CN103923304A - Hemin-grapheme/poly(3,4-ethylene thiophene dioxide) ternary complex synthesized by use of microwave-assisted method and preparation method thereof - Google Patents
Hemin-grapheme/poly(3,4-ethylene thiophene dioxide) ternary complex synthesized by use of microwave-assisted method and preparation method thereof Download PDFInfo
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Abstract
The invention discloses application of a hemin-grapheme/poly(3,4-ethylene thiophene dioxide) ternary complex synthesized by use of a microwave-assisted method. The ternary complex is composed of ferriheme chloride (hemin), reduced graphene oxide and poly(3,4-ethylene thiophene dioxide). The ternary complex disclosed by the invention overcomes the defect that the activity of the conventional enzyme is likely to be affected by the environment temperature, the pH value and toxic reagents and can be used for lots of times of long-time detection of hydrogen peroxide. The invention also discloses an electrochemical detection instrument and an electrochemical detection method which are low in cost, simple to operate, convenient and rapid so as to avoid the use of a conventional expensive time-consuming analysis and detection instrument which is complicated to operate.
Description
Technical field
The present invention relates to a kind of biological sensor electrode material and preparation method thereof, particularly relate to the synthetic Hemin-Graphene of a kind of microwave assisting method/poly-(3,4-ethylene dioxythiophene) ternary complex and preparation, belong to Graphene composite nano materials technical field.
Background technology
Hydrogen peroxide is a kind of important industrial raw material, is also the intermediate product of many Industrial processes, and it accurately detects monitoring to corresponding production process and the control of quality product has keying action.At present, mostly traditional hydrogen peroxide detection method be based on spectrography and chromatography etc., has instrument costliness, complicated operation, cannot realize the shortcoming of real-time remote monitoring.But electrochemical process detects hydrogen peroxide becomes a kind of important detection method gradually with its simple and quick, with low cost and portable feature.Poor without the common selectivity of enzyme hydrogen peroxide sensor, and Enzyme sensor lacks practicality because of the impact that the activity of enzyme is subject to envrionment temperature, pH and toxic reagent.Therefore, the hydrogen peroxide sensor of exploitation highly selective, highly sensitive and high stability has great importance.
Microwave assisting method is in recent years in the wide concerned emerging synthetic method of one in the synthetic field of material.Microwave has intensification fast and energy emission is concentrated, the feature of homogeneous, can shorten significantly generated time, save energy, and product quality is better.
Since new carbon Graphene in 2004 is born, the conductivity that it is excellent and mechanical property just obtain extensive concern, and many matrix materials based on Graphene have been successfully applied to electrochemical sensor field.Protohemin (Hemin) is the active centre of protoheme proteinoid, and many small molecules (as nitrogen protoxide, oxygen, hydrogen peroxide etc.) are had to good katalysis.Poly-(3,4-ethylene dioxythiophene) is (PEDOT) a kind of excellent property, uses functional materials widely in electrochemical field.At present, the people such as Yanfei Xu with hemin and graphene oxide prepared hemin-Graphene (H-GNs) binary complex (
advanced Materials, 2009,
21, 1275-1279.), the people such as Shaojun Dong based on H-GNs mixture realized mononucleotide colorimetric determination (
aCS nano, 2011,
5, 1282-1290.), the people such as Yanfei Xu prepared the Graphene of high conductivity, high flexibility and transparency and PEDOT matrix material (
nano Research, 2009,
2, 343-348.).But above-mentioned two kinds of binary complexs are all difficult to be directly used in Electrochemical Detection hydrogen peroxide.
Hemin-Graphene at present/poly-(3,4-ethylene dioxythiophene) tri compound nano material have not been reported.
Summary of the invention
For the problem of prior art, the object of this invention is to provide the synthetic Hemin-Graphene of a kind of microwave assisting method/poly-(3,4-ethylene dioxythiophene) ternary complex and preparation.
The technical solution that realizes the object of the invention is: Hemin-Graphene/poly-(3 that a kind of microwave assisting method is synthetic, 4-ethylenedioxy thiophene) ternary complex, described ternary complex is by the graphene oxide and poly-(3 of protohemin (hemin), reduction, 4-ethylenedioxy thiophene) form, wherein, the massfraction of hemin is 14% ~ 30%, poly-(3,4-ethylenedioxy thiophene) massfraction be 1% ~ 10%, the massfraction of the graphene oxide of reduction is about 60% ~ 84%.
The preparation of the synthetic Hemin-Graphene of microwave assisting method/poly-(3,4-ethylene dioxythiophene) ternary complex, comprises the steps:
(1), protohemin (hemin), graphene oxide (GO) and ammoniacal liquor are mixed to magnetic agitation;
(2), 3,4-ethylene dioxythiophene (EDOT) is added to above-mentioned dispersion liquid, magnetic agitation;
(3), step (2) gained solution is transferred in microwave tube, polymerization 5 ~ 40 min at 110 ~ 180 DEG C of temperature;
(4), reacted rear microwave tube and be cooled to room temperature, by step (3) reaction product centrifugation, filtration washing, vacuum-drying.
The mass ratio of the hemin described in step (1) and graphene oxide is 1:4 ~ 5:4, and pH value of solution is 9 ~ 12, churning time 3 ~ 6h.
The mass ratio of the EDOT described in step (2) and graphene oxide is 355:1 ~ 1420:1, and churning time is 0.5 ~ 2h.
Vacuum-drying temperature described in step (4) is 60 DEG C.
Hemin-Graphene/poly-(3 that a kind of microwave assisting method is synthetic, 4-ethylenedioxy thiophene) application of ternary complex, the Hemin-Graphene of said structure/poly-(3,4-ethylene dioxythiophene) ternary complex is applied to mensuration content of hydrogen peroxide as the modified electrode material of biosensor.
Described measuring method comprises cyclic voltammetry and electric current-time curve method.
In said determination step, adopt three-electrode system, taking modified electrode as working electrode, saturated calomel electrode is reference electrode, and platinum filament is to electrode.
In said determination step, described modified electrode is that Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) ternary complex is dripped to be coated on glass-carbon electrode and is prepared from.The concentration of wherein, Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) dispersion liquid is 1mgmL
-1, dripping quantity is 2 ~ 10 μ L.
The step that wherein adopts electric current-time curve method to measure content of hydrogen peroxide is: modified electrode is positioned in the electrolyzer of pH7.0 containing Sodium phosphate dibasic/SODIUM PHOSPHATE, MONOBASIC cocktail buffer of 0.1M, logical nitrogen 15min, add continuously hydrogen peroxide (0.5 ~ 70 μ M), use electric current-time curve method, setting initial potential is-0.1V ~-0.35V, detects the response of modified electrode to hydrogen peroxide.
Compared with prior art, tool of the present invention has the following advantages: (1) adopts microwave assisting method, replace conventional baking oven as heat source for reaction using microwave, prepared Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) trielement composite material by changing the parameter such as temperature and time of microwave.Compare traditional hydrothermal method, this preparation method has consuming time extremely short, and energy utilization rate is high, the advantage of solvent for use nontoxic pollution-free; (2) adopt the artificial enzyme hemin of good stability cheap and easy to get, overcome traditional biological enzymic activity and be subject to the shortcoming of envrionment temperature, pH value and toxic reagent impact, can be used for repeatedly detecting for a long time of hydrogen peroxide; (3) propose a kind of with low costly, simple to operate, conveniently Electrochemical Detection instrument and method, has avoided using the analysis and detecting instrument of traditional costliness, consuming time, complex operation.
Brief description of the drawings
Accompanying drawing 1 is the TEM photo of the Hemin-Graphene prepared of the embodiment of the present invention 1/poly-(3,4-ethylene dioxythiophene).
Accompanying drawing 2 is that UV-vis figure (A) and the IR of the Hemin-Graphene prepared of the embodiment of the present invention 2/poly-(3,4-ethylene dioxythiophene) schemes (B).
Accompanying drawing 3 is alternating-current impedance figure (A) and cyclic voltammograms (B) of the Hemin-Graphene prepared of the embodiment of the present invention 3/poly-(3,4-ethylene dioxythiophene).
Accompanying drawing 4 is that the Hemin-Graphene prepared of the embodiment of the present invention 3/poly-(3,4-ethylene dioxythiophene) cyclic voltammogram (A) and difference to different concns hydrogen peroxide swept the cyclic voltammogram to hydrogen peroxide (B) under speed.
Accompanying drawing 5 is the Hemin-Graphene prepared of the embodiment of the present invention 3/poly-(3,4-ethylene dioxythiophene) electric current-time plot (A) to continuous dropping hydrogen peroxide and matched curves (B) of respective peaks electric current and concentration.
Accompanying drawing 6 is Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) electric current-time plots to continuous dropping disturbance material prepared by the embodiment of the present invention 3.
Embodiment
The following examples can make the present invention of those skilled in the art comprehend.
embodiment 1:
(1), 2.0 mg hemin are added to 4 mL 2.0 mgmL
-1graphene oxide dispersion liquid, slowly adds 30 μ L ammoniacal liquor (pH 9.0) under stirring, magnetic agitation 3h forms the finely dispersed mixed solution of reddish-brown;
(2), 20mmol EDOT is added to above-mentioned dispersion liquid, magnetic agitation 0.5h;
(3), step (2) gained solution is transferred to and in microwave tube, carries out Microwave Emulsifier-Free Polymerization, set microwave constant power 250W, 110 DEG C of microwave temperature, time 5min;
(4), reacted rear microwave tube and be cooled to room temperature, by step (3) reaction product centrifugation, filtration washing, vacuum-drying at 60 DEG C.Obtain Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) ternary complex.
Ternary complex, by x-ray photoelectron power spectrum (XPS), is recorded to hemin content and is about 15%, and poly-(3,4-ethylene dioxythiophene) content is about 1%, and the graphene oxide content of reduction is about 84%.
As shown in Fig. 1 TEM, can see PEDOT cross-linked structure clearly on the graphene film of accordion, from illustration, can find out that PEDOT segment is short and thick fusiform.
embodiment 2:
(1), 2.0 mg hemin are added to 4 mL 2.0 mgmL
-1graphene oxide dispersion liquid, slowly adds 30 μ L ammoniacal liquor (pH 9.0) under stirring, magnetic agitation 3h forms the finely dispersed mixed solution of reddish-brown;
(2), 30mmol EDOT is added to above-mentioned dispersion liquid, magnetic agitation 0.5h;
(3), step (2) gained solution is transferred to and in microwave tube, carries out Microwave Emulsifier-Free Polymerization, set microwave constant power 250W, 120 DEG C of microwave temperature, time 30min;
(4), reacted rear microwave tube and be cooled to room temperature, by step (3) reaction product centrifugation, filtration washing, vacuum-drying at 60 DEG C.Obtain Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) ternary complex.
Ternary complex, by x-ray photoelectron power spectrum (XPS), is recorded to hemin content and is about 14%, and poly-(3,4-ethylene dioxythiophene) content is about 5%, and the graphene oxide content of reduction is about 81%.
Its UV, visible light figure (UV-vis) as shown in Figure 2 (A) shows, the absorption peak at 254nm place is from the graphene oxide of chemical reduction, the broad peak at 412nm place is from the Soret band of hemin, and the blue shift of its about 27nm has confirmed hemin and the interactional existence of graphene film interlayer π-π.Its infrared spectra (IR) is as shown in Fig. 2 (B), and absorption peak is from 1635 cm
-1be blue shifted to 1569 cm
-1, confirmed the successful preparation of ternary complex.Therefore prepared product is Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) ternary nano composite material.
embodiment 3:
(1), 6.2 mg hemin are added to 4 mL 2.0 mgmL
-1graphene oxide dispersion liquid, slowly adds 40 μ L ammoniacal liquor (pH 10.0) under stirring, magnetic agitation 4h forms the finely dispersed mixed solution of reddish-brown;
(2), 50mmol EDOT is added to above-mentioned dispersion liquid, magnetic agitation 1.5h;
(3), step (2) gained solution is transferred to and in microwave tube, carries out Microwave Emulsifier-Free Polymerization, set microwave constant power 250W, 120 DEG C of microwave temperature, time 30min;
(4), reacted rear microwave tube and be cooled to room temperature, by step (3) reaction product centrifugation, filtration washing, vacuum-drying at 60 DEG C.Obtain Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) ternary complex.
By ternary complex, by x-ray photoelectron power spectrum (XPS), recording hemin content is approximately 28%, and poly-(3,4-ethylene dioxythiophene) content is about 9%, and the graphene oxide content of reduction is about 63%.
Its alternating-current impedance (EIS), as shown in Fig. 3 (A), is compared monobasic and binary material, and the impedance of Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) ternary complex is obviously lower, and electroconductibility is better.Its cyclic voltammogram at Sodium phosphate dibasic/phosphate sodium dihydrogen buffer solution is as shown in Fig. 3 (B), can see corresponding to Fe(III in hemin) a pair of reversible peak of redox reaction, illustrate that prepared Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) ternary complex has good chemical property.
embodiment 4:
(1), 10.0 mg hemin are added to 4 mL 2.0 mgmL
-1graphene oxide dispersion liquid, slowly adds 50 μ L ammoniacal liquor (pH 12.0) under stirring, magnetic agitation 6h forms the finely dispersed mixed solution of reddish-brown;
(2), 80mmol EDOT is added to above-mentioned dispersion liquid, magnetic agitation 2h;
(3), step (2) gained solution is transferred to and in microwave tube, carries out Microwave Emulsifier-Free Polymerization, set microwave constant power 250W, 180 DEG C of microwave temperature, time 40min;
(4), reacted rear microwave tube and be cooled to room temperature, by step (3) reaction product centrifugation, filtration washing, vacuum-drying at 60 DEG C.Obtain Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) ternary complex.
Ternary complex, by x-ray photoelectron power spectrum (XPS), is recorded to hemin content and is about 30%, and poly-(3,4-ethylene dioxythiophene) content is about 10%, and the graphene oxide content of reduction is about 60%.
application example 1
1. the preparation of modified electrode, comprises the following steps:
(1), glass-carbon electrode is ground to respectively on the alumina powder of 0.1 and 0.03 μ m smooth, then at ultrapure water, dehydrated alcohol and ultrapure water supersound process 2 ~ 3min, dry up through nitrogen, obtain clean glass-carbon electrode, for subsequent use;
(2), Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) mixture is joined in redistilled water,, through ultrasonic dispersion 1h, obtain 1.0 mgmL of brown
-1uniform dispersion;
(3), getting the above-mentioned dispersant liquid drop of 2 μ L is coated in glass-carbon electrode surface, dry Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) modified electrode that obtains being covered with sensitive membrane of drying device;
2. the detection method of modified electrode to hydrogen peroxide, comprises the following steps:
Step (3) gained modified electrode is positioned in the 0.1M Sodium phosphate dibasic/phosphate sodium dihydrogen buffer solution of pH value 7.0, and logical nitrogen 15min, adds hydrogen peroxide and stirs after 2min, uses cyclic voltammetry, and potential window is-0.8 ~ 0.2V, sweeps speed for 50mVs
-1, detect the response of modified electrode to hydrogen peroxide.As shown in Figure 4 (A), along with concentration of hydrogen peroxide increases to 1.5mM gradually from 0.5mM, corresponding reduction peak current also progressively increases, and shows that modified electrode has good electro catalytic activity to hydrogen peroxide; As shown in Fig. 4 (B), sweeping speed 60 ~ 200mVs
-1in scope, hydrogen-peroxide reduction peak current and to sweep fast square root linear, shows that hydrogen peroxide is diffusion controlled process on modified electrode surface.
application example 2:
1. the preparation of modified electrode, comprises the following steps:
(1), glass-carbon electrode is ground to respectively on the alumina powder of 0.1 and 0.03 μ m smooth, then at ultrapure water, dehydrated alcohol and ultrapure water supersound process 2 ~ 3min, dry up through nitrogen, obtain clean glass-carbon electrode, for subsequent use;
(2), Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) mixture is joined in redistilled water,, through ultrasonic dispersion 1h, obtain 1.0 mgmL of brown
-1uniform dispersion;
(3), getting the above-mentioned dispersant liquid drop of 5 μ L is coated in glass-carbon electrode surface, dry Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) modified electrode that obtains being covered with sensitive membrane of drying device;
2. the detection method of modified electrode to hydrogen peroxide, comprises the following steps:
Step (3) gained modified electrode is positioned in the 0.1M Sodium phosphate dibasic/phosphate sodium dihydrogen buffer solution of pH value 7.0, and logical nitrogen 15min, uses electric current-time curve method, and initial potential-0.1V is set, and detects the response of modified electrode to hydrogen peroxide.Result shows, adds after hydrogen peroxide and does not occur responding clearly step, shows that modified electrode is not enough to catalytic reduction hydrogen peroxide under the initial potential of-0.1V.
application example 3:
1. the preparation of modified electrode, comprises the following steps:
(1), glass-carbon electrode is ground to respectively on the alumina powder of 0.1 and 0.03 μ m smooth, then at ultrapure water, dehydrated alcohol and ultrapure water supersound process 2 ~ 3min, dry up through nitrogen, obtain clean glass-carbon electrode, for subsequent use;
(2), Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) mixture is joined in redistilled water,, through ultrasonic dispersion 1h, obtain 1.0 mgmL of brown
-1uniform dispersion;
(3), getting the above-mentioned dispersant liquid drop of 5 μ L is coated in glass-carbon electrode surface, dry Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) modified electrode that obtains being covered with sensitive membrane of drying device;
2. the detection method of modified electrode to hydrogen peroxide, comprises the following steps:
Step (3) gained modified electrode is positioned in the 0.1M Sodium phosphate dibasic/phosphate sodium dihydrogen buffer solution of pH value 7.0, and logical nitrogen 15min, uses electric current-time curve method, and initial potential-0.2V is set, and detects the response of modified electrode to hydrogen peroxide.As shown in Fig. 5 (A), once there is immediately response step after adding hydrogen peroxide, show that modified electrode is very rapidly to the catalytic reduction of hydrogen peroxide, and within the scope of 0.5 ~ 70 μ M, response current and concentration linear (Fig. 5 (B)).
application example 4:
1. the preparation of modified electrode, comprises the following steps:
(1), glass-carbon electrode is ground to respectively on the alumina powder of 0.1 and 0.03 μ m smooth, then at ultrapure water, dehydrated alcohol and ultrapure water supersound process 2 ~ 3min, dry up through nitrogen, obtain clean glass-carbon electrode, for subsequent use;
(2), Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) mixture is joined in redistilled water,, through ultrasonic dispersion 1h, obtain 1.0 mgmL of brown
-1uniform dispersion;
(3), getting the above-mentioned dispersant liquid drop of 5 μ L is coated in glass-carbon electrode surface, dry Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) modified electrode that obtains being covered with sensitive membrane of drying device;
2. the detection method of modified electrode to hydrogen peroxide, comprises the following steps:
Step (3) gained modified electrode is positioned in the 0.1M Sodium phosphate dibasic/phosphate sodium dihydrogen buffer solution of pH value 7.0, and logical nitrogen 15min, uses electric current-time curve method, and initial potential-0.35V is set, and detects the response of modified electrode to hydrogen peroxide.Result shows, also there will be response step after adding hydrogen peroxide, and bench height is suitable with application example 2, show modified electrode-0.35V and-catalytic reduction ability under the initial potential of 0.2V is suitable.
the response of modified electrode to common interference material:
1. the preparation of modified electrode, comprises the following steps:
(1), glass-carbon electrode is ground to respectively on the alumina powder of 0.1 and 0.03 μ m smooth, then at ultrapure water, dehydrated alcohol and ultrapure water supersound process 2 ~ 3min, dry up through nitrogen, obtain clean glass-carbon electrode, for subsequent use;
(2), Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) mixture is joined in redistilled water,, through ultrasonic dispersion 1h, obtain 1.0 mgmL of brown
-1uniform dispersion;
(3), getting the above-mentioned dispersant liquid drop of 5 μ L is coated in glass-carbon electrode surface, dry Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) modified electrode that obtains being covered with sensitive membrane of drying device;
2. the detection method of modified electrode to hydrogen peroxide, comprises the following steps:
Step (3) gained modified electrode is positioned in the 0.1M Sodium phosphate dibasic/phosphate sodium dihydrogen buffer solution of pH value 7.0, and logical nitrogen 15min, uses electric current-time curve method, and initial potential-0.2V is set, and detects the response of modified electrode to common interference material; As shown in Figure 6, modified electrode all without obviously response, shows that modified electrode detects hydrogen peroxide and has good selectivity to common interference material Dopamine HCL, uric acid, ascorbic acid and the glucose of 10 times of concentration.
Claims (9)
1. Hemin-Graphene/poly-(3 that microwave assisting method is synthetic, 4-ethylenedioxy thiophene) ternary complex, it is characterized in that, described ternary complex is by the graphene oxide and poly-(3 of protohemin, reduction, 4-ethylenedioxy thiophene) form, wherein the massfraction of protohemin is 14% ~ 30%, poly-(3,4-ethylenedioxy thiophene) massfraction be 1% ~ 10%, the massfraction of the graphene oxide of reduction is 60% ~ 84%.
2. synthetic Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) ternary complex of microwave assisting method according to claim 1, is characterized in that, described ternary complex is prepared by following steps:
(1), protohemin, graphene oxide and ammoniacal liquor are mixed to magnetic agitation;
(2), 3,4-ethylene dioxythiophene is added to above-mentioned dispersion liquid, magnetic agitation;
(3), step (2) gained solution is transferred in microwave tube, polymerization 5 ~ 40 min at 110 ~ 180 DEG C of temperature;
(4), reacted rear microwave tube and be cooled to room temperature, by step (3) reaction product centrifugation, filtration washing, vacuum-drying.
3. synthetic Hemin-Graphene/poly-(3 of microwave assisting method according to claim 2,4-ethylenedioxy thiophene) ternary complex, it is characterized in that, the mass ratio of the protohemin described in step (1) and graphene oxide is 1:4 ~ 5:4, pH value of solution is 9 ~ 12, churning time 3 ~ 6h.
4. synthetic Hemin-Graphene/poly-(3 of microwave assisting method according to claim 2,4-ethylenedioxy thiophene) ternary complex, it is characterized in that, described in step (2) 3, the mass ratio of 4-ethylenedioxy thiophene and graphene oxide is 355:1 ~ 1420:1, and churning time is 0.5 ~ 2h.
5. synthetic Hemin-Graphene/poly-(3,4-ethylene dioxythiophene) ternary complex of microwave assisting method according to claim 2, is characterized in that, the vacuum-drying temperature described in step (4) is 60 DEG C.
6. the preparation of the synthetic Hemin-Graphene of microwave assisting method/poly-(3,4-ethylene dioxythiophene) ternary complex, is characterized in that, comprises the steps:
(1), protohemin, graphene oxide and ammoniacal liquor are mixed to magnetic agitation;
(2), 3,4-ethylene dioxythiophene is added to above-mentioned dispersion liquid, magnetic agitation;
(3), step (2) gained solution is transferred in microwave tube, polymerization 5 ~ 40 min at 110 ~ 180 DEG C of temperature;
(4), reacted rear microwave tube and be cooled to room temperature, by step (3) reaction product centrifugation, filtration washing, vacuum-drying.
7. synthetic Hemin-Graphene/poly-(3 of microwave assisting method according to claim 6,4-ethylenedioxy thiophene) preparation of ternary complex, it is characterized in that, the mass ratio of the protohemin described in step (1) and graphene oxide is 1:4 ~ 5:4, pH value of solution is 9 ~ 12, churning time 3 ~ 6h.
8. synthetic Hemin-Graphene/poly-(3 of microwave assisting method according to claim 6,4-ethylenedioxy thiophene) preparation of ternary complex, it is characterized in that, described in step (2) 3, the mass ratio of 4-ethylenedioxy thiophene and graphene oxide is 355:1 ~ 1420:1, and churning time is 0.5 ~ 2h.
9. the preparation of the synthetic Hemin-Graphene of microwave assisting method according to claim 6/poly-(3,4-ethylene dioxythiophene) ternary complex, is characterized in that, the vacuum-drying temperature described in step (4) is 60 DEG C.
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| CN106496552A (en) * | 2016-11-10 | 2017-03-15 | 过冬 | A kind of preparation method of the poly- aminobenzenesulfonic acid of ternary nano composite material Graphene polyaniline |
| CN113030195A (en) * | 2021-02-22 | 2021-06-25 | 华南师范大学 | Hemicidin-graphene composite material and application thereof in detection of nitric oxide gas |
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| CN105572188A (en) * | 2014-10-17 | 2016-05-11 | 南京理工大学 | (PANI/RGO)n/Hemin modified electrode and electrochemical detection method of (PANI/RGO)n/Hemin modified electrode to hydrogen peroxide |
| CN104597240A (en) * | 2015-02-02 | 2015-05-06 | 广西医科大学 | Biosensing method for detecting leukemia by graphene/mimetic peroxidase double-signal amplification |
| CN104597240B (en) * | 2015-02-02 | 2016-06-15 | 广西医科大学 | Graphene/class peroxidase leukemic bio-sensing method of dual signal amplification detection |
| CN106496552A (en) * | 2016-11-10 | 2017-03-15 | 过冬 | A kind of preparation method of the poly- aminobenzenesulfonic acid of ternary nano composite material Graphene polyaniline |
| US11786888B2 (en) | 2017-04-20 | 2023-10-17 | Heart Biotech Nano Limited | Electroactive composite comprising graphene, a metalloprotein and a conjugate polymer |
| CN113030195A (en) * | 2021-02-22 | 2021-06-25 | 华南师范大学 | Hemicidin-graphene composite material and application thereof in detection of nitric oxide gas |
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