dot/manganese dioxide nano-plates
Solution, the volume ratio of phosphate buffer solution are 5:4:16.
7. a kind of fluorescent optical sensor " on/off " according to claim 1 detects ascorbic method, it is characterised in that step
Suddenly in (2), described linear equation is Y=0.001566X+0.02494, R2=0.996, ascorbic detection is limited to
10.7μmol/L；Wherein Y is the fluorescence that graphene quantum dot and manganese dioxide nano-plates solution are added before and after vitamin C
The change of intensity, and X is ascorbic concentration, unit is μm ol/L.
8. a kind of fluorescent optical sensor " on/off " according to claim 1 detects ascorbic method, it is characterised in that step
Suddenly in (3), described vitamin c solution and graphene quantum dot/manganese dioxide nano-plates solution, the body of phosphate buffer solution
Product is than being 5:4:16.
9. a kind of fluorescent optical sensor " on/off " according to claim 1 detects ascorbic method, it is characterised in that step
Suddenly in (2) and step (3), the concentration of described phosphate buffer solution is 0.01mol/L, and pH is between 5.5-8.5, solution
Mixing duration of oscillation is 3-5min.
10. a kind of fluorescent optical sensor " on/off " according to claim 9 detects ascorbic method, it is characterised in that
The pH of described phosphate buffer solution is 6.0.
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| CN108645826A (en) * | 2018-05-02 | 2018-10-12 | 天津科技大学 | A kind of new method of quick detection ascorbic acid |
| CN109490261A (en) * | 2018-09-26 | 2019-03-19 | 中山大学 | Double fluorescent detection probes of high-efficiency multiple superparamagnetism fluorine ion and preparation method thereof |
| CN109520980A (en) * | 2018-11-14 | 2019-03-26 | 大连工业大学 | Fluorescence/nuclear-magnetism double function probe detection food vitamins C method |
| CN109575918A (en) * | 2018-12-20 | 2019-04-05 | 大连工业大学 | The preparation method of time-resolved fluorescence probe for ascorbic acid detection |
| CN110501494A (en) * | 2019-07-16 | 2019-11-26 | 中国农业大学 | A kind of microorganism detection method based on manganese dioxide nano flower and fluorescent material |
| CN111678889A (en) * | 2020-07-13 | 2020-09-18 | 北京碳世纪科技有限公司 | Quantum dot and fluorescent molecule doped graphene biosensor for detecting trace viruses |
| CN116449026A (en) * | 2023-06-19 | 2023-07-18 | 成都信息工程大学 | Method for detecting cardiac troponin I based on manganese dioxide nano-sheet |
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Cited By (12)
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|---|---|---|---|---|
| CN108645826A (en) * | 2018-05-02 | 2018-10-12 | 天津科技大学 | A kind of new method of quick detection ascorbic acid |
| CN109490261A (en) * | 2018-09-26 | 2019-03-19 | 中山大学 | Double fluorescent detection probes of high-efficiency multiple superparamagnetism fluorine ion and preparation method thereof |
| CN109490261B (en) * | 2018-09-26 | 2021-12-24 | 中山大学 | Efficient porous superparamagnetic fluorine ion dual-fluorescence detection probe and preparation method thereof |
| CN109520980A (en) * | 2018-11-14 | 2019-03-26 | 大连工业大学 | Fluorescence/nuclear-magnetism double function probe detection food vitamins C method |
| CN109520980B (en) * | 2018-11-14 | 2021-07-06 | 大连工业大学 | Method for detecting vitamin C in food by fluorescent/nuclear magnetic dual-function probe |
| CN109575918A (en) * | 2018-12-20 | 2019-04-05 | 大连工业大学 | The preparation method of time-resolved fluorescence probe for ascorbic acid detection |
| CN109575918B (en) * | 2018-12-20 | 2021-10-26 | 大连工业大学 | Preparation method of time-resolved fluorescent probe for ascorbic acid detection |
| CN110501494A (en) * | 2019-07-16 | 2019-11-26 | 中国农业大学 | A kind of microorganism detection method based on manganese dioxide nano flower and fluorescent material |
| CN110501494B (en) * | 2019-07-16 | 2020-10-09 | 中国农业大学 | Microorganism detection method based on manganese dioxide nanoflowers and fluorescent materials |
| CN111678889A (en) * | 2020-07-13 | 2020-09-18 | 北京碳世纪科技有限公司 | Quantum dot and fluorescent molecule doped graphene biosensor for detecting trace viruses |
| CN111678889B (en) * | 2020-07-13 | 2023-05-02 | 北京碳世纪科技有限公司 | Quantum dot and fluorescent molecule doped graphene biosensor for detecting trace viruses |
| CN116449026A (en) * | 2023-06-19 | 2023-07-18 | 成都信息工程大学 | Method for detecting cardiac troponin I based on manganese dioxide nano-sheet |
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