CN111268672A - Functionalized graphene compound and preparation method and application thereof - Google Patents
Functionalized graphene compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a functionalized graphene compound, and a preparation method and application thereof.A compound EDTA- β -CD-rGO is synthesized by a one-step hydrothermal method, and then the EDTA- β -CD-rGO is washed and dispersed and is modified on a glassy carbon electrode to obtain a modified electrode (EDTA- β -CD-rGO/GCE), and then the modified electrode is applied to the detection of free radicals.
Description
Technical Field
The invention relates to an electrode material and electrochemical detection, in particular to a functionalized graphene compound EDTA- β -CD-rGO and a preparation method thereof, and an application of EDTA- β -CD-rGO in free radical detection.
Background
The radical is an atom, molecule, ion or group having an unpaired electron formed by homolytic cleavage of a covalent bond in a molecule of a compound under an external condition such as photo-thermal conditions. About 95% or more of free radicals in the human body are oxygen radicals. Under normal physiological conditions, oxygen free radicals play an important role in metabolic processes such as cell respiration and thyroxine synthesis in human bodies, and are beneficial to human bodies. However, once the body is stressed or diseased, oxygen radicals are excessively generated, thereby causing harm to the human body. According to the free radical theory of human body aging and disease occurrence, the human body aging and disease occurrence is a process that oxidative free radicals continuously damage nucleic acid, protein, cells and organism tissues and is a process that active oxygen oxidation products are continuously accumulated. Numerous medical studies and clinical trials have demonstrated that: free radicals are electron-deficient structures that compete for electrons everywhere when they accumulate in large amounts in the body, and if electrons are removed from cellular protein molecules, the proteins are alkylated with branched chains to form aberrant molecules that are carcinogenic. This can cause damage to normal cells and tissues and even genetic mutations, which can lead to a variety of diseases and pathological processes, such as heart disease, senile dementia, parkinson's disease, tumors, etc. 1, 1-diphenyl-2-trinitrophenylhydrazine free radical (DPPH. cndot.) is taken as a stable nitrogen center free radical, and different electron losing conditions are obtained under different pH values, so that different chemical structures are formed. The sensitive detection of DPPH is beneficial to the intervention of free radicals in vivo, blocks the vicious circle of the free radicals and inhibits the generation of diseases, thereby achieving the aim of treating the diseases. Therefore, the DPPH detection method, which is efficient, rapid and sensitive, contributes to human survival and health. Moreover, electrochemical detection technology has the advantages of low cost, high sensitivity, short response time, portability and the like, and is widely favored.
The graphene nano material is formed by sp carbon atoms2In addition, the graphene has the characteristics of large specific surface area, good biocompatibility, easy functionalized modification and the like, which lays the application prospect and position of the graphene in the electrochemical field, and β -cyclodextrin (β -CD) is a three-dimensional annular structure which is formed by 7 glucose units through dehydration condensation and has a conical hollow water barrel shape, and has the characteristics of hydrophobic inner cavity and hydrophilic outer edge,the graphene nano material can provide a hydrophobic binding site like enzyme, and can be used as a host-guest enveloping effect to identify and enrich organic molecules, inorganic ions, gas molecules and the like, the graphene and β -CD with external hydrophilic characteristic form β -CD functionalized graphene through van der Waals force effect, on one hand, the solubility of the graphene in an aqueous solution can be increased, so that the graphene is prevented from being aggregated, on the other hand, the enrichment content of an object to be detected is effectively improved, so that the sensitivity of analysis and detection is improved, because 6 coordination atoms in an Ethylene Diamine Tetraacetic Acid (EDTA) structure have strong chelation on metal ions and the like in an aqueous phase, the EDTA is connected to the surface of the graphene, the enrichment capacity and the conductivity of the graphene nano material on a target object are further enhanced, and the compound EDTA- β -CD-rGO is prepared from the three materials through a hydrothermal method for the first time, and is used for DPPH detection for the first time.
Disclosure of Invention
The invention aims to provide a functionalized graphene compound EDTA- β -CD-rGO and a preparation method thereof, and the prepared compound can be used for electrochemical analysis and detection of free radicals.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a functionalized graphene compound EDTA- β -CD-rGO comprises the following steps:
β -CD and Graphene Oxide (GO) are uniformly dispersed in secondary water, the mixture is stirred for 10-25 minutes and fully mixed, then concentrated ammonia water is added in the stirring process to adjust the pH value of the solution to 9-10, hydrazine hydrate is added and stirred for 5-15 minutes, finally EDTA aqueous solution is added into the mixed system, the mixture is stirred and heated in a water bath at 50-70 ℃ for 3.0-5.0 hours, the mixture is cooled to room temperature, centrifugal washing is carried out, supernatant is removed, precipitates are washed twice by secondary water, and a compound EDTA- β -CD-rGO is obtained, wherein the centrifugation is carried out at the rpm of 00-13000 rpm for 10-30 minutes, and the mass ratio of GO, β -CD, concentrated ammonia water, hydrazine hydrate, EDTA and secondary water is 2.5:7-9:80-100:15-25:120 and 180: 7-8.
The preferable mass ratio of GO, β -CD, concentrated ammonia water, hydrazine hydrate, EDTA and secondary water is 2.5:8:90:20:154: 8.
The heating temperature of the water bath in the step is preferably 60 ℃, the heating time is preferably 3.5 hours, and the stirring is continuously carried out.
The preferred conditions for centrifugation in said step are centrifugation at 12000rpm for 20 min.
The prepared compound EDTA- β -CD-rGO can be applied to detection of free radicals, the compound EDTA- β -CD-rGO is firstly modified on the surface of a polished glassy carbon electrode, and the EDTA- β -CD-rGO modified electrode (EDTA- β -CD-rGO/GCE) is obtained after natural drying and is used for detecting a target object under optimized conditions, wherein the target object is DPPH.
Compared with the prior art, the EDTA- β -CD-rGO is prepared by a simple one-step hydrothermal method, the electrode prepared by the material can be applied to detecting free radicals, the excellent conductivity, large specific surface area, strong chelating capacity and host-guest envelope recognition and enrichment capacity of the rGO, the EDTA and the β -CD are fully utilized, the synthesized EDTA- β -CD-rGO shows stronger electrochemical behavior, higher electronic conductivity and larger surface area, and a simple and rapid detection means with high sensitivity and low detection line is provided for detecting DPPH.
Drawings
FIG. 1 is a characterization diagram of EDTA- β -CD-rGO material prepared by the invention, wherein A in FIG. 1 is a visible-ultraviolet spectrum of EDTA- β -CD-rGO, B in FIG. 1 is a near infrared spectrum of EDTA- β -CD-rGO, C in FIG. 1 is a scanning electron microscope diagram of β -CD-rGO, D in FIG. 1 is a scanning electron microscope diagram of EDTA- β -CD-rGO, E in FIG. 1 is an X-ray photoelectron energy spectrum diagram of β -CD-rGO, and F in FIG. 1 is an X-ray photoelectron energy spectrum diagram of EDTA- β -CD-rGO.
FIG. 2 shows EDTA- β -CD-rGO/GCE and other comparative materials prepared by the present invention in the presence of 10-6mol·L- 1Differential Pulse Voltammetry (DPV) curves in DPPH · phosphoric acid-methanol (pH 7.0) electrolyte.
FIG. 3 is a DPV curve of EDTA- β -CD-rGO/GCE prepared according to the present invention with different amounts of DPPH.added.
Detailed Description
The technical solution according to the invention is explained in further detail below with reference to embodiments and the accompanying drawings, which are not to be construed as limiting the technical solution according to the invention.
Example 1 procedure for the preparation of EDTA- β -CD-rGO:
(1) firstly, synthesizing graphite oxide by an improved Hummers method, weighing 10mg of prepared graphite oxide, placing the graphite oxide in 10mL of secondary water for ultrasonic dispersion, and obtaining 1.0mg/mL of Graphene Oxide (GO) suspension;
(2) 2.0mL of β -CD (4.0mg/mL) and 2.5mL of GO (1.0mg/mL of the graphene oxide suspension in the step 1) are fully stirred and mixed uniformly (stirred for 10 minutes), 100 mu L of ammonia water is added during stirring and stirring is continued for 10 minutes, then 80% of 20 mu L of hydrazine hydrate is added into the reaction solution, after stirring is continued for 10 minutes, 43.94mg/mL of 3.5mL of EDTA (prepared by dissolving 0.1538g of EDTA in 3.5mL of water) is added, secondary water is added until the reaction system is 10mL, then the mixed solution is transferred to a water bath and reacted for 3.5 hours at the temperature of 60 ℃ to obtain a black suspension.
(3) Standing the reaction product, cooling to room temperature, and centrifuging at 12000rpm for 20 minutes; and centrifuging and washing the obtained black precipitate twice with secondary water, and finally, using the secondary water to prepare the prepared material into 1.0mg/mL suspension, and placing the suspension into a refrigerator at 4 ℃ for later use.
The visible-ultraviolet spectrum of the prepared EDTA- β -CD-rGO material is shown in figure 1A, the ultraviolet visible absorption of graphene oxide has strong absorption at 230nm, and a shoulder peak exists at 290-300 nm, the absorption peak is obviously observed in curves of β -CD-rGO and EDTA- β -CD-rGO and is red-shifted to 269nm, and the reduction of the graphene oxide is proved, figure 1B is the infrared spectrum of EDTA- β -CD-rGO, and is 1095cm-1And 1050cm-1Wave number represents the stretching vibration and bending vibration of N-H, and the vibration is-NH from EDTA and β -CD2，1396cm-1and 1406cm-1Respectively represent the stretching vibration of C-N bond in the material, 1633cm-1To further illustrate the synthesis of the material, the material was characterized by scanning electron microscopy and X-ray photoelectron spectroscopy, and the transmission of the prepared β -CD-rGO and EDTA- β -CD-rGO was determinedThe electron microscopy images, see fig. 1C and 1D, show that the reduced graphene is thin and soft and smooth in texture, and that the addition of EDTA and β -CD deepens and roughens the surface wrinkles, as well as the XPS images of fig. 1E and 1F, clearly observe the C1s absorption peaks from graphene and the N1s absorption peaks from EDTA, β -CD.
Example 3 the electrode prepared in example 2 was used to detect DPPH, specifically:
the EDTA- β -CD-rGO modified Glassy Carbon Electrode (GCE) is taken as a Working Electrode (WE), a saturated calomel electrode is taken as a Reference Electrode (RE), a platinum wire is taken as a Counter Electrode (CE) to form a three-electrode system, and the three-electrode system is immersed in 0.1mM phosphoric acid-methanol electrolyte, before electrochemical testing is carried out, the electrode is calibrated, and fig. 2 shows that compared with other material modified glassy carbon electrodes, the EDTA- β -CD-rGO modified glassy carbon electrode has the highest catalytic oxidation current and has a better peak shape, which shows that the EDTA- β -CD-rGO plays roles in enriching, conducting and amplifying signals, thereby enhancing the sensitivity of analysis and detection.
Taking DPPH as an example, the detection conditions are optimized, and the quantitative analysis of the target substance is realized, FIG. 3 is a DPV curve of EDTA- β -CD-rGO prepared by the invention when different amounts of DPPH are added, and the curve is shown in 10-8～0.01mol·L-1In the range of (1), the oxidation peak current of DPPH & has a good linear relationship with the concentration, and the equation is as follows: ip 9.2396+83.5996logc (R)20.9981) with a detection limit of 3 nmol.l-1The method has the advantages of wide linear range, high sensitivity, and sensitive detection of DPPH by using the material, and the EDTA- β -CD-rGO prepared by the method is simpler and more environment-friendly in preparation, higher in repeatability, stronger in operability and high in sensitivity of DPPH detection.
Claims (9)
1. A preparation method of a functionalized graphene compound EDTA- β -CD-rGO is characterized by comprising the following steps:
β -CD and Graphene Oxide (GO) are uniformly dispersed in secondary water, the mixture is stirred for 10-25 minutes and fully mixed, then concentrated ammonia water is added in the stirring process to adjust the pH value of the solution to 9-10, hydrazine hydrate is added and stirred for 5-15 minutes, finally EDTA aqueous solution is added into the mixed system, the mixture is stirred and heated in a water bath at 50-70 ℃ for 3.0-5.0 hours, the mixture is cooled to room temperature, centrifugal washing is carried out, supernatant is removed, precipitates are washed twice by secondary water, and a compound EDTA- β -CD-rGO is obtained, wherein the centrifugation is carried out at the rpm of 00-13000 rpm for 10-30 minutes, and the mass ratio of GO, β -CD, concentrated ammonia water, hydrazine hydrate, EDTA and secondary water is 2.5:7-9:80-100:15-25:120 and 180: 7-8.
2. The method for preparing EDTA- β -CD-rGO according to claim 1, wherein the mass ratio of GO, β -CD, concentrated ammonia water, hydrazine hydrate, EDTA and secondary water in the step is 2.5:8:90:20:154: 8.
3. The method of preparing EDTA- β -CD-rGO of claim 1, wherein the water bath heating temperature is 60 ℃ and the heating time is 3.5 h.
4. The method of preparing EDTA- β -CD-rGO of claim 1, wherein said centrifugation is at 12000rpm for 20 min.
5. EDTA- β -CD-rGO prepared according to the process of any one of claims 1 to 4.
6. A modified glassy carbon electrode, wherein the EDTA- β -CD-rGO of claim 5 is modified on the glassy carbon electrode.
7. The method of claim 6, comprising the steps of dispersing the EDTA- β -CD-rGO of claim 5 into 1mg/mL black uniform suspension with deionized water, dropping the suspension on the glassy carbon electrode, and drying naturally to obtain the modified electrode (EDTA- β -CD-rGO/GCE).
8. The modified glassy carbon electrode of claim 6 for use in free radical detection.
9. The modified glassy carbon electrode of claim 8, wherein the free radical is DPPH.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102183557A (en) * | 2011-01-22 | 2011-09-14 | 青岛大学 | Preparation method of cyclodextrin functionalized graphene |
| CN103675064A (en) * | 2013-12-18 | 2014-03-26 | 天津工业大学 | Preparation of EDTA (ethylene diamine tetraacetic acid) functionalized graphene modified electrode and heavy metal detection method thereof |
| CN109613081A (en) * | 2018-11-23 | 2019-04-12 | 天津科技大学 | A kind of detection junket amine molecule electrochemical sensor and its preparation method and application |
| WO2020034141A1 (en) * | 2018-08-16 | 2020-02-20 | 中国科学院宁波材料技术与工程研究所 | Graphene nano-container-based coating material and self-repairing coating layer, preparation method therefor, and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102183557A (en) * | 2011-01-22 | 2011-09-14 | 青岛大学 | Preparation method of cyclodextrin functionalized graphene |
| CN103675064A (en) * | 2013-12-18 | 2014-03-26 | 天津工业大学 | Preparation of EDTA (ethylene diamine tetraacetic acid) functionalized graphene modified electrode and heavy metal detection method thereof |
| WO2020034141A1 (en) * | 2018-08-16 | 2020-02-20 | 中国科学院宁波材料技术与工程研究所 | Graphene nano-container-based coating material and self-repairing coating layer, preparation method therefor, and application thereof |
| CN109613081A (en) * | 2018-11-23 | 2019-04-12 | 天津科技大学 | A kind of detection junket amine molecule electrochemical sensor and its preparation method and application |
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