The preparation of molecular engram sensor based on the chitosan-modified glass-carbon electrode of carbon dots-and
Using
Technical field
The invention belongs to electrochemical sensor preparation technical field, it is related to preparing the sensor of no enzyme detection glucose, especially
It is related to a kind of preparation method and application of molecular engram sensor based on the chitosan-modified glass-carbon electrode of carbon dots-.
Background technique
In recent years, as countries in the world, Chinese diabetes prevalence is being gradually increasing, and diabetes are strong to our people
The influence of health is on the rise.Though China belongs to the low illness rate country of diabetes in the world, the world number Yi Ju of diabetic
Second is increased speed surprising.Therefore, the concentration for rapidly and efficiently detecting glucose in blood of human body, it is aobvious to the diagnosis of diabetes
It obtains particularly important.
The method of detection glucose has much at present, such as spectrophotometry, colorimetric method and chromatography, these methods are not only
It is laborious time-consuming, and sensitivity is lower.Electrochemica biological sensor structure is simple, easy to operate, and method is simple, quickly in real time,
With higher sensitivity and selectivity, it is easy to minimize, micromation.Wherein without enzyme electrochemical sensor due to active material pair
The non-specific electrocatalysis of analyte causes the selectivity of sensor to be deteriorated.It is using molecular imprinting technology that its is distinctive
It is highly selective to combine with electrochemical sensor, the molecular engram sensing for having specific recognition to respond glucose can be prepared
Device.
The carbon nanomaterial that fluorescent carbon point goes out as new exploration in recent years, is a kind of particle that form is spherical in shape, size is general
All within 10nm, surface typically contains a large amount of oxygen-containing group, can make it with different synthetic method and surface treatment mode
The oxygen content on surface generates difference.In addition to this, the discontinuous transmitting due to fluorescent carbon point with fluorescence, discrete, fluorescent stabilization
Property it is high, the small toxicity of partial size is low the features such as, Pu is once being found to receive great attention.Chitosan is the natural polysaccharide of green non-pollution
Macromolecule is extremely promising natural polymer membrane material, has good fibre forming property.With carbon dots-chitosan solution pair
Electrode is modified, its optical property is preferably improved, and binding molecule engram technology realizes the rapidly and efficiently inspection to glucose
It surveys.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, a kind of poly- based on carbon dots-shell it is an object of the invention to disclose
The preparation method of the molecular engram sensor of sugar-modified glass-carbon electrode.
The present invention prepares environmentally friendly carbon quantum dot solution using biological material, with carbon quantum dot-chitosan solution
Glass-carbon electrode is modified;Then poly- in carbon dots-shell by electrochemical polymerization method using 3- amino phenyl boric acid as function monomer
The molecular engram sensor that the glassy carbon electrode surface preparation of sugar-modified mistake has specific recognition to respond template molecule glucose.
A kind of preparation method of the molecular engram sensor based on the chitosan-modified glass-carbon electrode of carbon dots-, including walk as follows
It is rapid:
A) pure cotton material and distilled water are placed in closed reaction vessel, 180~220 DEG C of 12~18h of laser heating, it is cooling
To room temperature, the solution of carbon quantum dot can be obtained, wherein the mass ratio of the pure cotton material and distilled water is 1:40~1:80,
It is preferred that 1:60;
B) solution containing carbon dots is filtered, be centrifuged, dialysed and is freeze-dried to get solid state fluorescence carbon quantum dot;
C) it by solid state fluorescence carbon quantum dot, is mixed with 1% chitosan-acetic acid solution, drop coating is in processed glass-carbon electrode table
Face is placed in 60 DEG C of baking ovens dry 30min, up to modified electrode after being cooled to room temperature, wherein the carbon quantum dot and chitosan
The solid-to-liquid ratio of solution is 1mg:1mL~5mg:1mL, and preferably 3mg:1mL, drop coating amount is 5~20 μ L, preferably 9 μ L;
D) glucose, 3- amino phenyl boric acid and borate buffer solution being added to the container, stirring is allowed to uniformly mixed at room temperature,
Wherein the molar ratio of glucose, 3- amino phenyl boric acid and borax is 1:0.5:40~1:2:40, preferably 1:1:40;
E) modified electrode prepared by step c) is placed in above-mentioned system, pH is 8~11, and preferable ph 9 utilizes electrification
Method polymerization film formation;
F) use inorganic acid eluent by template molecule elution to get molecular engram sensor.
The more excellent disclosed example of the present invention, laser heating 15h at 200 DEG C of temperature described in step a).
The more excellent disclosed example of the present invention, the treated glass-carbon electrode of step c), respectively with 0.3 μm and 0.05 μm of α-oxygen
After change aluminium paste liquid polishes glass-carbon electrode, successively it is cleaned by ultrasonic in distilled water, ethyl alcohol and distilled water, naturally dry.
The more excellent disclosed example of the present invention, eluent described in step f) be hydrochloric acid or sulfuric acid, 0.05~1.0 mol/L of concentration,
It is preferred that 0.1mol/L hydrochloric acid.
The more excellent disclosed example of the present invention, electrochemical method described in step f), design parameter are as follows: in the current potential model of 0~1.5V
In enclosing, with 50mV s-1Sweep speed cyclic voltammetry scan 250 enclose.
Another object of the present invention is that prepared sensor is that have to glucose specifically according to linear fit
Property identification response molecular engram sensor, the glucose detection that can be used under physiological condition.
Beneficial effect
The invention discloses environmentally friendly carbon quantum dot solution is prepared using biological material, gathered with carbon quantum dot-shell
Sugar juice modifies glass-carbon electrode;Then using 3- amino phenyl boric acid as function monomer, by electrochemical polymerization method in carbon
The preparation of point-chitosan-modified mistake glassy carbon electrode surface passes the molecular engram that template molecule glucose has specific recognition to respond
Sensor.It is environmentally protective with carbon quantum dot-chitosan solution modified electrode, significantly improve the chemical property of electrode.In conjunction with point
Sub- engram technology, prepare to glucose have specific recognition respond molecular engram sensor, have it is easy to operate, it is at low cost
Honest and clean, selectivity and the advantages that high sensitivity is expected to practical.
Detailed description of the invention
Cyclic voltammogram of Fig. 1 modified electrode in potassium ferricyanide solution :(a) glass-carbon electrode, (b) carbon quantum dot-shell are poly-
Molecular imprinting modification electrode and (e) absorption 20 after molecular imprinting modification electrode that sugar-modified electrode, (c) are not eluted, (d) elution
The molecular imprinting modification electrode of μM glucose.
The anti-interference capability testing figure of Fig. 2 molecular imprinting electrochemical sensor.
Electrochemical response of Fig. 3 molecular imprinting electrochemical sensor to different glucose: (A) differential pulse voltammetry
Method detects the glucose of various concentration and the linear relationship of (B) concentration of glucose and electrochemical signals.The concentration of glucose is distinguished
For 0.5,5,10,20,30,40,50,100,200,400 and 600 μm of ol/L.
Specific embodiment
The following describes the present invention in detail with reference to examples, so that those skilled in the art more fully understand this hair
It is bright, but the invention is not limited to following embodiments.
Embodiment 1
A) preparation of modified electrode: the pure cotton material of mass ratio 1:40 and distilled water are placed in closed reaction vessel,
12h is heated at 180 DEG C, is cooled to room temperature, the solution of carbon quantum dot can be obtained.Solution containing carbon dots is filtered, is centrifuged,
Dialysis and freeze-drying are to get solid state fluorescence carbon quantum dot.1mg carbon quantum dot is mixed with 1mL chitosan solution example, 5 μ of drop coating
L is placed in 60 DEG C of baking ovens dry 30min, up to modified electrode after being cooled to room temperature in processed glassy carbon electrode surface.
B) preparation of molecular imprinting electrochemical sensor: by glucose, 3- amino phenyl boric acid and borate buffer solution by mole
Than being added to the container for 1:2:40, stirring is allowed to uniformly mixed at room temperature;Modified electrode prepared by step a) is placed in above-mentioned
System, by electrochemical method at pH 8 polymerization film formation.With 0.05mol/L hydrochloric acid eluted template molecule to get molecular engram
Sensor.
Embodiment 2
A) preparation of modified electrode: the pure cotton material of mass ratio 1:50 and distilled water are placed in closed reaction vessel,
14h is heated at 190 DEG C, is cooled to room temperature, the solution of carbon quantum dot can be obtained.Solution containing carbon dots is filtered, is centrifuged,
With freeze-drying to get solid state fluorescence carbon quantum dot.2mg carbon quantum dot is mixed with 1mL chitosan solution example, 10 μ L of drop coating in
Processed glassy carbon electrode surface is placed in 60 DEG C of baking ovens dry 30min, up to modified electrode after being cooled to room temperature.
B) preparation of molecular imprinting electrochemical sensor: by glucose, 3- amino phenyl boric acid and borate buffer solution by mole
Than being added to the container for 1:1.5:40, stirring is allowed to uniformly mixed at room temperature;Modified electrode prepared by step a) is placed in
State system, by electrochemical method at pH 8.5 polymerization film formation.With 0.05mol/L sulfuric acid eluted template molecule to get molecule
Trace sensor.
Embodiment 3
A) preparation of modified electrode: the pure cotton material of mass ratio 1:60 and distilled water are placed in closed reaction vessel,
15h is heated at 200 DEG C, is cooled to room temperature, the solution of carbon quantum dot can be obtained.Solution containing carbon dots is filtered, is centrifuged,
Dialysis and freeze-drying are to get solid state fluorescence carbon quantum dot.3mg carbon quantum dot is mixed with 1mL chitosan solution example, 9 μ of drop coating
L is placed in 60 DEG C of baking ovens dry 30min, up to modified electrode after being cooled to room temperature in processed glassy carbon electrode surface.
B) preparation of molecular imprinting electrochemical sensor: by glucose, 3- amino phenyl boric acid and borate buffer solution by mole
Than being added to the container for 1:1:40, stirring is allowed to uniformly mixed at room temperature;Modified electrode prepared by step a) is placed in above-mentioned
System, by electrochemical method at pH 9 polymerization film formation.With 0.1mol/L hydrochloric acid eluted template molecule to get molecular engram biography
Sensor.
Embodiment 4
A) preparation of modified electrode: the pure cotton material of mass ratio 1:70 and distilled water are placed in closed reaction vessel,
16h is heated at 210 DEG C, is cooled to room temperature, the solution of carbon quantum dot can be obtained.Solution containing carbon dots is filtered, is centrifuged,
Dialysis and freeze-drying are to get solid state fluorescence carbon quantum dot.4mg carbon quantum dot is mixed with 1mL chitosan solution example, drop coating 15
μ L is placed in 60 DEG C of baking ovens dry 30min, up to modified electrode after being cooled to room temperature in processed glassy carbon electrode surface.
B) preparation of molecular imprinting electrochemical sensor: by glucose, 3- amino phenyl boric acid and borate buffer solution by mole
Than being added to the container for 1:0.6:40, stirring is allowed to uniformly mixed at room temperature;Modified electrode prepared by step a) is placed in
State system, by electrochemical method at pH 10 polymerization film formation.With 0.1mol/L sulfuric acid eluted template molecule to get molecule print
Mark sensor.
Embodiment 5
A) preparation of modified electrode: the pure cotton material of mass ratio 1:80 and distilled water are placed in closed reaction vessel,
18h is heated at 220 DEG C, is cooled to room temperature, the solution of carbon quantum dot can be obtained.Solution containing carbon dots is filtered, is centrifuged,
Dialysis and freeze-drying are to get solid state fluorescence carbon quantum dot.5mg carbon quantum dot is mixed with 1mL chitosan solution example, drop coating 20
μ L is placed in 60 DEG C of baking ovens dry 30min, up to modified electrode after being cooled to room temperature in processed glassy carbon electrode surface.
B) preparation of molecular imprinting electrochemical sensor: by glucose, 3- amino phenyl boric acid and borate buffer solution by mole
Than being added to the container for 1:0.5:40, stirring is allowed to uniformly mixed at room temperature;Modified electrode prepared by step a) is placed in
State system, by electrochemical method at pH 11 polymerization film formation.With 1mol/L hydrochloric acid eluted template molecule to get molecular engram
Sensor.
The test experience of glucose
In 5mmol/L K3[Fe(CN)6] and 0.1mol/L KCl mixed liquor in, with carbon dots-shell made from above-described embodiment
Glycan modified glassy carbon electrode is working electrode, and Ag/AgCl/ electrode is reference electrode, and platinum filament is auxiliary electrode.Use electrochemical operation
It stands and detects the electrochemical signals of working electrode, the chemical property compared with before modification of the glass-carbon electrode after discovery modification significantly mentions
It is high;It is detected with differential pulse voltammetry, it was demonstrated that in 0.5~40 μm of ol/L and 50~600 μm of ol/L concentration range, with grape
The increase of sugared concentration, current value are substantially reduced, and detection is limited to 0.09 μm of ol/L(S/N=3).
In Figure of description, test system: cyclic voltammogram of Fig. 1 modified electrode in potassium ferricyanide solution contains
0.1mol/L KCl and 5mmol/L K3[Fe(CN)6] PBS solution (0.05mol/L, pH 7.0), sweep speed: 50
mV/ s。
The anti-interference capability testing figure of Fig. 2 molecular imprinting electrochemical sensor.Test system: KCl containing 0.1mol/L and
5mmol/L K3[Fe(CN)6] PBS solution (0.05mol/L, pH 7.0), sweep speed: 50 mV/ s, it is all to test sample
Product concentration is 20 μm of ol/L.
Electrochemical response of Fig. 3 molecular imprinting electrochemical sensor to different glucose, test system: contains
0.1mol/L KCl and 5mmol/L K3[Fe(CN)6] PBS solution (0.05mol/L, pH 7.0), sweep speed: 50 mV/
s。
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright specification is applied directly or indirectly in other relevant technical fields,
Similarly it is included within the scope of the present invention.