CN104048957B - The glucose sensing approach of the class Peroxidative Characteristics based on graphene quantum dot - Google Patents
The glucose sensing approach of the class Peroxidative Characteristics based on graphene quantum dot Download PDFInfo
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Abstract
The invention discloses a kind of glucose sensing approach of the class Peroxidative Characteristics based on graphene quantum dot, belong to optical sensing technology field.Graphene quantum dot has the catalysis activity of class peroxidase, hydrogen peroxide can be catalyzed in the presence of hydrogen peroxide to reduce, colourless reduced form tetramethyl benzidine is oxidized to oxidized form tetramethyl benzidine simultaneously and aobvious blueness, ultraviolet absorption peak is produced at 652 nm.When oxygen is present, the glucose oxidase catalysis glycoxidative generation hydrogen peroxide of grape, recycles the class Peroxidative Characteristics catalysis hydrogen peroxide reduction of graphene quantum dot, and the reduced form tetramethyl benzidine in solution then occurs to aoxidize and develop the color.The concentration of glucose is bigger, and the blueness of solution is deeper, and UV absorption intensity is stronger, and quick, the sensitive and Visual retrieval of glucose can be realized accordingly.
Description
Technical field
The present invention relates to a kind of glucose sensing approach of the class Peroxidative Characteristics based on graphene quantum dot,
Belong to optical sensing technology field.
Background technology
Native enzyme is biocatalyst exist in vivo, effective.Due to they have it is very high biological single-minded
Property and catalysis activity, are applied to the fields such as medicine, biotechnology, chemical industry and environmental science.In these native enzymes, mistake
Oxide enzyme is widely used in the fields such as analyzing and diagnosing because various chemical reactions can be carried out with catalyzing hydrogen peroxide.It is peppery
Root peroxidase is a kind of most common peroxidase, is commonly used in the detection of hydrogen peroxide and glucose.But, native enzyme
Catalysis activity easily by the natural environments such as pH, temperature change influenceed.Additionally, the extraction of enzyme, purifying and carrying cost are also all
Compare high.Therefore, the bionical thing of peroxidase that is new, effective, can be used for practical application is studied significant.
Graphene quantum dot（GQD）It is a kind of graphene film of particle diameter less than 100 nm, with good optics and electronics
Characteristic, and scattered, fluorescence is strong, low toxicity, good biocompatibility.These properties make GQD be widely used in bio-imaging, biology
In sensing and photovoltaic device.But, the research on GQD at present is all based on the carboxyl or electric charge on its surface and designs,
Research about GQD catalysis activities is still less.
The content of the invention
Object of the present invention is to provide a kind of Portugal of the class Peroxidative Characteristics based on graphene quantum dot
Grape sugar detection method.
The present invention is achieved like this, by glucose oxidase（GOx）Mix with glucose solution, using GOx to Portugal
The catalytic reaction of grape sugar produces hydrogen peroxide（H2O2）；Add GQD and reduced form tetramethyl benzidine（TMB）Mixed solution,
GQD is catalyzed H2O2Reduce, meanwhile, TMB is oxidized to oxidized form TMB（oxTMB）, solution is changed into blue from colourless, 652
Ultraviolet absorption peak is produced at nm；Concentration of glucose is bigger, the H that GOx catalysis glucose is produced2O2It is more, in the catalytic action of GQD
Under, the oxTMB amounts of generation are more, and the blueness of solution is deeper, and absorbance increase establishes the class peroxidase based on GQD and urges
Change the glucose sensing approach of characteristic.Additionally, the selectivity that is catalyzed to glucose of GOx and GQD are to H2O2Good catalysis live
Property, it is capable of achieving the sensitivity and selective enumeration method to glucose.
The present invention uses following technical scheme：
（1）Graphene oxide（GO）Preparation：0.5 g graphite powders and 0.5 g sodium nitrate are added to 23 mL mass percentages
During concentration is 98% concentrated sulfuric acid, stirred under condition of ice bath, then be slowly added into 3 g potassium permanganate, in 35 °C of water-baths
Stirring to solution forms brown paste, adds 40 mL ultra-pure waters and continues stirring 30 minutes, adds 100 mL ultra-pure waters
Afterwards, the hydrogen peroxide that mass percentage concentration is 30% is dropwise instilled, untill solution colour is changed into glassy yellow；By product mistake while hot
It is neutral, 50 °C of dryings in vacuum drying chamber to filter and cleaned with ultra-pure water to filtrate, that is, graphene oxide is obtained；
（2）The preparation of graphene film：Graphene oxide is placed in tube furnace, it is small in 300 °C of reductase 12s under nitrogen protection
When, be cooled to room temperature, that is, graphene film is obtained；
（3）The preparation of GQD：0.05 g graphene films are placed in volume ratio 1:3 mass percentage concentration is respectively 98% He
Ultrasound 17 hours in 68% concentrated sulfuric acid and the mixed solution of concentrated nitric acid, add the dilution of 250 mL ultra-pure waters, micro- with 0.22 μm
Hole filter membrane suction filtration is to neutrality；Filter cake is dissolved in 20 mL ultra-pure waters, the pH that solution is adjusted with NaOH is 8 or so, by solution
It is transferred in autoclave and is reacted 12 hours in 200 °C, is cooled to room temperature；The solution that will be obtained is filtered with 0.22 μm of micropore
Membrane filtration removes the graphene film of large volume, the brown filtrate for obtaining as GQD solution.
（4）Glucose detection：GOx and glucose solution are mixed, is reacted 30 minutes at 37 °C, GOx catalysis glucose is anti-
H should be produced2O2；The mixed solution of GQD and TMB is added, is reacted 1 hour at room temperature, under the catalytic action of GQD, H2O2Occur
Reduction, while TMB is oxidized into oxTMB so that solution is changed into blueness by colourless, produces obvious ultraviolet suction at 652 nm
Receive peak；Concentration of glucose is bigger, the H of generation2O2More, under the catalytic action of GQD, the oxTMB amounts of generation are more, solution
Blue deeper, the absorbance at 652 nm increases, and the degree of absorbance increase is in the range of 1-100 μM with concentration of glucose
Linear relationship, the detection to glucose is limited to 0.1 μM, shows that the sensor of present invention foundation can be used for the quick of glucose
And Sensitive Detection.
The solution have the advantages that：The present invention produces H using the catalysis glucose of GOx in the presence of oxygen2O2, Jin Erjie
The catalysis characteristics of the class peroxidase of GQD is closed, in catalysis H2O2While reduction, TMB is set oxidation to occur and develop the color, according to molten
The intensification of liquid color and the increase of UV absorption intensity, are capable of achieving the quick of glucose, sensitivity and selective enumeration method, have
Good application prospect.
Brief description of the drawings
Fig. 1 is the glucose sensing approach schematic diagram of the class Peroxidative Characteristics based on GQD.
Fig. 2 is（A）The Fourier transform infrared spectroscopy figure of GO and GQD,（B）The ultraviolet-visible spectrogram and fluorescence light of GQD
Spectrogram（Excitation wavelength is 310 nm）, interior illustration is photos of the GQD under radiation of visible light and ultra violet lamp.
Fig. 3 is（A）The atomic force microscopy diagram of GQD, interior illustration is grain size distribution,（B）The transmission electron microscope of GQD
Figure, interior illustration is grain size distribution.
Fig. 4 is（A）The H of various concentrations2O2In the presence of ultraviolet-visible spectrogram, the H from a to o2O2Concentration is successively 0,
0.0012nd, 0.0024,0.012,0.024,0.05,0.1,0.2,0.4,0.72,1.5,3,6,12,24 mM,（B）At 652 nm
Absorbance and H2O2The linearity curve of concentration, interpolation photo is the H that there are various concentrations2O2When solution colour change shine
Piece.
Fig. 5 is（A）Ultraviolet-visible spectrogram in the presence of the glucose of various concentrations, from a to l, concentration of glucose is followed successively by
It is 0,0.001,0.002,0.005,0.01,0.02,0.05,0.1,0.2,0.5,1,2 mM,（B）Absorbance at 652 nm
With the linearity curve of concentration of glucose, the change photo of solution colour when interpolation photo is the glucose that there are various concentrations.
Fig. 6 is the selectivity experiment to glucose, other species sugar and amino acid.
Specific embodiment
The present invention is further elaborated with specific embodiment below in conjunction with the accompanying drawings, but the present invention is not limited thereto.
The preparation of graphene quantum dot：
（1）The preparation of graphene oxide：0.5 g graphite powders and 0.5 g sodium nitrate are added to 23 mL mass percentage concentrations
In for 98% concentrated sulfuric acid, stirred under condition of ice bath, then be slowly added into 3 g potassium permanganate, in 35 °C of stirred in water bath
Brown paste is formed to solution, 40 mL ultra-pure waters is added and is continued stirring 30 minutes, after adding 100 mL ultra-pure waters, by
Drop instills the hydrogen peroxide that mass percentage concentration is 30%, untill solution colour is changed into glassy yellow；Product is filtered while hot and is used in combination
It is neutrality that ultra-pure water is cleaned to filtrate, and 50 °C of dryings in vacuum drying chamber are obtained graphene oxide；
（2）The preparation of graphene film：Graphene oxide is placed in tube furnace, it is small in 300 °C of reductase 12s under nitrogen protection
When, be cooled to room temperature, that is, graphene film is obtained；
（3）The preparation of graphene quantum dot：0.05 g graphene films are placed in volume ratio 1:3 mass percentage concentration difference
It is ultrasound 17 hours in 98% and 68% concentrated sulfuric acid and the mixed solution of concentrated nitric acid, the dilution of 250 mL ultra-pure waters is added, with 0.22
μm miillpore filter suction filtration to neutrality；Filter cake is dissolved in 20 mL ultra-pure waters, the pH for adjusting solution with NaOH is 8 or so,
Transfer the solution into autoclave and reacted 12 hours in 200 °C, be cooled to room temperature；The solution that will be obtained is with 0.22 μm
Filtering with microporous membrane removes the graphene film of large volume, the brown filtrate for obtaining as graphene quantum dot solution.
The GO and GQD that synthesize are characterized using Fourier transform infrared, as a result as shown in Figure 2 A.With GO（Curve a）
Compare, GQD（Curve b）CO/COOH in 1240 cm-1The stretching vibration intensity at place substantially diminishes, and the epoxide group in GQD
In 1052 cm-1The shuttle belt at place is almost wholly absent, and shows that GQD successfully synthesizes.Fig. 2 B are the ultraviolet-ray visible absorbing light of GQD
Spectrogram（Curve a）And fluorescence spectra（Curve b）, GQD has an absorption band for very little at 310 nm, when excitation wavelength is
During 310 nm, GQD has the very strong emission peak of fluorescence at 450 nm.Interior illustration is GQD under visible ray and ultraviolet light
Photo, GQD solution is under visible light illumination weak yellow liquid, and very strong blue light is sent under ultraviolet light.Tie above
Really show, fluorescence GQD has been synthesized using the inventive method.
Fig. 3 is that the AFM and transmission electron microscope of GQD are characterized.From atomic force microscopy diagram, GQD is in uniform point
The sheet of cloth, is highly 1.0 nm or so（Fig. 3 A）, and from transmission electron microscope picture, a diameter of 7-8 nm of GQD or so, shape
State is consistent with AFM result, further demonstrates that and uses the inventive method, has been made individual layer or bilayer GQD.
Class Peroxidative Characteristics detection H based on GQD2O2：Cleaning Principle is as shown in figure 1, by 10 μ g/mL's
The TMB of GQD and 0.8 mM is well mixed, and adds the H of various concentrations2O2, ultraviolet spectroscopy is carried out after reacting 1 hour at room temperature,
Result is as shown in Figure 4.Work as H2O2When concentration is smaller, with H2O2The increase of concentration, the absorbance at 652 nm rises rapidly；
Work as H2O2When concentration increases to 6 mM, the absorbance rate of climb is gradually slow, until H2O2When concentration reaches 12 mM, absorbance
Value no longer rises.Absorbance and H2O2Concentration in the range of 0.05-3 mM be in good linear relationship（Illustration in Fig. 4 B）,
Detection is limited to 0.1 μM.Fig. 4 B interpolation photos are with H2O2Concentration increases, the situation of change of solution colour, with H2O2Concentration
Increase, solution blueness is gradually deepened, and be can be used for H2O2Quick visualization detection.
Class peroxidase activity detection glucose based on GQD：Cleaning Principle is as shown in figure 1, in the presence of oxygen, incite somebody to action
The glucose solution mixing of GOx and various concentrations, reacts 30 minutes at 37 °C, adds the GQD and 0.8 mM of 10 μ g/mL
TMB solution, carries out ultraviolet spectroscopy, as a result as shown in Figure 5 after reacting 1 hour at room temperature.With the increase of concentration of glucose,
The H that GOx catalysis glucose is produced2O2More, under the catalytic action of GQD, the oxTMB amounts of generation are more, and the blueness of solution is got over
It is deep, the absorbance increase at 652 nm（Fig. 5 A）；Absorbance increase degree be in the range of 1-100 μM with concentration of glucose
Linear relationship（Fig. 5 B）, the detection to glucose is limited to 0.1 μM.Fig. 5 B interpolation photos are that solution colour increases with concentration of glucose
Big situation of change, from photo, with the increase of concentration of glucose, the color of solution is gradually deepened, and be can be used for grape
The quick visualization detection of sugar.
In order to verify selectivity of the inventive method to glucose detection, glucose is replaced with other by the same way
Sugar（Such as, fructose, sucrose, galactolipin, maltose）And amino acid（Such as, fruit methyllanthionine, proline, threonine, lysine）, survey
Amount result is as shown in Figure 6.In addition to having strong absorption to glucose, to other sugar and absorbance all very littles of amino acid, show
The method that the present invention builds has good selectivity to glucose detection, can be used for the selectivity inspection of glucose in complex system
Survey.
Claims (2)
1. the glucose sensing approach of the class Peroxidative Characteristics of graphene quantum dot is based on, it is characterised in that glucose
Detection：Glucose oxidase and glucose solution are mixed, is reacted 30 minutes at 37 °C, glucose oxidase catalysis grape
Sugar reaction produces hydrogen peroxide；The mixed solution of graphene quantum dot and reduced form tetramethyl benzidine is added, 1 is reacted at room temperature
Hour, under the catalytic action of graphene quantum dot, hydrogen peroxide is reduced, while reduced form tetramethyl benzidine is oxidized to
Oxidized form tetramethyl benzidine so that solution is changed into blueness by colourless, produces obvious ultraviolet absorption peak at 652 nm；Inhale
The degree of luminosity increase is linear in the range of 1-100 μM with concentration of glucose, can be used for the quick and sensitive inspection to glucose
Survey；
Described graphene quantum dot preparation process is as follows：
（1）The preparation of graphene oxide：0.5 g graphite powders and 0.5 g sodium nitrate are added into 23 mL mass percentage concentrations is
In 98% concentrated sulfuric acid, stirred under condition of ice bath, then be slowly added into 3 g potassium permanganate, in 35 °C of stirred in water bath extremely
Solution forms brown paste, adds 40 mL ultra-pure waters and continues stirring 30 minutes, after adding 100 mL ultra-pure waters, dropwise
The hydrogen peroxide that mass percentage concentration is 30% is instilled, untill solution colour is changed into glassy yellow；Product is filtered while hot and with super
It is neutrality that pure water is cleaned to filtrate, and 50 °C of dryings in vacuum drying chamber are obtained graphene oxide；
（2）The preparation of graphene film：Graphene oxide is placed in tube furnace, under nitrogen protection, in 300 °C of reductase 12s hour,
Room temperature is cooled to, that is, graphene film is obtained；
（3）The preparation of graphene quantum dot：0.05 g graphene films are placed in volume ratio 1:The mixing of 3 concentrated sulfuric acid and concentrated nitric acid
Ultrasound 17 hours in solution, add the dilution of 250 mL ultra-pure waters, with 0.22 μm of miillpore filter suction filtration to neutrality；Will filter
Cake is dissolved in 20 mL ultra-pure waters, and the pH that solution is adjusted with NaOH is 8 or so, is transferred the solution into autoclave in 200 °
C reacts 12 hours, is cooled to room temperature；The solution that will be obtained removes the Graphene of large volume with 0.22 μm of filtering with microporous membrane
Piece, the brown filtrate for obtaining as graphene quantum dot solution.
2. the glucose detection side of the class Peroxidative Characteristics based on graphene quantum dot according to claim 1
Method, it is characterised in that step（3）In, the mass percentage concentration of the described concentrated sulfuric acid is 98%, and the mass percentage concentration of concentrated nitric acid is
68%。
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| CN104316503A (en) * | 2014-10-29 | 2015-01-28 | 安徽师范大学 | Use and detection method of sensor based on grapheme quantum dot (GQDs) |
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| CN107101986A (en) * | 2017-06-13 | 2017-08-29 | 南昌大学 | A kind of blood coagulation enzyme assay method based on graphene quantum dot/erbium ion fluorescent nano probe |
| CN107561070B (en) * | 2017-08-28 | 2018-11-13 | 菏泽学院 | A kind of glucose quick visualization detection method and its preparation and application |
| CN110609032A (en) * | 2019-09-03 | 2019-12-24 | 东华理工大学 | Glucose detection method based on application of molybdenum oxide quantum dots as peroxide mimic enzyme |
| CN110779914B (en) * | 2019-11-05 | 2022-05-20 | 湖南科技大学 | Preparation method of kit based on hemoglobin and four-carbon or five-carbon dicarboxylic acid compound |
| CN110907589B (en) * | 2019-11-21 | 2022-07-15 | 福建师范大学福清分校 | Visible Cu detection based on GQDs photocatalysis2+Method (2) |
| CN111504995B (en) * | 2020-05-13 | 2021-10-12 | 暨南大学 | Method for detecting phospholipase A2 based on colorimetric principle and application thereof |
| CN112014336A (en) * | 2020-08-18 | 2020-12-01 | 济南大学 | Universal method for detecting activity of alpha-glucosidase based on cascade reaction |
| CN112763438B (en) * | 2020-12-28 | 2023-06-02 | 济南大学 | Application of carbon dot peroxidase CDs@NC in detection of D-alanine and D-proline |
| CN115521778B (en) * | 2022-09-13 | 2023-08-01 | 青岛大学 | Glucose colorimetric probe based on copper-doped boron quantum dots and cascade enzyme catalytic reaction and preparation method thereof |
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| CN103512878A (en) * | 2013-08-16 | 2014-01-15 | 南昌大学 | Sensor preparation method based on ECL-RET action between GO and GQDs and application on kinas detection |
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| CN102807209B (en) * | 2012-08-02 | 2014-04-16 | 清华大学 | Method for preparing graphene quantum dots |
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| Highly-efficient peroxidase-like catalytic activity of graphene dots for biosensing;Ai-Xian Zheng et al.;《Biosensors andBioelectronics》;20130608;第49卷;第520页右栏倒数第1段至第521页左栏第1段，第522页左栏倒数第1段至第523页左栏第2段、图1A和4A * |
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