CN102507693A - Functional-material-based glucose biosensor and manufacturing method thereof - Google Patents
Functional-material-based glucose biosensor and manufacturing method thereof Download PDFInfo
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Abstract
The invention relates to a functional-material-based glucose biosensor. A working electrode of the glucose biosensor is made from a graphene nanomaterial, the glucose biosensor is formed by using the working electrode made from the graphene nanomaterial in the assembling of the glucose biosensor, belongs to a quantitative test technology and shows excellent linearity and resolution, and the detection sensitivity, the detection range and the detection speed are increased; and particularly in the concentration range of human blood glucose, the amplitude of a response current can be increased by 50%, and the resolution can be increased by over twice. The functional-material-based glucose biosensor and a preparation method thereof have the advantages that: immobilized enzyme of a nano-functional membrane prepared from the graphene nanomaterial can be continuously analyzed for over 1,000 times, so that the cost for measurement is low, the accuracy of analysis is higher than that of other methods, the relative error reaches about 1%, the response time is shortened to 20 seconds, the service life is also greatly prolonged, the precise timing measurement of the concentration of glucose can be achieved; and the functional-material-based glucose biosensor has the characteristics of high specificity, short-time performance, low-cost analysis, no special requirements on analyzing substances, safety and simplicity and convenience in operation, and convenience for on-site measurement and the like and can be applied to the daily measurement of blood glucose of diabetes patients.
Description
Technical field
The present invention relates to biochemical analysis and detect, specifically is biology sensor, more specifically is based on glucose biological sensor of functionalization material and preparation method thereof.
Background technology
Biology sensor (biosensor) converts the instrument that electric signal detects into to the biological substance sensitivity and with its concentration.Be to make recognition component (comprising bioactivators such as enzyme, antibody, antigen, microorganism, cell, tissue, nucleic acid) and the suitable physics and chemistry transducer (like oxygen electrode, photosensitive tube, FET, piezoelectric crystal or the like) and the analysis tool or the system of signal amplifying apparatus formation by immobilized biological sensitive materials.Biology sensor has the function of receptacle and converter.
Since the sixties in 20th century, enzyme electrode came out, biology sensor had obtained huge development, has become an ingredient that becomes more and more important of enzyme assay.The generation of biology sensor be multi-door subjects such as biology, medical science, galvanochemistry, calorifics, optics and electronic technology intersect each other the infiltration product; Have selectivity height, fast, simple to operate, the lower-price characteristic of analysis speed, obtained in fields such as industrial and agricultural production, environmental protection, food industry, medical diagnosiss using widely.
The advantage of biology sensor is: expense and cost are low, adopt immobilised enzymes to make catalyzer, can repeat repeatedly to use; Selectivity is good, only specific substrate is reacted, and therefore generally need not carry out The pretreatment, disturbs few; Analysis speed is fast, can in l minute, obtain the result usually; Accuracy is high, and general relative error is less than 1%; Operating system is simple, realizes automated analysis easily.
Biology sensor comprises following several types: (one) enzyme sensor is to develop the earliest, also is one type of the most ripe at present biology sensor.It is under the catalytic action of immobilised enzymes, behind the biomolecule generation chemical change, goes out testing concentration thereby change indirect determination through the transducer record.Kind surplus the enzyme sensor of having succeeded in developing in the world at present has 20, wherein the most ripe is glucose sensor.During use enzyme electrode is immersed in the sample solution; Glucose in the solution promptly is diffused on the enzyme membrane, under the glucose oxidase effect of being fixed on the enzyme membrane, generates gluconic acid, simultaneously consume oxygen; Through the variation of oxygen concentration in the oxygen electrode mensuration solution, infer the concentration that glucose in the sample; (2) tissus sensor utilizes that the catalytic action of multienzyme system detects determinand in the animal vegetable tissue.Because what utilized is the enzyme in the tissue, need not artificial purification process, thereby more stable, service time is long; (3) microbiological sensor is fixed on microorganism on the bio-sensitive film, utilizes respiration of microorganism or the enzyme that is contained, and measures the especially material concentration in the sweat of test substance; (4) immunosensor utilizes the high degree of specificity between antigen and the antibody, and antigen (or antibody) is combined on the bio-sensitive film, comes the concentration of corresponding antibodies in the working sample (or antigen); (5) the field effect transistor biology sensor has combined transistor technology, and required enzyme or antibody amount seldom are considered to third generation biology sensor.Practical application at present is few, but development potentiality is huge.
In recent years, the development of biology sensor and exploitation have obtained significant progress, all have potential using value in many industries.Following with the cohesive process of front subjects such as molectronics, biological electronics in, will create sensitiveer more novel biology sensor, and will make biology sensor towards microminiaturized, portability and practicability development.
Chinese patent 99249332.2 has proposed a kind of fixing means of glucose carbohydrate oxidase, and this method is used fixedly glucose carbohydrate oxidase of titania paste, and as the electronics intermedium.This invention is comparatively novel, can use repeatedly, but the titanic oxide electronic transmission effect is excellent unlike the potassium ferricyanide, and sensitivity and accuracy are also limited, and repeatedly use is prone to run into problems such as enzymatic activity keeps, the enzyme body comes off.Chinese patent CN1219676A adopts the two enzyme biologic sensors of disposable bielectron in order to cholesterol in the detection blood and glucose etc., but this type sensor needs the participation of oxygen, and receives the interference that oxygen content changes in the blood easily.
Summary of the invention
The purpose of this invention is to provide glucose biological sensor based on the functionalization material.
Another object of the present invention provides the preparation method based on the glucose biological sensor of functionalization material.
The present invention is based on standard GB 7665-87 to the definition under the sensor is: " can experience specified measuring range and convert the device or the device of available signal according to certain rules to; be made up of sensitive element and conversion element usually " exploitation forms; Its developing principle is based under the effect of glucose oxidase (GOD) film; Glucose generation oxidation reaction, oxygen consumed and generate gluconic acid lactone and hydrogen peroxide.The change of amount of substance can be exchanged into electric signal, and its signal changes available above-mentioned biology sensor and detects.
Glucose biological sensor based on the functionalization material of the present invention, its working electrode is processed by the graphene nano material.
Wherein, the graphene nano material is selected from: palladium nano-particles/graphene composite material, Pt nanoparticle/graphene composite material, gold nano grain/graphene composite material, silver nano-grain/graphene composite material, copper nano particles/graphene composite material, germanium nano particle/graphene composite material, di-iron trioxide nano particle/graphene composite material, ferroferric oxide nano granules/graphene composite material, tin indium oxide nano particle/graphene composite material and tin indium oxide-platinum binary composite nanometer particle/graphene nano compound substance.
Among the present invention, its preparation method of graphene is selected from: the hydrazine hydrate reduction method is outer, draw together in adhesive tape method, the SiC substrate epitaxial growth method, sodium borohydride and hydrazine hydrate two step reduction method, alkali reducing process, sour reducing process, hydro-thermal method, solvent-thermal method, chemical vapour deposition technique, graphite directly peels off method, microwave-assisted reducing process, carbon pipe shearing method, electrochemical reducing, flame method and radical reduction method.
Graphene nano material preparation method of the present invention comprises the steps:
A. graphene oxide is distributed to thionyl chloride and N, in the blending agent of dinethylformamide, room temperature is ultrasonic, refluxes subsequently, prepares brown chloride compounds;
B. meanwhile, phthalyl shitosan, LiCl and DMAC N,N are mixed, under nitrogen protection 120～150
oThe C reaction; After cooling off this reaction system,
C. product and the pyridine with a joins in the reaction system, and the nitrogen protection refluxed is filtered, washing, vacuum drying;
D. dried solid stirs in distilled water, filters, and solid retained is scattered in the distilled water again, and is ultrasonic, filter, and washing, vacuum drying gets intermedium PHCS-GO;
E. d gained intermedium is scattered in the hydrazine hydrate in 60～90
oC reaction is filtered, washing, and vacuum drying must contain the intermedium CSGR-NH of active amine
2
The intermedium CSGR-NH that f. will contain active amine
2Add in the entry, add monoethylene glycol again, dropwise add the ethylene glycol solution or the WS of metal nanoparticle precursor under the ultrasonic state, nitrogen protection is reaction under acid condition earlier down, and the back is at alkali condition 120～140
oC is reaction down;
G. behind the cool to room temperature, filter, washing, vacuum drying gets graphene nano material nano particle/graphene composite material.
Only graphene nano material preparation method comprises the steps:
A. graphene oxide is distributed to thionyl chloride and N, in the blending agent of dinethylformamide, the ultrasonic 20～40min of room temperature refluxed 40～60 hours subsequently, prepared brown chloride compounds;
B. meanwhile, phthalyl shitosan, LiCl and DMAC N,N are mixed, in nitrogen protection following 120～150
oC reaction 2～4 hours; After cooling off this reaction system,
C. product and the pyridine with a joins in the reaction system, and nitrogen protection refluxed 40～60 hours after the cooling, is filtered washing, vacuum drying;
D. solid stirred in distilled water 3～9 hours after dry, filtered, and solid retained is scattered in the distilled water again, and ultrasonic 0.5～2 hour, filter, washing, the gained solid is dry under vacuum, gets intermedium PHCS-GO;
E. d gained intermedium is scattered in the hydrazine hydrate 60～90
oC reacted 10～24 hours down, filters, and washing, vacuum drying must contain the intermedium CSGR-NH of active amine
2
The intermedium CSGR-NH that f. will contain active amine
2Add in the entry.Add monoethylene glycol again, after ultrasonic 20～30 minutes, dropwise add the ethylene glycol solution or the WS of metal nanoparticle precursor, nitrogen protection was reacted 12～24 hours under pH value 5-6 acid condition earlier down, and the back is at pH value 12-13 alkali condition 120～140
oC is reaction down;
G. behind the cool to room temperature, filter, water washing, washing with alcohol, dry under the vacuum, get graphene nano material nano particle/graphene composite material.
Glucose biological sensor based on the functionalization material of the present invention; Be that the working electrode that the graphene nano material is processed is used for the assembling of glucose biological sensor and processes, the preparation method of the working electrode of being processed by the graphene nano material comprises the steps:
A. with the glass-carbon electrode polishing, carry out polishing then;
B. after cleaning up, room temperature is dried subsequent use;
C. the graphene nano material is ultrasonic is scattered in 3%～10% the acetic acid;
D. get the glass-carbon electrode of above-mentioned dispersant liquid drop after b, drying; Then,
E. at room temperature this electrode is soaked with 0.1%～1% glutaraldehyde solution, subsequently with deionized water wash and dry;
F. with on the electrode of glucose carbohydrate oxidase drips of solution after e, 1～4
oC is dry; Afterwards,
G. be immersed in the PBS of pH=7.5, in 1～4
oC preserves subsequent use.
The preparation method of the only working electrode of being processed by the graphene nano material comprises the steps:
Glass-carbon electrode earlier with polishing on the 1200# abrasive paper for metallograph, is used 1 μ m, 0.3 μ m, 0.05 μ m Al then successively
2O
3Carry out polishing;
A. after cleaning up with distilled water, successively at the HNO of 1:1
3Each ultrasonic cleaning 5～10 min in the WS, absolute ethyl alcohol, the distilled water, room temperature is dried subsequent use;
B. get the graphene nano material, with its ultrasonic being scattered in 5% the acetic acid;
C. get above-mentioned dispersion liquid 5～10 μ L and drip, promptly get nano particle functionalization graphene material modified electrode after the drying in above-mentioned glass-carbon electrode surface;
D. at room temperature this electrode is soaked with 0.5% glutaraldehyde solution, subsequently with deionized water wash and drying at room temperature;
E. with the glucose carbohydrate oxidase drips of solution of 5～10 μ L, 4 mg/ml on nano particle functionalization graphene material modified electrode, 1～4
oC is dry, promptly gets nano particle functionalization graphene material glucose carbohydrate oxidase modified electrode;
F. above-mentioned nano particle functionalization graphene material glucose carbohydrate oxidase modified electrode soaked 10～30 minutes with 0.05 M pH=7.5 PBSs; Be immersed in again after the taking-up in 0.05 M pH=7.5 PBSs, in 1～4
oPreserve subsequent use in the C refrigerator.
The present invention is on the basis of years of researches; The graphene nano material is used for the assembling of glucose biological sensor, forms the nano functional film, compare with using traditional enzyme electrode; Have high selectivity, in short-term, low cost analysis, handling safety; Being convenient to significant advantages such as on-site measurement, is the first-selected device of the daily blood glucose measurement of diabetes patient, has important economy and social effect.Nano functional film immobilization enzyme can be analyzed more than 1000 times continuously, and can reach the identical current-responsive height of disposable consumption enzyme, and the cost of mensuration is money in a measure only, and analysis precision is higher than other method, and relative error reaches about 1%.And the response time shortens to 20 seconds; Also prolong greatly serviceable life; This current type glucose sensor can be accurately measure glucose concentration regularly, high selectivity, in short-term, low cost analysis, amalyzing substances is not had special requirement, handling safety, easy; Be convenient to on-site measurement etc., can be used for the daily blood glucose measurement of diabetes patient.Also for the universal advantageous conditions that provides of GB.
Glucose biological sensor based on the functionalization graphene nano material of the present invention; It is a kind of quantitative measuring technology; Data are accurate, and error is little, can be used for efficient, easy, measure patient's blood sugar concentration fast; Therefore having wide potential applicability in clinical practice, is development trend clinical, the family expenses biology sensor.
Description of drawings
Fig. 1 a is palladium nano-particles/graphene composite material sem photograph;
Fig. 1 b is palladium nano-particles/graphene composite material high-resolution-ration transmission electric-lens figure;
Fig. 1 c is palladium nano-particles/graphene composite material electron diffraction diagram;
Fig. 1 d is palladium nano-particles/graphene composite material X-ray energy spectrum (EDS);
Fig. 2 is a graphene nano compound substance typical case Raman spectrum;
Fig. 3 is the infrared spectrogram of palladium nano-particles/graphene composite material and associated materials;
Fig. 4 is the X-ray diffraction of palladium nano-particles/graphene composite material and associated materials.
Embodiment
The preparation of preparation embodiment 1 Graphene
Improve the Hummers method and combine the hydrazine hydrate reducing process: at first, graphite (1.5 g, 325 orders) is joined the dense H of 12 ml
2SO
4, 2.5 g K
2S
2O
8With 2.5 g P
2O
5Potpourri in, heat above-mentioned mixed system to 80
oC keeps this temperature, magnetic agitation 5 hours.Cooling reaction system is to room temperature subsequently, in potpourri impouring 500ml deionized water, and hold over night.Through 0.2 micron membrane filtration, washing is also dried naturally, gets pre-oxidation graphite with the above-mentioned thing that leaves standstill.The graphite of this pre-oxidation is joined 0
oThe dense H of C
2SO
4Among 120 ml, slowly add 15 g KMnO subsequently
4, and the control temperature of reaction is 20
oC stirs.Potassium permanganate finishes, and the control reaction system is 35
oC stirred 4 hours, subsequently, added 250 ml deionized waters, and controlled temperature 50 through peripheral ice bath
oBelow the C.Stir after 1.5 hours, add 700 ml deionized waters again, after half an hour, dropwise splash into 20 ml, 30% H
2O
2, reaction system changes pale brown look into by brown rapidly.Remove stirring apparatus, filter this pale brown potpourri, to remove metallic ion, use 1 L deionized water cyclic washing subsequently again with HCl 1 L washing in 1: 10; Get brown solid, after the drying at room temperature, it is 0.5% w/w aqueous dispersions that above-mentioned brown solid is processed weight ratio; Continuously one week of dialysis, filter washing at last; Again disperseed ultrasonic 1 hour, and filtered 60
oC vacuum drying 24 hours can prepare graphene oxide.It is 1 mg/ml dispersion liquid that above-mentioned graphene oxide is processed 100 ml concentration, adds hydrazine hydrate 1 ml, after ultrasonic 30 minutes again 100
oC refluxed 24 hours, filtered washing, 60
oC vacuum drying 24 hours can prepare Graphene;
Preparation embodiment 2 graphene nano material preparations (palladium nano-particles/graphene composite material Pd NPs/CSGR)
At first, graphene oxide 200 mg are distributed to 40ml thionyl chloride and 1 ml N, in the blending agent of dinethylformamide, ultrasonic 0.5 hour of room temperature refluxed 52 hours subsequently, prepared brown chloride compounds 219.2 mg.Meanwhile, with phthalyl shitosan 1.753 g) LiCl 1.201 g and DMAC N,N 120 ml mix, under nitrogen protection 140
oC reaction 2 hours.After cooling off this reaction system, brown chloride compounds 219.2 mg and 14 ml pyridines that back is made join in the reaction system, and nitrogen protection refluxed 48 hours after the cooling, is filtered washing, vacuum drying.Dry back solid stirred 6 hours in 120 ml distilled water, filtered, and solid retained is scattered in the 200 ml water again, ultrasonic 1 hour, filtered washing.The gained solid is in vacuum 65
oC dry 24 hours down gets intermedium PHCS-GO (205 g).This intermedium is scattered in the 15 ml hydrazine hydrates 80
oC reaction down removed the phthalyl protection in 16 hours.Filter, washing, vacuum drying must contain the intermedium CSGR-NH of active amine
2(175 mg).The intermedium CSGR-NH that will contain active amine
2(100 mg) adds 1.5 ml water.Subsequently, add 10 ml monoethylene glycol, ultrasonic 20 minutes, dropwise add palladium bichloride ethylene glycol solution 10 ml of concentration 2.03 mg Pd/ml, regulate the pH value to 5-6, violent ultrasonic 5 minutes of reaction system stirred 20 hours subsequently.Subsequently, regulate pH value to 13,140 with the sodium hydroxide solution of 2.5 M
oReaction is 3 hours during C, and entire reaction course is all taked nitrogen protection.Behind the cool to room temperature, filter water and washing with alcohol each three times, vacuum 65
oC dry 24 hours down gets palladium nano-particles/graphene composite material (Pd NPs/CSGR);
Material characterizes
The sign of product size and pattern is at JEM-2010F transmission electron microscope (TEM), carries out on JEOL-2010F high-resolution-ration transmission electric-lens (HRTEM) and the JSM-7401F field emission scanning electron microscope (FESEM), and the WV of Electronic Speculum is 200 kV.X-ray energy spectrum (EDS) and selected diffraction (SAED) experiment are accomplished under the JEOL-2010F high-resolution-ration transmission electric-lens.The powder x-ray diffraction of product (XRD) characterizes and on German Bruker D8-advance X-ray diffractometer, carries out, and X ray is monochromatic CuK α radiant rays (λ=1.5418), from 10 to 70 ° of 2 θ scanning angles, 0.02 ° of step-length.Carry out on Fourier's infrared spectrum (FTIR) experiment FTIR-8201 (PerkinElmer company) infrared spectrometer.IR spectroscopy is tested after through sample and KBr compressing tablet.Raman spectrum is selected the Renishaw microprobe RM1000 of Britain Lei Shaoni company type Raman spectrometer, excitation wavelength 633 nm (He/Ne laser instrument) for use.Atomic force test (Atomic force microscopic, AFM) Nanoscope III MultiMode SPM (digital display) the type scan-probe atomic force microscope of employing U.S. Wei Yike exact instrument company limited.The CE-440 elemental analyser of U.S. EAI company is adopted in ultimate analysis.
Palladium nano-particles/graphene composite material characterization result is following: the diameter range of Pd nano particle has smaller particle size and reaches than arrowband size distribution (according to sem photograph 1a and transmission electron microscope picture 1b characterization result) between 2-8 nm; Electron diffraction diagram (seeing Fig. 1 c) can be observed from interior encircle outer shroud by strong to weak four diffraction rings, correspond respectively to (111), (200), (220), (311) and the crystal faces such as (400) of crystalline state palladium.The Raman spectrum (see figure 2) shows that it is at 1331 cm
-1And 1590 cm
-1Have the characteristic Raman peaks, ownership is the D band and the G band of Graphene respectively; (Fig. 3 d.) has 890,1150 cm to infrared spectrum (seeing Fig. 3, a. shitosan wherein, b. Graphene, the Graphene that c. is chitosan-modified, d. palladium nano-particles/graphene composite material) to show this electrode material
-1And 1545 cm
-1Characteristic peak, preceding two characteristic peaks that the peak is a shitosan, the 3rd the skeleton vibrations that the peak ownership is a Graphene.X-ray diffractogram (XRD figure is seen Fig. 4, a. Graphene wherein, b. palladium nano-particles/graphene composite material) is observed palladium nano-particles/graphene composite material 24.7
o, four Bragg reflection peaks such as 39.6 °, 45.5 ° and 67.3 °, first is corresponding to (002) crystal face of Graphene, back three peaks are (111) of corresponding palladium successively, (200), (220) crystal face;
Preparation embodiment 3 working sensor electrode preparation
Glass-carbon electrode earlier with polishing on the 1200# abrasive paper for metallograph, is used 1 μ m, 0.3 μ m, 0.05 μ m Al then successively
2O
3Carry out polishing, after cleaning up with distilled water, at 1:1 HNO
3Each ultrasonic cleaning 5 min in the WS, absolute ethyl alcohol, the distilled water, room temperature is dried subsequent use.Get nano particle functionalization graphene material 2 mg of above-mentioned preparation, it be scattered in the acetic acid of 1 ml 5%, ultrasonic after, get above-mentioned dispersion liquid 8 μ L and drip in above-mentioned glass-carbon electrode surface, promptly get nano particle functionalization graphene material modified electrode after the drying.At room temperature this electrode is soaked with 0.5% glutaraldehyde solution, subsequently with deionized water wash and drying at room temperature.With glucose carbohydrate oxidase (GOD) drips of solution of 8 μ L, 4 mg/ml on nano particle functionalization graphene material modified electrode, 4
oDry during C.Above-mentioned glucose carbohydrate oxidase modified electrode soaks 20 minutes to remove unconjugated GOD with the 0.05 M PBS of pH=7.5.The 0.05 M PBS that the glucose sugar biology sensor working electrode for preparing above-mentioned is immersed in pH=7.5 is in 4
oPreserve subsequent use in the C refrigerator.
Application implementation example 1
Cyclic voltammetric and ac impedance measurement adopt CHI830B electrochemical workstation (Shanghai occasion China instrument company), and three-electrode system is: saturated calomel electrode is as the rubble electrode, and platinum electrode is an auxiliary electrode, and enzyme electrode is a working electrode.The glucose sugar biology sensor working electrode for preparing is immersed in the 0.05 M PBS of 5 mL pH=7.5; Evenly stir the glucose standard solution or the solution to be measured that add different volumes down; After the dissolved oxygen DO signal was caught by oxygen electrode, the variation of electrode potential was transfused in the computer data processor, and exported with the form that dissolved oxygen concentration changes; Record dissolved oxygen concentration decline curve is with glucose content in the calibration curve method test sample.
The result shows; Glucose biological sensor based on the functionalization material of the present invention; Have characteristics such as the range of linearity is wide, detection limit is low, favorable reproducibility, life-span length: between concentration of glucose 0.010～1.10 mmol/L, present good linear relationship, equation of linear regression is y (mg/L)=6.7471x (mmol/L)-0.00501 (r=0.9989); Be limited to 0.2 μ mol/L (S/N=3) with the standard deviation of 3 times of blank divided by the detecting of slope calculating sensor of standard working curve.The sensor of being processed by same enzyme membrane is to 0.25 mmol/L glucose solution replication 10 times, response mean value RSD=2.5%.Place the oxygen electrode surface to make 4 glucose biological sensors respectively the different fixed enzyme membrane, 0.25 mmol/L glucose solution is measured RSD=4.7%; To this concentration glucose follow-on test 200 times (about 24 h), response signal still can reach more than 98% of initial value; This glucose biological sensor is deposited in 4 ℃ of refrigerators, every at a distance from 3～4 days duplicate detection.0.25 the response of mmol/L glucose solution.Response signal is 86.5% of an initial value after 3 months.
Claims (6)
1. based on the glucose biological sensor of functionalization material, comprise working electrode, it is characterized in that: working electrode is processed by the graphene nano material.
2. according to the said biology sensor of claim 1, it is characterized in that: the graphene nano material is selected from: palladium nano-particles/graphene composite material, Pt nanoparticle/graphene composite material, gold nano grain/graphene composite material, silver nano-grain/graphene composite material, copper nano particles/graphene composite material, germanium nano particle/graphene composite material, di-iron trioxide nano particle/graphene composite material, ferroferric oxide nano granules/graphene composite material, tin indium oxide nano particle/graphene composite material and tin indium oxide-platinum binary composite nanometer particle/graphene nano compound substance.
3. biology sensor according to claim 1 and 2 is characterized in that: the graphene nano material preparation method comprises the steps:
A. graphene oxide is distributed to thionyl chloride and N, in the blending agent of dinethylformamide, room temperature is ultrasonic, refluxes subsequently, prepares brown chloride compounds;
B. meanwhile, phthalyl shitosan, LiCl and DMAC N,N are mixed, under nitrogen protection 120～150
oThe C reaction; After cooling off this reaction system,
C. product and the pyridine with a joins in the reaction system, and the nitrogen protection refluxed is filtered, washing, vacuum drying;
D. dried solid stirs in distilled water, filters, and solid retained is scattered in the distilled water again, and is ultrasonic, filter, and washing, vacuum drying gets intermedium PHCS-GO;
E. d gained intermedium is scattered in the hydrazine hydrate in 60～90
oC reaction is filtered, washing, and vacuum drying must contain the intermedium CSGR-NH of active amine
2
The intermedium CSGR-NH that f. will contain active amine
2Add in the entry, add monoethylene glycol again, dropwise add the ethylene glycol solution or the WS of metal nanoparticle precursor under the ultrasonic state, nitrogen protection is reaction under acid condition earlier down, and the back is at alkali condition 120～140
oC is reaction down;
G. behind the cool to room temperature, filter, washing, vacuum drying gets graphene nano material nano particle/graphene composite material.
4. biology sensor according to claim 1 and 2 is characterized in that: the graphene nano material preparation method comprises the steps:
A. graphene oxide is distributed to thionyl chloride and N, in the blending agent of dinethylformamide, the ultrasonic 20～40min of room temperature refluxed 40～60 hours subsequently, prepared brown chloride compounds;
B. meanwhile, phthalyl shitosan, LiCl and DMAC N,N are mixed, in nitrogen protection following 120～150
oC reaction 2～4 hours; After cooling off this reaction system,
C. product and the pyridine with a joins in the reaction system, and nitrogen protection refluxed 40～60 hours after the cooling, is filtered washing, vacuum drying;
D. solid stirred in distilled water 3～9 hours after dry, filtered, and solid retained is scattered in the distilled water again, and ultrasonic 0.5～2 hour, filter, washing, the gained solid is dry under vacuum, gets intermedium PHCS-GO;
E. d gained intermedium is scattered in the hydrazine hydrate 60～90
oC reacted 10～24 hours down, filters, and washing, vacuum drying must contain the intermedium CSGR-NH of active amine
2
The intermedium CSGR-NH that f. will contain active amine
2Add in the entry; Add monoethylene glycol again, after ultrasonic 20～30 minutes, dropwise add the ethylene glycol solution or the WS of metal nanoparticle precursor, nitrogen protection was reacted 12～24 hours under pH value 5-6 acid condition earlier down, and the back is at pH value 12-13 alkali condition 120～140
oC is reaction down;
G. behind the cool to room temperature, filter, water washing, washing with alcohol, dry under the vacuum, get graphene nano material nano particle/graphene composite material.
5. according to the preparation method of the said biology sensor of claim 1; It is characterized in that: the working electrode that the graphene nano material is processed is used for the assembling of glucose biological sensor and processes, and the preparation method of the working electrode of being processed by the graphene nano material comprises the steps:
A. with the glass-carbon electrode polishing, carry out polishing then;
B. after cleaning up, room temperature is dried subsequent use;
C. the graphene nano material is ultrasonic is scattered in 3%～10% the acetic acid;
D. get the glass-carbon electrode of above-mentioned dispersant liquid drop after b, drying; Then,
E. at room temperature this electrode is soaked with 0.1%～1% glutaraldehyde solution, subsequently with deionized water wash and dry;
F. with on the electrode of glucose carbohydrate oxidase drips of solution after e, 1～4
oC is dry; Afterwards,
G. be immersed in the PBS of pH=7.5, in 1～4
oC preserves subsequent use.
6. according to the preparation method of claim 1 or 5 said biology sensors; It is characterized in that: the working electrode that the graphene nano material is processed is used for the assembling of glucose biological sensor and processes, and the preparation method of the working electrode of being processed by the graphene nano material comprises the steps:
A. glass-carbon electrode is first with polishing on the 1200# abrasive paper for metallograph, use 1 μ m then successively, 0.3 μ m, 0.05 μ m Al
2O
3Carry out polishing;
B. after cleaning up with distilled water, successively at the HNO of 1:1
3Each ultrasonic cleaning 5～10 min in the WS, absolute ethyl alcohol, the distilled water, room temperature is dried subsequent use;
C. get the graphene nano material, with its ultrasonic being scattered in 5% the acetic acid;
D. get above-mentioned dispersion liquid 5～10 μ L and drip, promptly get nano particle functionalization graphene material modified electrode after the drying in above-mentioned glass-carbon electrode surface;
E. at room temperature this electrode is soaked with 0.5% glutaraldehyde solution, subsequently with deionized water wash and drying at room temperature;
F. with the glucose carbohydrate oxidase drips of solution of 5～10 μ L, 4 mg/ml on nano particle functionalization graphene material modified electrode, 1～4
oC is dry, promptly gets nano particle functionalization graphene material glucose carbohydrate oxidase modified electrode;
G. above-mentioned nano particle functionalization graphene material glucose carbohydrate oxidase modified electrode soaked 10～30 minutes with 0.05 M pH=7.5 PBSs, was immersed in after the taking-up in 0.05 M pH=7.5 PBSs, in 1～4 again
oPreserve subsequent use in the C refrigerator.
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