CN106622288A - Platinum-sulfonated graphene composite nano material with characteristics of simulated peroxidase - Google Patents
Platinum-sulfonated graphene composite nano material with characteristics of simulated peroxidase Download PDFInfo
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Abstract
The invention discloses a platinum-sulfonated graphene composite nano material with characteristics of simulated peroxidase. Sulfonated graphene is taken as the substrate, platinum nano particles are synthesized by a sodium borohydride reduction method, and sulfonated graphene and platinum nano particles are used to prepare the platinum-sulfonated graphene composite nano material. The platinum-sulfonated graphene composite nano material has an excellent activity of peroxidase and can catalyze the oxidation reactions between 3,3',5,5'-tetramethylbenzidine hydrochloride to trigger color development. The composite nano material has good affinity on the substrate namely 3,3',5,5'-tetramethylbenzidine hydrochloride. The composite nano material can be used to detect hydrogen peroxide with a low concentration. The absorbance of catalytic product and the concentration (0.01-0.1 mmol/L) of hydrogen peroxide are in a linear relationship, and the detection limit is 0.0025 mmol/L.
Description
Technical field
The present invention relates to have the platinum-sulfonated graphene composite nano materials of Mimetic enzyme characteristic, belong to nanometer
Technology and bionics techniques field.
Background technology
Native enzyme is mainly protein, is on a small quantity nucleic acid, is basic in the vital movement and chemical reaction for maintaining biology etc.
During the material that plays a significant role.Because enzyme causes it each to the specificity and its efficient catalysis activity of Binding Capacity
Individual field receives much concern.However, native enzyme limited source, the complicated difficulty of purification, preservation condition harshness, easily by many in operating process
Planting physics, chemistry affect causes many drawbacks such as deactivation to limit the application of native enzyme.With the similar work(of native enzyme
Can artificial mimic enzyme can exactly overcome the above-mentioned shortcoming of native enzyme, and heat stability, preparation cost, catalysis activity,
The aspects such as biological detection show big advantage.Therefore, the development and application of artificial mimic enzyme is more and more subject to
The attention of people.
Peroxidase is usually catalyzing hydrogen peroxide or other peroxide, is shown as easily to gas chromatography or inorganic
Thing produces Oxidation.In Peroxidase Study, it is the carbon with Mimetic enzyme activity to study most commonly used
Nano material.Due to the low cost of carbon nanomaterial, easy large-scale production longer-term storage and can keep high in adverse circumstances
The advantages of degree stability so as to be widely used in the fields such as environment measuring and biomedicine.At present, Graphene, graphite oxide
Alkene, CNT, carbon quantum dot, graphene quantum dot etc. are reported with Mimetic Peroxidase activity, but compared to certainly
Right enzyme, the low catalytic performance of these material with carbon elements limits its application.
The platinum particles of Nano grade have the physics and chemical property of uniqueness, are widely used in biosensor, light
The field such as chemistry and electrochemical catalysis, semiconductor fluorescence probe, opto-electronic device.In recent years, researchers endeavour study platinum receive
Rice corpuscles stabilizer is overcoming its low dispersibility in the solution, be also easy to produce reunion sedimentation phenomenon, electron transport route easily by portion
Point blocking and surface activity site such as are easily blanked at the defect.It has been reported that nano platinum particle stabilizer have soluble small molecular
Compound sodium citrate, alkylamine, ethylene glycol, it is water-soluble polymer polyvinylpyrrolidone, poly-（Amide-amine）, it is poly-（Acrylic acid）,
Protein-based bovine serum albumin, apoferritin, lysozyme, material with carbon element carbon nanometer, graphene oxide, redox graphene
Deng.The composite prepared with above-mentioned stabilizer overcomes to a certain extent some defects of nano platinum particle presence itself,
But its building-up process complex operation, consuming reagent are more and preparation time is long, or reduce the catalysis work of script nano platinum particle
Property.Therefore, seek quick, easy preparation method acquisition high stability, highly active platinum nano material to be significant.
By the use of sulfonated graphene as carrier is supported, the method synthesized by sodium borohydride reduction prepares sulfonation to the present invention
Graphene-Platinum Nanoparticles composite, the composite is to substrate TMB（TMB）And hydrogen peroxide
（H2O2）There is high-affinity simultaneously.
The content of the invention
It is an object of the invention to provide one kind is with sulfonated graphene as substrate, platinum nanometer is synthesized by sodium borohydride reduction
Particle-sulfonated graphene composite, was simulated using the superior catalytic properties of nano platinum particle-sulfonated graphene composite
Oxide enzyme.
To achieve these goals, the present invention is employed the following technical solutions：
Platinum of the present invention-sulfonated graphene composite nano materials Mimetic enzyme, is characterized in that platinum-sulfonated graphene
Composite nano materials have peroxidase activity, and catalyzing hydrogen peroxide oxidation TMB hydrochlorate shows
Color；Described platinum-sulfonated graphene composite nano materials are prepared by following methods：It is 2.389 mg/ toward 12.559 mL concentration
The chloroplatinic acid aqueous solution of the mmol/L of 1.796 mL concentration 7.9, mixing is added to be stirred vigorously 15 points in the sulfonated graphene solution of mL
Zhong Hou, it is 2.5 mg/mL sodium borohydride aqueous solutions to be added dropwise over 0.645 mL concentration, and stirring obtains final product platinum-sulfonated graphite after 4 hours
Alkene composite nano materials aqueous solution, obtains platinum-sulfonated graphene composite nano materials powder after vacuum drying.
The preparation method of the sulfonated graphene is：The graphene oxide that Hummers methods are prepared is scattered in into deionization
In water, supersound process obtains the dispersion of 4 mg/mL graphene oxides for 3 hours, adds toward graphene oxide dispersion
5wt% sodium carbonate liquors so that system pH is 9 ~ 10, it is 0.16 g/mL sodium borohydride solutions to be subsequently adding 30 mL concentration,
Stirring reaction 1 hour at 80 DEG C, after 8000 revs/min of centrifugations precipitation is washed with water, obtains the reduction-oxidation graphite of neutrality
Alkene, redox graphene is scattered in deionized water, obtains the mL of redox graphene suspension 75, then will be to amino
Benzenesulfonic acid diazol is added in redox graphene suspension and stirring reaction 2 hours under condition of ice bath, is used after centrifugation
Distilled water washing is precipitated to pH value for 7, obtains in neutral couplings, by the couplings of above-mentioned gained be scattered in 150 mL go from
In sub- water, 10 mL concentration of addition are 1.6 g/mL hydrazine hydrates, and the stirring at 100 DEG C carries out reduction reaction in 24 hours, then drips
Plus 5 wt % sodium carbonate liquors precipitation sulfonated graphene, sulfonated graphene obtained above is thoroughly washed with distilled water,
Then sulfonated graphene is vacuum dried at a certain temperature, is obtained sulfonated graphene solid, taken 119.45 mg sulfonation stones
In 50 mL distilled waters, ultrasound 5 hours under room temperature obtain the palm fibre of the transparent clarifications of 2.389 mg/mL to black solid dissolving after fully peeling off
Black sulfonated graphite aqueous solution.
The mean diameter of nano platinum particle is 7.5 nm in the platinum-sulfonated graphene composite nano materials, and platinum element is with 0
Two kinds of forms of valency and+4 valency are present.
Catalyzing hydrogen peroxide oxidation TMB hydrochlorate generates blue product, and the product is 652
There is maximum absorption band at nm.
Platinum-sulfonated graphene composite nano materials catalyzing hydrogen peroxide oxidation TMB hydrochlorate
The optimum condition of reaction system is：PH is 5.0, and temperature is 37 DEG C, and the consumption of platinum-sulfonated graphene composite nano materials is
1.125 μ g/mL, the concentration of TMB hydrochlorate is 0.338 mmol/L, and the response time is 10
min。
Platinum-sulfonated graphene composite nano materials are to the Michaelis constant of TMB hydrochlorate
0.06244 mmol/L, is 47.76 mmol/L to the Michaelis constant of hydrogen peroxide.
Platinum-sulfonated graphene composite nano materials catalyzing hydrogen peroxide oxidation TMB hydrochlorate
Color product light absorption value it is linear with the hydrogen peroxide in 0.01 ~ 1 mmol/L concentration ranges, detection be limited to 0.0025
mmol/L。
Platinum of the present invention-sulfonated graphene composite nano materials Mimetic enzyme, concrete technical scheme is：
（One）The preparation of sulfonated graphene：First, the graphene oxide that Hummers methods are prepared is scattered in deionized water,
Supersound process obtains the dispersion of 4 mg/mL graphene oxides for 3 hours.5% sodium carbonate is added toward graphene oxide dispersion
Solution so that system pH is 9 ~ 10, it is 0.16 g/mL sodium borohydride solutions to be subsequently adding 30 mL concentration, at 80 DEG C
Stirring reaction 1 hour, after 8000 revs/min of centrifugations precipitation is washed with water, obtains the redox graphene of neutrality.By oxygen reduction
Graphite alkene is scattered in deionized water, obtains the mL of redox graphene suspension 75, then by Diazosalt of sulfanilic acid
It is added in redox graphene suspension and stirring reaction 2 hours under condition of ice bath, washs heavy with distilled water after centrifugation
It is 7 to form sediment to pH value, is obtained in neutral couplings.The couplings of above-mentioned gained are scattered in 150 mL deionized waters, are added
10 mL concentration are 1.6 g/mL hydrazine hydrates, and the stirring at 100 DEG C carries out reduction reaction in 24 hours, and then the sodium carbonate of Deca 5% is molten
Liquid precipitate sulfonated graphene, sulfonated graphene obtained above is thoroughly washed with distilled water, then by sulfonated graphene
It is vacuum dried at a certain temperature, is obtained sulfonated graphene solid.119.45 mg sulfonated graphite solid dissolvings are taken in 50
ML distilled waters, ultrasound 5 hours under room temperature, obtain the brownish black sulfonated graphene of the transparent clarifications of 2.389 mg/mL after fully peeling off
Aqueous solution.
（Two）The preparation of platinum-sulfonated graphene composite nano materials：
The mmol/L of 1.796 mL concentration 7.9 is added toward the sulfonated graphene solution that 12.559 mL concentration are 2.389 mg/mL
Chloroplatinic acid aqueous solution, after mixing is stirred vigorously 15 minutes, be added dropwise over 0.645 mL concentration for 2.5 mg/mL sodium borohydride water
Solution, stirring obtains final product platinum-sulfonated graphene composite nano materials aqueous solution after 4 hours.The average grain of nanometer platinum particles for being loaded
Footpath is 7.5 nm, and 4 DEG C of preservations can keep more than 2 months relatively stable.All glass drying ovens used in above procedure are equal
Through chloroazotic acid immersion, and distilled water thoroughly cleaning is used, dried.
（Three）Platinum-sulfonated graphene composite nano materials Mimetic enzyme activity：
Peroxidase substrate TMB hydrochloric acid is catalyzed by platinum-sulfonated graphene composite nano materials
Salt（TMB）Blue substrate is produced, its peroxidase activity is verified and compare.In sodium dihydrogen phosphate-disodium hydrogen phosphate buffer
In sequentially add hydrogen peroxide, TMB hydrochlorate and platinum-sulfonated graphene composite nano materials water
Solution, temperature bath 10 minutes after mixing, the absorbance at the 652 nm wavelength of change or measure of visual color.According to solution
Color is compared peroxidase activity by mensuration absorbance value.
（Four）Platinum-sulfonated graphene composite nano materials Mimetic enzyme detection hydrogen peroxide：
Peroxidase substrate TMB hydrochloric acid is catalyzed by platinum-sulfonated graphene composite nano materials
Salt produces blue substrate, detects low concentration hydrogen peroxide.Under optimal conditionss, in sodium dihydrogen phosphate-disodium hydrogen phosphate buffer
Sequentially add hydrogen peroxide, TMB hydrochlorate and platinum-sulfonated graphene composite nano materials water-soluble
Liquid, temperature bath 10 minutes, determine the absorbance at 652 nm wavelength after mixing.By absorbance standard curve to hydrogen peroxide
Concentration is carried out quantitatively.
Advantages of the present invention：
（1）Platinum obtained by the present invention-sulfonated graphene composite nano materials good stability and preparation method is simple.
（2）Platinum of the present invention-sulfonated graphene composite nano materials have good peroxidase activity.
（3）Platinum of the present invention-sulfonated graphene composite nano materials are to substrate TMB hydrochlorate
Affinity it is high.
（4）Platinum of the present invention-sulfonated graphene composite nano materials energy detection by quantitative hydrogen peroxide, test limit is low, sensitivity
It is high.
Description of the drawings
Fig. 1 is platinum-sulfonated graphene composite nano materials transmission electron microscope figure.
Fig. 2 is the x-ray photoelectron energy spectrum diagram of platinum-sulfonated graphene composite nano materials platinum element.
Fig. 3 is the X-ray diffractogram of platinum-sulfonated graphene composite nano materials.
Fig. 4 is platinum-sulfonated graphene composite nano materials catalyzing hydrogen peroxide oxidation TMB
The color change figure of hydrochlorate color development system.From left to right it is followed successively by TMB+H2O2Solution, sulfonated graphene+TMB+H2O2Solution,
Platinum-sulfonated graphene composite nano materials+TMB+H2O2Solution, solution is changed into blue from colourless.
Fig. 5 is platinum-sulfonated graphene composite nano materials final concentration to catalyzing hydrogen peroxide oxidation 3,3 ', 5,5 '-tetramethyl
The impact figure of base benzidine dihydrochloride color development system.
Fig. 6 is pH value to platinum-sulfonated graphene composite nano materials catalyzing hydrogen peroxide oxidation 3,3 ', 5,5 '-tetramethyl
The impact figure of benzidine dihydrochloride color development system.
Fig. 7 is warm bath temperature to platinum-sulfonated graphene composite nano materials catalyzing hydrogen peroxide oxidation 3,3 ', 5,5 '-four
The impact figure of methyl biphenyl amine hydrochlorate color development system.
Fig. 8 is TMB hydrochloride concentration to platinum-sulfonated graphene composite nano materials catalysis
The impact figure of hydrogen peroxide oxidation TMB hydrochlorate color development system.
Fig. 9 is the response time to platinum-sulfonated graphene composite nano materials catalyzing hydrogen peroxide oxidation 3,3 ', 5,5 '-four
The impact figure of methyl biphenyl amine hydrochlorate color development system.
Figure 10 is platinum-sulfonated graphene composite nano materials for the stable state of TMB hydrochlorate
Dynamic curve diagram.
Figure 11 is platinum-sulfonated graphene composite nano materials for the stability kineticses curve chart of hydrogen peroxide.
Figure 12 is platinum-sulfonated graphene composite nano materials detection peroxide standard curve figure.
Specific embodiment
Example 1：
Hummers methods prepare graphene oxide：The g of 325 mesh crystalline flake graphite 2.7 is weighed, 316 mL concentration is added to for 18.4
In the concentrated sulphuric acid of mol/L and the mixed solution of phosphoric acid that 36 mL concentration are 14.7 mol/L.After being sufficiently stirred for, 0 DEG C is placed at
In ice bath.By 16.2 g potassium permanganate on a small quantity repeatedly, in being slowly added into solution mixed above.0 DEG C of ice bath, magnetic force is kept to stir
After mixing 3 hours, the blackish green suspension of gained is transferred in 35 DEG C of tepidariums, temperature control 1 hour, then by the blackish green suspension of gained
In being transferred to 50 DEG C of tepidariums, temperature control obtains atropurpureuss suspension mixture in 12 hours.360 mL frozen water are slowly added into and obtain
Atropurpureuss suspension mixture in, be stirred vigorously 1 hour.Then the dropwise mL 30wt% hydrogen peroxide of Deca 12 toward solution
Solution, solution colour sports glassy yellow, stirs 30 minutes.Resulting solution Jing G1 sand core funnels（Aperture 20-30 microns）Cross
Filter, then 4000 rpms are centrifuged 30 minutes, abandoning supernatant；180 mL ultra-pure waters are added fully to vibrate washing, 4000
Rpm centrifugation 30 minutes, abandoning supernatant, precipitation color be in khaki；Add 180 mL 30wt% hydrochloric acid fully to shake
Swing washing, Jing G1 sand core funnels（Aperture 20-30 microns）Filter and remove insoluble particles, 4000 rpms of filtrate is centrifuged 30 points
Clock, abandoning supernatant, precipitation color continues to deepen；Then repeatedly with dehydrated alcohol by precipitate be washed till pH value be it is neutral, 4000
Rpm centrifugation 30 minutes, abandoning supernatant, precipitation be in brown color；Finally precipitated with washed with ether, Jing G5 sand core funnels（Hole
Footpath 1.5-2.5 microns）Filter.Filter cake overnight dries at room temperature, obtains the graphene oxide of brown.
Example 2：
It is prepared by Diazosalt of sulfanilic acid：In the 150 mL four-necked bottles equipped with condensing tube, agitator, Dropping funnel and thermometer
In be put into the wt% sodium carbonate liquors of 10 mL 5 and 2.1 g p-aminobenzene sulfonic acid crystal, the lower warm of stirring dissolves it, adds
The solution that 0.8 g sodium nitrite is made into 6 mL water, with ice bath 0 ~ 5 DEG C is cooled to.In the case where being stirred continuously, by 3 mL concentrated hydrochloric acid with
The solution that 10 mL water are made into is instilled in above-mentioned mixed solution, continues to stir 15 min in ice bath, obtains p-aminobenzene sulfonic acid weight
Nitrogen salt.
Example 3：
The graphene oxide that Hummers methods are prepared is scattered in deionized water, supersound process obtains 4 mg/mL oxygen for 3 hours
The dispersion of graphite alkene.5wt% sodium carbonate liquors are added toward graphene oxide dispersion so that system pH is 9 ~ 10,
30 mL concentration are subsequently adding for 0.16 g/mL sodium borohydride solutions, stirring reaction 1 hour at 80 DEG C, 8000 revs/min
Wash precipitation after centrifugation with water, obtain the redox graphene of neutrality.Redox graphene is scattered in deionized water,
The mL of redox graphene suspension 75 is obtained, then Diazosalt of sulfanilic acid is added to into redox graphene suspension
Stirring reaction 2 hours in liquid and under condition of ice bath, are washed with distilled water after centrifugation and are precipitated to pH value for 7, are obtained in neutral
Couplings.The couplings of above-mentioned gained are scattered in 150 mL deionized waters, 10 mL concentration is added for 1.6 g/mL hydrations
Hydrazine, the stirring at 100 DEG C carries out reduction reaction in 24 hours, then the wt % sodium carbonate liquors of Deca 5 precipitation sulfonated graphene, will
Sulfonated graphene obtained above is thoroughly washed with distilled water, then sulfonated graphene is carried out into vacuum at 60 DEG C and is done
It is dry, obtain sulfonated graphene solid.119.45 mg sulfonated graphites solid dissolvings are taken in 50 mL distilled waters, ultrasound 5 is little under room temperature
When, the brownish black sulfonated graphite aqueous solution of the transparent clarifications of 2.389 mg/mL is obtained after fully peeling off.
Example 4：
The mmol/L of 1.796 mL concentration 7.9 is added toward the sulfonated graphene solution that 12.559 mL concentration are 2.389 mg/mL
Chloroplatinic acid aqueous solution, after mixing is stirred vigorously 15 minutes, be added dropwise over 0.645 mL concentration for 2.5 mg/mL sodium borohydride water
Solution, stirring obtains final product platinum-sulfonated graphene composite nano materials aqueous solution after 4 hours.Obtain after being vacuum dried under uniform temperature
Platinum-sulfonated graphene composite nano materials powder.
Example 5：
By the platinum obtained by embodiment 4-water-soluble drop-coated of sulfonated graphene composite nano materials on copper mesh, transmitted electron is carried out
Microscope is tested, and the mean diameter for as a result showing nano platinum particle in platinum-sulfonated graphene composite nano materials is 7.5 nm（See
Fig. 1）.
Example 6：
Platinum-sulfonated graphene composite nano materials the powder obtained by a certain amount of embodiment 4 is taken, x-ray photoelectron power spectrum is carried out
Test, as a result shows that platinum element exists in two kinds of forms of 0 valency and+4 valency in platinum-sulfonated graphene composite nano materials（See Fig. 2）.
Example 7：
Platinum-sulfonated graphene composite nano materials the powder obtained by a certain amount of embodiment 4 is taken, X-ray diffraction test is carried out.Such as
It is the characteristic peak of platinum at 2 θ=40.08,46.02 and 60.27 shown in Fig. 3, platinum is corresponded to respectively（111）、（200）With
（220）Crystal face；It is the characteristic peak of sulfonated graphene at 2 θ=24.1.
Example 8：
In 1.74 mL sodium dihydrogen phosphate-disodium hydrogen phosphate buffer（The mmol/L of pH 5,200）In to sequentially add 0.18 mL dense
Spend the hydrogen peroxide for 0.1 mmol/L, the TMB hydrochloric acid that 0.04 mL concentration is 16.9 mmol/L
Salt and platinum-sulfonated graphene composite nano materials aqueous solution that 40 μ L concentration are 1.125 g/mL, 37 DEG C of temperature baths 10 after mixing
Minute, solution is changed into blue from colourless.When be not added with platinum-sulfonated graphene composite nano materials or add sulfonated graphene solution
When, there is no color reaction in reaction system（See Fig. 4）.
Example 9：
In 1.74 mL sodium dihydrogen phosphate-disodium hydrogen phosphate buffer（The mmol/L of pH 5,200）In to sequentially add 0.18 mL dense
Spend the hydrogen peroxide for 0.1 mmol/L, the TMB hydrochloric acid that 0.04 mL concentration is 16.9 mmol/L
The platinum of salt and 40 μ L variable concentrations-sulfonated graphene composite nano materials aqueous solution, 37 DEG C of temperature are bathed 10 minutes after mixing, are determined
Absorbance at 652 nm wavelength.As shown in figure 5, the absorbance of color product is with platinum-sulfonated graphene composite nano materials end
Concentration increases and increases, but after the concentration of platinum-sulfonated graphene composite nano materials reaches 1.125 μ g/mL, the suction of system
Light value tends towards stability, therefore selects the optimum amount of platinum-sulfonated graphene composite nano materials to be 1.125 μ g/mL.
Example 10：
3,4,4.5,5,5.5,6,7,8 1.74 mL sodium dihydrogen phosphate-disodium hydrogen phosphate buffer is respectively in pH value（200
mmol/L）In sequentially add 0.18 mL concentration be the hydrogen peroxide of 0.1 mmol/L, 0.04 mL concentration be 16.9 mmol/L
TMB hydrochlorate and platinum-sulfonated graphene composite Nano material that 40 μ L concentration are 1.125 g/mL
Material aqueous solution, 37 DEG C of temperature are bathed 10 minutes after mixing, determine absorbance at 652 nm wavelength.Platinum-sulfonated graphene composite Nano material
The relative catalytic activity of material reaches maximum when phosphate buffer pH value is 4.5 ~ 5.0（See Fig. 6）, therefore selective response system
Optimal pH is 5.0.
Example 11：
In 1.74 mL sodium dihydrogen phosphate-disodium hydrogen phosphate buffer（The mmol/L of pH 5,200）In to sequentially add 0.18 mL dense
Spend the hydrogen peroxide for 0.1 mmol/L, the TMB hydrochloric acid that 0.04 mL concentration is 16.9 mmol/L
Salt and platinum-sulfonated graphene composite nano materials aqueous solution that 40 μ L concentration are 1.125 g/mL, in different temperatures after mixing
10 DEG C, 20 DEG C, 30 DEG C, 37 DEG C, 45 DEG C, 50 DEG C, 60 DEG C temperature bath 10 minutes, determine 652 nm wavelength at absorbance.Such as Fig. 7 institutes
Show, between 10 ~ 37 DEG C of temperature, absorbance slowly increases, when temperature is higher than 37 DEG C, light absorption value then occurs significantly declining
Gesture, therefore the optimum temperature of selective response system is 37 DEG C.
Example 12：
In 1.74 mL sodium dihydrogen phosphate-disodium hydrogen phosphate buffer（The mmol/L of pH 5,200）In to sequentially add 0.18 mL dense
Spend hydrogen peroxide for 0.1 mmol/L, the TMB hydrochlorate of 0.04 mL variable concentrations and 40 μ L
Concentration is the platinum-sulfonated graphene composite nano materials aqueous solution of 1.125 g/mL, and 37 DEG C of temperature are bathed 10 minutes after mixing, are determined
Absorbance at 652 nm wavelength.As shown in figure 8, the absorbance of color product is with TMB hydrochlorate
Final concentration increases and increases, and absorbance almost no longer increases after concentration reaches 0.338 mmol/L, therefore reaction system is optimal
TMB concentration is 0.338 mmol/L.
Example 13：
In 1.74 mL sodium dihydrogen phosphate-disodium hydrogen phosphate buffer（The mmol/L of pH 5,200）In to sequentially add 0.18 mL dense
Spend the hydrogen peroxide for 0.1 mmol/L, the TMB hydrochloric acid that 0.04 mL concentration is 16.9 mmol/L
Salt and platinum-sulfonated graphene composite nano materials aqueous solution that 40 μ L concentration are 1.125 g/mL, 37 DEG C of temperature baths are anti-after mixing
Should, absorbance at 652 nm wavelength under measure different time.As shown in figure 9, with the prolongation in response time, absorbance is gradually
Increase, in the response time up to after 10 min, absorbance change is slow, therefore the optimum reacting time of selective response system is 10
min。
Example 14：
In 1.74 mL sodium dihydrogen phosphate-disodium hydrogen phosphate buffer（The mmol/L of pH 5,200）In to sequentially add 0.18 mL dense
Spend hydrogen peroxide for 0.1 mmol/L, the TMB hydrochlorate of 0.04 mL variable concentrations and 40 μ L
Concentration is the platinum-sulfonated graphene composite nano materials aqueous solution of 1.125 g/mL, and 37 DEG C of temperature baths after mixing are reacted 1 minute, are surveyed
Absorbance at fixed 652 nm wavelength, calculates initial velocity.It is fitted by Michaelis-Menten equation, it can be deduced that platinum-sulfonated graphene is compound to be received
Rice material is 0.06244 mmol/L to the Michaelis constant of substrate TMB hydrochlorate（See Figure 10）.
Example 15：
In 1.74 mL sodium dihydrogen phosphate-disodium hydrogen phosphate buffer（The mmol/L of pH 5,200）In sequentially add 0.18 mL not
With TMB hydrochlorate and 40 μ that the hydrogen peroxide of concentration, 0.04 mL concentration are 16.9 mmol/L
L concentration is the platinum-sulfonated graphene composite nano materials aqueous solution of 1.125 g/mL, and 37 DEG C of temperature baths after mixing are reacted 1 minute,
Absorbance at 652 nm wavelength is determined, initial velocity is calculated.It is fitted by Michaelis-Menten equation, it can be deduced that platinum-sulfonated graphene is combined
Nano material is 47.76 mmol/L to the Michaelis constant of substrate hydrogen peroxide（See Figure 11）.
Example 16：
In 1.74 mL sodium dihydrogen phosphate-disodium hydrogen phosphate buffer（The mmol/L of pH 5,200）In sequentially add 0.18 mL not
With TMB hydrochlorate and 40 μ that the hydrogen peroxide of concentration, 0.04 mL concentration are 16.9 mmol/L
L concentration is the platinum-sulfonated graphene composite nano materials aqueous solution of 1.125 g/mL, and 37 DEG C of temperature baths after mixing are reacted 10 minutes,
Determine absorbance at 652 nm wavelength.Concentration of hydrogen peroxide in the range of 0.01 ~ 1 mmol/L, the absorbance and mistake of color product
Hydrogen peroxide concentration is linearly related（r=0.997）, r refers to correlation coefficient in formula, and detection is limited to 0.0025 mmol/L（See Figure 12）.
Presently preferred embodiments of the present invention is the foregoing is only, not to limit the present invention, all essences in the present invention
Any modification made within god and principle, equivalent and improvement etc., should be included within the scope of the present invention.
Claims (7)
1. a kind of platinum-sulfonated graphene composite nano materials Mimetic enzyme, is characterized in that platinum-sulfonated graphene is compound and receives
Rice material has peroxidase activity, catalyzing hydrogen peroxide oxidation TMB hydrochlorate colour developing；Institute
The platinum stated-sulfonated graphene composite nano materials are prepared by following methods：It is 2.389 mg/mL toward 12.559 mL concentration
The chloroplatinic acid aqueous solution of the mmol/L of 1.796 mL concentration 7.9, mixing is added to be stirred vigorously 15 minutes in sulfonated graphene solution
Afterwards, it is 2.5 mg/mL sodium borohydride aqueous solutions to be added dropwise over 0.645 mL concentration, and stirring obtains final product platinum-sulfonated graphene after 4 hours
Composite nano materials aqueous solution, obtains platinum-sulfonated graphene composite nano materials powder after vacuum drying.
2. a kind of platinum according to claim 1-sulfonated graphene composite nano materials Mimetic enzyme, is characterized in that
The sulfonated graphene is prepared by following methods：The graphene oxide that Hummers methods are prepared is scattered in deionized water,
Supersound process obtains the dispersion of 4 mg/mL graphene oxides for 3 hours, and toward graphene oxide dispersion 5wt% carbonic acid is added
Sodium solution so that system pH is 9 ~ 10, it is 0.16 g/mL sodium borohydride solutions to be subsequently adding 30 mL concentration, at 80 DEG C
Lower stirring reaction 1 hour, after 8000 revs/min of centrifugations precipitation is washed with water, obtains the redox graphene of neutrality, will be reduced
Graphene oxide is scattered in deionized water, obtains the mL of redox graphene suspension 75, then by p-aminobenzene sulfonic acid diazonium
Salt is added in redox graphene suspension and stirring reaction 2 hours under condition of ice bath, is washed with distilled water after centrifugation
It is 7 to be precipitated to pH value, obtains, in neutral couplings, the couplings of above-mentioned gained being scattered in 150 mL deionized waters, plus
It is 1.6 g/mL hydrazine hydrates to enter 10 mL concentration, and the stirring at 100 DEG C carries out reduction reaction in 24 hours, then the wt % carbon of Deca 5
Acid sodium solution precipitates sulfonated graphene, sulfonated graphene obtained above is thoroughly washed with distilled water, then by sulfonation
Graphene is vacuum dried at a certain temperature, obtains sulfonated graphene solid, takes 119.45 mg sulfonated graphite solid dissolvings
In 50 mL distilled waters, ultrasound 5 hours under room temperature obtain the brownish black sulfonation stone of the transparent clarifications of 2.389 mg/mL after fully peeling off
Black aqueous solution.
3. a kind of platinum according to claim 1-sulfonated graphene composite nano materials Mimetic enzyme, is characterized in that
The mean diameter of nano platinum particle is 7.5 nm in the platinum-sulfonated graphene composite nano materials, and platinum element is with 0 valency and+4 valencys
Two kinds of forms are present.
4. a kind of platinum according to claim 1 or 3-sulfonated graphene composite nano materials Mimetic enzyme, it is special
It is that catalyzing hydrogen peroxide oxidation TMB hydrochlorate generates blue product to levy, and the product is at 652 nm
There is maximum absorption band.
5. a kind of platinum according to claim 1 or 3-sulfonated graphene composite nano materials Mimetic enzyme, it is special
It is platinum-sulfonated graphene composite nano materials catalyzing hydrogen peroxide oxidation TMB hydrochloric acid reactant salt to levy
The optimum condition of system is：PH is 5.0, and temperature is 37 DEG C, and the consumption of platinum-sulfonated graphene composite nano materials is 1.125 μ
G/mL, the concentration of TMB hydrochlorate is 0.338 mmol/L, and the response time is 10 min.
6. a kind of platinum according to claim 1 or 3-sulfonated graphene composite nano materials Mimetic enzyme, it is special
Levy is that platinum-sulfonated graphene composite nano materials are to the Michaelis constant of TMB hydrochlorate
0.06244 mmol/L, is 47.76 mmol/L to the Michaelis constant of hydrogen peroxide.
7. a kind of platinum according to claim 1 or 3-sulfonated graphene composite nano materials Mimetic enzyme, it is special
It is the aobvious of platinum-sulfonated graphene composite nano materials catalyzing hydrogen peroxide oxidation TMB hydrochlorate to levy
Color product light absorption value is linear with the hydrogen peroxide in 0.01 ~ 1 mmol/L concentration ranges, and detection is limited to 0.0025
mmol/L。
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