CN109777100A - A kind of preparation method of redox graphene-poly-dopamine-glutathione composite material - Google Patents

A kind of preparation method of redox graphene-poly-dopamine-glutathione composite material Download PDF

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CN109777100A
CN109777100A CN201910124179.4A CN201910124179A CN109777100A CN 109777100 A CN109777100 A CN 109777100A CN 201910124179 A CN201910124179 A CN 201910124179A CN 109777100 A CN109777100 A CN 109777100A
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dopamine
poly
redox graphene
glutathione
composite material
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CN109777100B (en
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莫尊理
杨星
牛小慧
赵盼
刘振宇
郭瑞斌
刘妮娟
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Northwest Normal University
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Northwest Normal University
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Abstract

The present invention provides a kind of preparation methods of redox graphene-poly-dopamine-glutathione composite material, are that graphite oxide ultrasonic disperse is formed unit for uniform suspension in deionized water;Dopamine hydrochloride is dissolved in the Tris-Hcl buffer solution of pH=8.5, is then added in graphite oxide suspension, the then stirring 22 ~ for 24 hours at 60 DEG C ~ 65 DEG C stands, separates, washes, and it is dry, obtain redox graphene-poly-dopamine composite material;Continue for redox graphene-poly-dopamine to be dissolved in pH=8.5Tris-Hcl buffer solution, is ultrasonically treated 5 ~ 6h;Addition glutathione and manganese dioxide, room temperature reaction 22 ~ for 24 hours, filtering is dry to get black solid redox graphene-poly-dopamine-glutathione.The test result of chemical property shows that redox graphene-poly-dopamine-glutathione composite material prepared by the present invention has excellent electrical property.

Description

A kind of preparation of redox graphene-poly-dopamine-glutathione composite material Method
Technical field
The present invention relates to a kind of redox graphene-poly-dopamine-glutathione composite material with excellent properties Preparation method, belong to technical field of composite materials.
Background technique
Redox graphene is by carbon atom with sp2The New Two Dimensional that the carbon monoatomic layer of hybrid form connection is constituted is former Sub- crystal, basic structural unit are most stable of benzene hexatomic rings in organic material, are two-dimension nano materials most thin at present, Thickness is only 0.35nm.Redox graphene has impayable high electron mobility, and electronics is in graphene molecules Electron transfer rate is up to 15000cm2.V-1.s-1, and the mobility of silicon only has 1400cm2.V-1.s-1.However, single oxygen reduction Graphite alkene make it using narrow, therefore synthesizing to restore petrochemical industry graphene is that the composite material of base material has more Good performance and application.
Summary of the invention
The object of the present invention is to provide a kind of preparations of redox graphene-poly-dopamine-glutathione composite material Method.
The present invention simultaneously to prepared redox graphene-poly-dopamine-glutathione composite material structure and Electrochemistry can be carried out characterization and test.
One, redox graphene-poly-dopamine-glutathione composite material preparation
The preparation method of redox graphene-poly-dopamine-glutathione composite material of the present invention, including following technique step It is rapid:
(1) redox graphene-poly-dopamine preparation: graphite oxide ultrasonic disperse is formed in deionized water uniformly outstanding Supernatant liquid;Dopamine hydrochloride is dissolved in Tris-HCl(pH=8.5) buffer solution in, be added in graphite oxide suspension, mix The stirring 22 ~ for 24 hours at 60 DEG C ~ 65 DEG C, stands, separates, wash after closing uniformly, dry, obtains redox graphene-poly-dopamine Composite material is labeled as rGO-PDA.Wherein graphite oxide and the mass ratio of poly-dopamine are 1:1 ~ 2:1.
(2) redox graphene-poly-dopamine-glutathione composite material preparation: by above-mentioned reduction-oxidation graphite Alkene-poly-dopamine is dissolved in Tris-HCl(pH=8.5) buffer solution in, be ultrasonically treated 5 ~ 6h;Add glutathione and catalysis Agent manganese dioxide, room temperature reaction 22 ~ for 24 hours;It filters after the reaction was completed, it is dry, it is poly- more to obtain black solid redox graphene- Bar amine-glutathione is labeled as rGO-PDA-GSH.Wherein, the quality of redox graphene-poly-dopamine and glutathione Than for 1:1 ~ 1:2.
In order to promote sulfydryl on glutathione and poly-dopamine that addition reaction occurs well, and connect glutathione Onto poly-dopamine, the additional amount of manganese dioxide be redox graphene-poly-dopamine, glutathione total amount 10% ~ 15%.
The drying is dry 8 ~ 10h in freeze drying box.
Two, redox graphene-poly-dopamine-glutathione composite material structure
Fig. 1 is the scanning electron microscope (SEM) photograph of redox graphene-poly-dopamine-glutathione composite material prepared by the present invention.From Fig. 1 can be seen that redox graphene-poly-dopamine-glutathione with three-dimensional structure, regular appearance, distribution of pores Uniformly, and it can see the spherical structure of poly-dopamine, this also illustrates that the preparation of composite material is successful.
Three, redox graphene-poly-dopamine-glutathione composite material chemical property
The test of chemical property: bare glassy carbon electrode uses 1 μm, 0.3 μm and 0.05 μm of Al respectively2O3Suspension is polished, Respectively in two bare glassy carbon electrode surface drop coatings rGO-PDA, rGO-PDA-GSH, it is prepared into electrode rGO-PDA/GCE, rGO- PDA-GSH/GCE.Then it is respectively placed in 5.0mM [Fe (CN)6]4-/3-Solution (KCl comprising 0.1M) is 50mV/s sweeping speed, Scanning range -0.2V ~ 0.6V condition carries out its electric conductivity of cyclic voltammetry.
Fig. 2 is the cyclic voltammetry curve of rGO-PDA/GCE, rGO-PDA-GSH/GCE.From fig. 2 it can be seen that rGO- The peak current of PDA-GSH can be apparently higher than 2 times that rGO-PDA(is almost rGO-PDA), this illustrates that redox graphene-is poly- Dopamine-glutathione composite material has excellent electrical property.
The principle of the present invention: dopamine, its chemical name is 4- (2- amino-ethyl) -1,2- benzenediols, in specific pH Under condition or oxidizing condition, the phenolic hydroxyl group of dopamine is easily oxidized to quinone, and then finally aggregates into poly-dopamine material.Due to Poly-dopamine material surface has functional group (- OH ,-NH abundant2), it almost can be compound with any material progress, and have pole Good biocompatibility and biodegradability.Glutathione (glutathione, GSH) is by glutamic acid, cysteine and sweet Propylhomoserin combines, and is a kind of tripeptides containing γ-amido bond and sulfydryl, has antioxidation and integrates detoxication.Cysteine On sulfydryl be glutathione active group, the sulfydryl on glutathione can and poly-dopamine addition reaction occurs so that paddy Guang Sweet peptide can be good at being connected to above redox graphene by poly-dopamine, make redox graphene, dopamine, paddy The sweet peptide collaboration of Guang, composite material obtained have excellent chemical property.
Detailed description of the invention
Fig. 1 is redox graphene-poly-dopamine-glutathione composite material scanning electron microscope (SEM) photograph.
Fig. 2 is redox graphene-poly-dopamine-glutathione composite material cyclic voltammetry curve.
Specific embodiment
Below by specific example to redox graphene-poly-dopamine of the present invention-glutathione composite material rGO- Preparation, performance of PDA-GSH etc. are described further.
Embodiment 1
(1) preparation of graphite oxide: the process of first step pre-oxidation: under magnetic stirring by 1.25gK2S2O8And 1.25gP2O5 It is added at one time the dense H of 12.5mL2SO4In, 1g graphite powder is then added, mixed solution will be changed and be heated to 80 DEG C, stirred in magnetic force It mixes down and is heated to reflux 5h, after cooling, the dilution of 200mL water, the neutrality being then filtered, washed, in 60 DEG C of vacuum are added into solution Under the conditions of it is dry.The further oxidation process of second step: the graphite oxide of above-mentioned drying is weighed 1g, is scattered under condition of ice bath In the nitration mixture (volume ratio of the concentrated sulfuric acid and phosphoric acid is 3:1) of the 120mL concentrated sulfuric acid and phosphoric acid, temperature is kept to be 0 ~ 5 DEG C and constantly stir Lower addition 9g potassium permanganate is mixed, temperature is then risen into 50 DEG C of stirring 12h.System temperature is cooled to room temperature, is separately added into The hydrogen peroxide of 200mL ice water 5mL30%, and be stirred continuously, the HCl of 5mL5% is added, is finally washed, filters, is dried to obtain Graphite oxide rGO;
(2) redox graphene-poly-dopamine preparation: taking 100mg graphite oxide to be dispersed in 100mL deionized water, surpasses Sonication forms uniform suspension;Take 100mg Dopamine hydrochloride to be dissolved in Tris-HCl(pH=8.5 of 150mL) buffering it is molten It in liquid, is then added in graphite oxide suspension, is vigorously stirred at 60 DEG C ~ 65 DEG C for 24 hours, stand 30 ~ 40min, separation, water It washes, it is dry to get redox graphene-poly-dopamine composite material rGO-PDA;
(3) redox graphene-poly-dopamine-glutathione preparation: take 30mg redox graphene-poly-dopamine molten In Tris-HCl(pH=8.5 30mL) buffer solution in, be ultrasonically treated 5 ~ 6 hours;30mg glutathione is taken to be added to reduction In graphene oxide-poly-dopamine solution, the manganese dioxide of a small amount of (6mg) is added, it is small to be stirred to react 24 at 40 DEG C ~ 50 DEG C When;After the reaction was completed, it filters, is freeze-dried 8 ~ 10h, obtains black solid rGO-PDA-GSH;
(4) preparation of modified electrode rGO-PDA/GCE, rGO-PDA-GSH/GCE: 5mg rGO-PDA, rGO-PDA- are taken respectively GSH is dispersed in respectively in 5mL deionized water, and 1 ~ 2h of ultrasound obtains equal phase dispersant liquid.8 μ L this points are taken with microsyringe respectively The direct drop coating of dispersion liquid in the bare glassy carbon electrode surface that diameter is 3mm, (use on chamois leather respectively before being modified by bare glassy carbon electrode 0.3 μm and 0.05 μm of Al2O3Powder is polished to mirror surface, after washing surface dirt, is transferred in ultrasonic water bath successively with anhydrous second Alcohol, nitric acid (1:1, V/V) and ultrapure water continuously wash 2min), finally, modified electrode is placed to 6min at room temperature makes electrode table The solvent evaporating completely in face obtains electrode rGO-PDA/GCE, rGO-PDA-GSH/GCE of composite material modification, that is, work electricity Pole;
(5) electric performance test: respectively using modified electrode rGO-PDA/GCE, rGO-PDA-GSH/GCE as working electrode, platinum electrode For to electrode, saturated calomel electrode is reference electrode, electrochemical workstation is established;Modified electrode rGO-PDA-GSH/GCE is set In 5.0mM [Fe (CN)6]4-/3-Be 50mV/s sweeping speed in KCl solution comprising 0.1M, under scanning range -0.2V ~ 0.6V into Its electric conductivity of row cyclic voltammetry.The results show that electric current 104.21 the μ A, rGO-PDA of the composite material (rGO-PDA-GSH) 55.34 μ A of electric current.
Embodiment 2
(1) preparation of graphite oxide: with embodiment 1;
(2) 100mg graphite oxide redox graphene-poly-dopamine preparation: is dispersed in (concentration in 50mL deionized water 2mg/ml), ultrasonic treatment forms uniform suspension;Then 50mg Dopamine hydrochloride is dissolved in the Tris-Hcl(pH of 150mL =8.5) it in buffer solution, then adds it in the suspension of graphite oxide, is vigorously stirred for 24 hours at 60 DEG C ~ 65 DEG C, it is quiet 30 ~ 40min is set, is separated, washing is dry to get redox graphene-poly-dopamine composite material;
(3) redox graphene-poly-dopamine-glutathione preparation: take 30mg redox graphene-poly-dopamine molten In Tris-Hcl(pH=8.5 of 30mL) buffer solution in, be ultrasonically treated 5 ~ 6 hours;60mg glutathione is added to reduction In graphene oxide-poly-dopamine solution, the manganese dioxide of a small amount of (13.5mg) is then added, it is anti-in 40 DEG C ~ 50 DEG C stirrings It answers 24 hours;After the reaction was completed, it filters, is freeze-dried 8 ~ 10h, obtains black solid redox graphene-poly-dopamine-paddy The sweet peptide rGO-PDA-GSH of Guang;
(4) preparation of modified electrode rGO-PDA/GCE, rGO-PDA-GSH/GCE: with embodiment 1;
(5) rGO-PDA-GSH electric performance test: test method is the same as embodiment 1.The results show that composite material rGO-PDA-GSH The 79.04 μ A of electric current of electric current 142.12 μ A, rGO-PDA.

Claims (5)

1. a kind of preparation method of redox graphene-poly-dopamine-glutathione composite material, including following technique step It is rapid:
(1) redox graphene-poly-dopamine preparation: graphite oxide ultrasonic disperse is formed in deionized water uniformly outstanding Supernatant liquid;Dopamine hydrochloride is dissolved in the Tris-HCl buffer solution of pH=8.5, is then added in graphite oxide suspension, is mixed The stirring 22 ~ for 24 hours at 60 DEG C ~ 65 DEG C, stands, separates, wash after closing uniformly, dry, obtains redox graphene-poly-dopamine Composite material;
(2) redox graphene-poly-dopamine-glutathione composite material preparation: by the poly- DOPA of redox graphene- Amine is dissolved in the Tris-HCl buffer solution of pH=8.5, is ultrasonically treated 5 ~ 6h;Glutathione, catalyst manganese dioxide are added, Reaction 22 ~ for 24 hours at room temperature, is filtered after the reaction was completed, dry, obtains black solid redox graphene-poly-dopamine-paddy Guang Sweet peptide.
2. a kind of preparation method of redox graphene-poly-dopamine-glutathione composite material as described in claim 1, It is characterized by: the mass ratio of graphite oxide and poly-dopamine is 1:1 ~ 2:1 in step (1).
3. a kind of preparation method of redox graphene-poly-dopamine-glutathione composite material as described in claim 1, It is characterized by: the mass ratio of redox graphene-poly-dopamine and glutathione is 1:1 ~ 1:2 in step (2).
4. a kind of preparation method of redox graphene-poly-dopamine-glutathione composite material as described in claim 1, It is characterized by: the additional amount of catalyst manganese dioxide is redox graphene-poly-dopamine, glutathione in step (2) Gross mass 10% ~ 15%.
5. a kind of preparation method of redox graphene-poly-dopamine-glutathione composite material as described in claim 1, It is characterized by: the drying is dry 8 ~ 10h in freeze drying box in step (1), (2).
CN201910124179.4A 2019-02-19 2019-02-19 Preparation method of reduced graphene oxide-polydopamine-glutathione composite material Expired - Fee Related CN109777100B (en)

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CN111529682A (en) * 2020-05-11 2020-08-14 中国人民解放军陆军军医大学第一附属医院 Chemotaxis antibacterial nano material and preparation method and application thereof
CN112759807A (en) * 2021-01-18 2021-05-07 中北大学 High-thermal-conductivity three-dimensional graphene oxide composite functional particle modified natural rubber and preparation method thereof
CN113092558A (en) * 2021-03-31 2021-07-09 中国药科大学 Molecularly imprinted polymer electrode, preparation method and application thereof in electrochemical analysis of domoic acid
WO2021243825A1 (en) * 2020-06-05 2021-12-09 青岛理工大学 Hollow graphene oxide lubricating additive, super-lubricating water lubricant, preparation method therefor and use thereof

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111529682A (en) * 2020-05-11 2020-08-14 中国人民解放军陆军军医大学第一附属医院 Chemotaxis antibacterial nano material and preparation method and application thereof
WO2021243825A1 (en) * 2020-06-05 2021-12-09 青岛理工大学 Hollow graphene oxide lubricating additive, super-lubricating water lubricant, preparation method therefor and use thereof
CN112759807A (en) * 2021-01-18 2021-05-07 中北大学 High-thermal-conductivity three-dimensional graphene oxide composite functional particle modified natural rubber and preparation method thereof
CN112759807B (en) * 2021-01-18 2022-05-24 中北大学 High-thermal-conductivity three-dimensional graphene oxide composite functional particle modified natural rubber and preparation method thereof
CN113092558A (en) * 2021-03-31 2021-07-09 中国药科大学 Molecularly imprinted polymer electrode, preparation method and application thereof in electrochemical analysis of domoic acid

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