CN103592350B - Melanin nanoparticle-graphene electrochemical sensor as well as preparation method and application thereof - Google Patents
Melanin nanoparticle-graphene electrochemical sensor as well as preparation method and application thereof Download PDFInfo
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- CN103592350B CN103592350B CN201310600457.1A CN201310600457A CN103592350B CN 103592350 B CN103592350 B CN 103592350B CN 201310600457 A CN201310600457 A CN 201310600457A CN 103592350 B CN103592350 B CN 103592350B
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Abstract
The invention discloses a melanin nanoparticle-graphene electrochemical sensor. The sensor mainly comprises a glassy carbon electrode and a melanin nanoparticle-graphene sensitive film, wherein the surface of the carbon electrode is coated with the melanin nanoparticle-graphene sensitive film; the invention further discloses a preparation method of the electrochemical sensor modified on the basis of a melanin nanoparticle-graphene nanometer composite material; the electrochemical sensor is used for simultaneously and sensitively detecting guanine and adenine. The preparation material of the electrochemical sensor is a full-solid-state inorganic nanometer material harmless to human bodies and without polluting environment, the preparation method is simple and quick, and low in cost. The prepared electrochemical sensor has the advantages of good stability, high sensitivity, good reproducibility and the like. The simultaneous and sensitive detection to the guanine and the adenine can be achieved by using the sensor; the detecting limits of the two are respectively reach 1*10 minus 7 mol/L and 5*10 minus 8 mol/L; the differences of oxidation spike potentials of the two reaches 0.316 V.
Description
Technical field
The present invention relates to electrochemical sensor field and Electroanalytical Chemistry field, be specially a kind of melanin Nano microsphere-Graphene electrochemical sensor and preparation method thereof and application.
Background technology
The DNA (deoxyribonucleic acid) in vivo storage of hereditary information and the biosynthesizing aspect of protein plays vital effect.Guanine (Guanine) and adenine (Adenine) are the important component parts of DNA (deoxyribonucleic acid), all play an important role in the life processes such as cellular energy transfer and enzymatic signal transmission.They affect the control of blood flow in coronary artery and Brain circlulation, ARR prevention, the release of inhibitory neurotransmitter and the modulation of adenylate cyclase activity widely.The ANOMALOUS VARIATIONS of guanine and adenine shows immune defect and sudden change in organism, and may cause producing various disease.The concentration level of guanine and adenine is the important parameter responded for assessment of cancer and AIDS diagnosis, cardiac muscle cell's energy state, progression of disease and treatment.Therefore the quantitative determination and analysis of guanine and adenine all seems most important.
At present, the quantitative detecting method of bibliographical information purine bases mainly contains high performance liquid chromatography, Capillary Electrophoresis.The methods such as spectroscopic methodology, chemiluminescence, mass spectrum.But these methods not only waste time and energy, complex operation, general sensitivity is not high, and needs special instrument and equipment and expensive reagent.Electrochemical sensing technology have instrument simply inexpensive, measure quick and precisely, method is sensitive, accuracy is high, selectivity and reappearance better, stability and antijamming capability is strong, sample does not need, through advantages such as pre-service can directly measure, to have broad application prospects.Therefore, develop the electrochemical sensing new method that simple, quick, high-sensitive purine bases quantitatively detect and seemed very urgent.
Graphene is a kind of Two-dimensional Carbon nano material of novel individual layer atomic thickness, and it is by sp
2six side's honeycomb two-dimensional structures of the individual layer that hydbridized carbon atoms is formed.The special construction of Graphene makes it show the character of many excellences, as good electric conductivity, larger surface area, chemistry and physical stability and stronger physical strength, it also has the advantages such as with low cost, processibility is strong simultaneously, makes it have wide doing something for the occasion in fields such as conductive material, catalysis material, energy storage material and nano electron devices.At present, the report much based on graphene nanocomposite material technology of preparing and application thereof is had.
Melanin is the XC polymer be extensively present in biosome, and has unique function, mainly comprises: protection human body and animal from ultraviolet injury, antibacterial, temperature regulates, free radical quencher and participate in some neural activities.The gluey Nano microsphere of melanin is made up of the dopamine-melanin of Nature creating completely, and its synthetic method is simply efficient.The gluey Nano microsphere of melanin and naturally occurring melanin have many similarities in character and configuration aspects, less to the toxic and side effect of human body, have therefore become the effective ways for the treatment of live body cancer cell.Existing bibliographical information, the gluey Nano microsphere of melanin can be used as the photo-thermal therapy of effective near infrared light heat cure reagent for cancer in human body, has vital role in its early diagnosis in cancer and effective treatment.But the electrochemical properties research of the gluey Nano microsphere of melanin is not almost reported.
Therefore, a kind of advantages by gluey for melanin Nano microsphere and Graphene is provided to get up gluey for melanin Nano microsphere-graphene nanometer composite, use it for structure novel electrochemical sensor, simultaneously for guanine and adenine quick, detect simultaneously, and improve the electrochemical sensor of detection sensitivity, be a good problem to study.
Summary of the invention
In order to overcome above-mentioned deficiency of the prior art, the invention provides and a kind ofly can detect high-sensitive solid-state electrochemical sensor of guanine and adenine and preparation method thereof simultaneously.
The object of the present invention is achieved like this:
A kind of melanin Nano microsphere-Graphene electrochemical sensor, comprise the sensitive membrane that glass-carbon electrode and surface thereof scribble, glass-carbon electrode substrate surface scribbles melanin Nano microsphere-graphene nanocomposite material sensitive membrane.
The preparation method of described melanin Nano microsphere-Graphene sensitive membrane is: take that the Graphene solid of the melanin Nano microsphere solid of 1 ~ 10 mg and 1 ~ 10 mg is ultrasonic to be dispersed in the redistilled water of 10 ~ 20 mL.
Described melanin Nano microsphere-Graphene electrochemical sensor, is characterized in that its preparation method, comprises the following steps:
(1) pretreatment of glassy carbon electrode;
(2) melanin Nano microsphere and Graphene solid are dissolved in redistilled water obtain through ultrasonic disperse the uniform dispersion that concentration is 0.1 ~ 1 mg/mL;
(3) the finely dispersed melanin Nano microsphere-graphene dispersion drop obtained in step (2) is coated onto glassy carbon electrode surface pretreated in step (1), nitrogen fluidized drying obtains melanin Nano microsphere-graphene nano material modified glassy carbon electrode.
In step (1), pretreatment of glassy carbon electrode process is: polish to glass-carbon electrode with burnishing powder, then in absolute ethyl alcohol and redistilled water, carry out ultrasonic cleaning.
In step (2), the concentration of melanin Nano microsphere-graphene dispersing solution is 0.1 ~ 1 mg/mL, and dripping the volume being coated onto the melanin Nano microsphere-graphene dispersing solution of glassy carbon electrode surface is 5 ~ 10 microlitres.
Sensor can be used for simultaneously, highly sensitive detection guanine and adenine, and measuring medium is 0.1 mol/L acetate buffer solution (pH 4.5); Adopt differential pulse voltammetry (DPV), its location parameter is: pulse-response amplitude 0.05 V, recurrence interval 0.5 s, electric potential scanning scope: 0.5 ~ 1.5 V.
Positive beneficial effect:
(1) use cheap material with carbon element to prepare electrode sensitive material, it is all solid state for preparing material, to human non-toxic, environmentally safe;
(2) adopt melanin Nano microsphere-graphene nanometer composite as sensitive material, highly sensitive sensitive membrane can be obtained, achieve the Simultaneously test of guanine and adenine;
(3) sensor stability prepared is good, highly sensitive, selectivity is good, be easy to carry, cost is lower;
(4) detection limit of guanine and adenine reaches 1 × 10 respectively
-7mol/L and 5 × 10
-8mol/L, the difference of the two oxidation peak current potential reaches 0.316 V.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of melanin Nano microsphere;
Fig. 2 is the scanning electron microscope (SEM) photograph of melanin Nano microsphere-graphene nanometer composite;
Fig. 3 is guanine and the differential pulse voltammetry figure of adenine on different modifying electrode;
The wherein curve a differential pulse voltammetry figure that is naked glass-carbon electrode to guanine and adenine Simultaneously test, curve b is the differential pulse voltammetry figure of glass-carbon electrode to guanine and adenine Simultaneously test of graphene modified, curve c be the glass-carbon electrode modified of melanin Nano microsphere to guanine and adenine Simultaneously test differential pulse voltammetry figure, curve d be the glass-carbon electrode modified of melanin Nano microsphere-graphene nanometer composite to guanine and adenine Simultaneously test differential pulse voltammetry figure.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further:
A kind of melanin Nano microsphere-Graphene electrochemical sensor, comprise the sensitive membrane that glass-carbon electrode and surface thereof scribble, glass-carbon electrode substrate surface scribbles melanin Nano microsphere-graphene nanocomposite material sensitive membrane.
The preparation method of described melanin Nano microsphere-Graphene sensitive membrane is: take that the Graphene solid of the melanin Nano microsphere solid of 1 ~ 10 mg and 1 ~ 10 mg is ultrasonic to be dispersed in the redistilled water of 10 ~ 20 mL.
Described melanin Nano microsphere-Graphene electrochemical sensor, is characterized in that its preparation method, comprises the following steps:
(1) pretreatment of glassy carbon electrode;
(2) melanin Nano microsphere and Graphene solid are dissolved in redistilled water obtain through ultrasonic disperse the uniform dispersion that concentration is 0.1 ~ 1 mg/mL;
(3) the finely dispersed melanin Nano microsphere-graphene dispersion drop obtained in step (2) is coated onto glassy carbon electrode surface pretreated in step (1), nitrogen fluidized drying obtains melanin Nano microsphere-graphene nano material modified glassy carbon electrode.
In step (1), pretreatment of glassy carbon electrode process is: polish to glass-carbon electrode with burnishing powder, then in absolute ethyl alcohol and redistilled water, carry out ultrasonic cleaning.
In step (2), the concentration of melanin Nano microsphere-graphene dispersing solution is 0.1 ~ 1 mg/mL, and dripping the volume being coated onto the melanin Nano microsphere-graphene dispersing solution of glassy carbon electrode surface is 5 ~ 10 microlitres.
Sensor can be used for simultaneously, highly sensitive detection guanine and adenine, and measuring medium is 0.1 mol/L acetate buffer solution (pH 4.5); Adopt differential pulse voltammetry (DPV), its location parameter is: pulse-response amplitude 0.05 V, recurrence interval 0.5 s, electric potential scanning scope: 0.5 ~ 1.5 V.
embodiment 1
Melanin Nano microsphere-Graphene electrochemical sensor of the present invention, comprise the sensitive membrane that glass-carbon electrode and surface thereof scribble, glass-carbon electrode substrate surface scribbles dopamine-melanin Nano microsphere sensitive membrane;
Melanin Nano microsphere-Graphene sensitive membrane is obtained by the melanin Nano microsphere solid of 1 mg and ultrasonic being dispersed in the redistilled water of 20 mL of 1 mg Graphene solid;
Melanin Nano microsphere-Graphene electrochemical sensor preparation method: melanin Nano microsphere and Graphene solid are dissolved in redistilled water and obtains through ultrasonic disperse the uniform dispersion that concentration is 0.1 mg/mL, after pretreatment of glassy carbon electrode, the melanin of 5 microlitres Nano microsphere-graphene dispersion drop is coated onto its surface, nitrogen fluidized drying obtains melanin Nano microsphere-graphene nanometer composite modified glassy carbon electrode.
embodiment 2
Melanin Nano microsphere-Graphene electrochemical sensor of the present invention, comprise the sensitive membrane that glass-carbon electrode and surface thereof scribble, glass-carbon electrode substrate surface scribbles dopamine-melanin Nano microsphere sensitive membrane;
Melanin Nano microsphere-Graphene sensitive membrane is obtained by the melanin Nano microsphere solid of 5 mg and ultrasonic being dispersed in the redistilled water of 20 mL of 5 mg Graphene solid;
Melanin Nano microsphere-Graphene electrochemical sensor preparation method: melanin Nano microsphere and Graphene solid are dissolved in redistilled water and obtains through ultrasonic disperse the uniform dispersion that concentration is 0.5 mg/mL, after pretreatment of glassy carbon electrode, the melanin of 8 microlitres Nano microsphere-graphene dispersion drop is coated onto its surface, nitrogen fluidized drying obtains melanin Nano microsphere-graphene nanometer composite modified glassy carbon electrode.
embodiment 3
Melanin Nano microsphere-Graphene electrochemical sensor of the present invention, comprise the sensitive membrane that glass-carbon electrode and surface thereof scribble, glass-carbon electrode substrate surface scribbles dopamine-melanin Nano microsphere sensitive membrane;
Melanin Nano microsphere-Graphene sensitive membrane is obtained by the melanin Nano microsphere solid of 10 mg and ultrasonic being dispersed in the redistilled water of 20 mL of 10 mg Graphene solid;
Melanin Nano microsphere-Graphene electrochemical sensor preparation method: melanin Nano microsphere and Graphene solid are dissolved in redistilled water and obtains through ultrasonic disperse the uniform dispersion that concentration is 1 mg/mL, after pretreatment of glassy carbon electrode, the melanin of 10 microlitres Nano microsphere-graphene dispersion drop is coated onto its surface, nitrogen fluidized drying obtains melanin Nano microsphere-graphene nanometer composite modified glassy carbon electrode.
embodiment 4
The sign of melanin Nano microsphere: Fig. 1 is the scanning electron microscope (SEM) photograph of melanin Nano microsphere, and as can be seen from Fig., the melanin Nano microsphere of preparation is the chondritic that particle diameter is about about 200 nm.Fig. 2 is the scanning electron microscope (SEM) photograph of melanin Nano microsphere-graphene nanocomposite material, and as can be seen from Fig., the gluey Nano microsphere of spherical melanin is embedded in the schistose texture of Graphene closely, illustrates and has successfully prepared nano composite material.
embodiment 5
As shown in Figure 3, melanin Nano microsphere-Graphene electrochemical sensor of the present invention is used for simultaneously, Sensitive Detection guanine and adenine, and measuring medium is 0.1 mol/L acetate buffer solution (pH 4.5); Adopt differential pulse voltammetry (DPV), its location parameter is: pulse-response amplitude 0.05 V, recurrence interval 0.5 s, electric potential scanning scope: 0.5 ~ 1.5 V.
The wherein curve a differential pulse voltammetry figure that is naked glass-carbon electrode to guanine and adenine Simultaneously test, curve b is the differential pulse voltammetry figure of glass-carbon electrode to guanine and adenine Simultaneously test of graphene modified, curve c be the glass-carbon electrode modified of melanin Nano microsphere to guanine and adenine Simultaneously test differential pulse voltammetry figure, curve d be the glass-carbon electrode modified of melanin Nano microsphere-graphene nanometer composite to guanine and adenine Simultaneously test differential pulse voltammetry figure.
As we know from the figure, relative to the glass-carbon electrode that naked glass electrode, Graphene and melanin Nano microsphere are modified, guanine and the adenine electrochemical response on the glass-carbon electrode of melanin Nano microsphere-graphene complex modification obtains significant raising, peak shape is best, the difference of the two oxidation peak current potential reaches 0.316 V, illustrates that this modified electrode detects while can be used for guanine and adenine.
Above embodiment is only for illustration of the preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; in the ken that described exercising ordinary skill possesses; the any amendment done within the spirit and principles in the present invention, equivalent to substitute and improvement etc., it all should be encompassed within the technical scheme scope of request of the present invention protection.
Claims (6)
1. melanin Nano microsphere-Graphene electrochemical sensor, comprises the sensitive membrane that glass-carbon electrode and surface thereof scribble, it is characterized in that: the sensitive membrane that glass-carbon electrode substrate surface scribbles is melanin Nano microsphere-graphene composite material sensitive membrane.
2. a kind of melanin Nano microsphere-Graphene electrochemical sensor according to claim 1, it is characterized in that, the preparation method of described melanin Nano microsphere-graphene composite material sensitive membrane is: take that the Graphene solid of the melanin Nano microsphere solid of 1 ~ 10 mg and 1 ~ 10 mg is ultrasonic to be dispersed in the redistilled water of 10 ~ 20 mL.
3., as required a kind of melanin Nano microsphere-Graphene electrochemical sensor as described in 1, it is characterized in that its preparation method, comprising the following steps:
(1) pretreatment of glassy carbon electrode;
(2) melanin Nano microsphere and Graphene solid are dissolved in redistilled water obtain through ultrasonic disperse the uniform dispersion that concentration is 0.1 ~ 1 mg/mL;
(3) the finely dispersed melanin Nano microsphere-graphene dispersion drop obtained in step (2) is coated onto glassy carbon electrode surface pretreated in step (1), nitrogen fluidized drying obtains melanin Nano microsphere-graphene nano material modified glassy carbon electrode.
4. the preparation method of a kind of melanin Nano microsphere-Graphene electrochemical sensor according to claim 3, it is characterized in that: in described step (1), pretreatment of glassy carbon electrode process is: polish to glass-carbon electrode with burnishing powder, then in absolute ethyl alcohol and redistilled water, carry out ultrasonic cleaning.
5. the preparation method of a kind of melanin Nano microsphere-Graphene electrochemical sensor according to claim 3, it is characterized in that: in described step (2), the concentration of melanin Nano microsphere-graphene dispersing solution is 0.1 ~ 1 mg/mL, dripping the volume being coated onto the melanin Nano microsphere-graphene dispersing solution of glassy carbon electrode surface is 5 ~ 10 microlitres.
6. a kind of melanin Nano microsphere-Graphene electrochemical sensor as claimed in claim 1, is characterized in that it is applied: for simultaneously, Sensitive Detection guanine and adenine, and measuring medium is 0.1 mol/L acetate buffer solution, and pH is 4.5; Adopt differential pulse voltammetry (DPV), its location parameter is: pulse-response amplitude 0.05 V, recurrence interval 0.5 s, electric potential scanning scope: 0.5 ~ 1.5 V.
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CN105784686B (en) * | 2016-03-16 | 2018-08-03 | 济南大学 | A kind of preparation method and application of the hydrogen peroxide optical electro-chemistry sensor based on electrochemical luminescence excitation |
CN105784687B (en) * | 2016-03-16 | 2018-03-27 | 济南大学 | A kind of preparation method and application based on spontaneous light activated hydrogen peroxide optical electro-chemistry sensor |
CN111733472B (en) * | 2020-06-01 | 2023-04-04 | 中科悦达(上海)材料科技有限公司 | Composite material composed of graphene and melanin and preparation method and application thereof |
CN112331864A (en) * | 2020-10-23 | 2021-02-05 | 同济大学 | Biological melanin/graphene composite material and preparation method and application thereof |
CN112349917B (en) * | 2020-10-23 | 2022-07-26 | 同济大学 | Melanin/graphene nanocomposite material for improving electron transfer efficiency and preparation method and application thereof |
CN112858424B (en) * | 2020-12-31 | 2023-05-23 | 广东省现代农业装备研究所 | Preparation method of compound modified electrode for simultaneously detecting lead and cadmium ions |
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CN102914580A (en) * | 2012-10-27 | 2013-02-06 | 信阳师范学院 | Silver-poly dopamine-graphene-modified electrochemical sensor and preparation method thereof |
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CN102914580A (en) * | 2012-10-27 | 2013-02-06 | 信阳师范学院 | Silver-poly dopamine-graphene-modified electrochemical sensor and preparation method thereof |
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