CN106353390B - The method that Electron Beam Irradiation prepares graphite oxide alkenyl enzyme-free glucose sensor - Google Patents

The method that Electron Beam Irradiation prepares graphite oxide alkenyl enzyme-free glucose sensor Download PDF

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CN106353390B
CN106353390B CN201610847831.1A CN201610847831A CN106353390B CN 106353390 B CN106353390 B CN 106353390B CN 201610847831 A CN201610847831 A CN 201610847831A CN 106353390 B CN106353390 B CN 106353390B
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enzyme
glucose sensor
electron beam
graphene oxide
free glucose
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CN106353390A (en
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程伶俐
王瑞
焦正
蒋晓濛
胡亦杨
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University of Shanghai for Science and Technology
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • G01N27/48Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/347Ionic or cathodic spraying; Electric discharge

Abstract

The present invention relates to a kind of methods that Electron Beam Irradiation prepares graphite oxide alkenyl enzyme-free glucose sensor, belong to radiation chemistry and graphene nano Material Field.Graphene oxide is produced using existing known technology method first;Then it is configured to mixed solution with silver nitrate, aniline according to a certain percentage;Perchloric acid solution is added thereto again to be uniformly mixed;It is placed in electron beam generating apparatus and carries out electron beam irradiation, irradiation dose is 150~300 KGy;Then washed, dry obtained graphite oxide alkenyl enzyme-free glucose sensor.The resulting graphite oxide alkenyl enzyme-free glucose sensor of this method, good biocompatibility prove it in the case where not adding enzyme by detection, have more sensitive glucose detection activity;Preparation process is simple, at low cost, is not related to toxic substance, environmentally friendly.

Description

The method that Electron Beam Irradiation prepares graphite oxide alkenyl enzyme-free glucose sensor
Technical field
The present invention relates to a kind of methods that Electron Beam Irradiation prepares graphite oxide alkenyl enzyme-free glucose sensor, belong to Radiation chemistry and graphene nano Material Field.
Background technique
The glucose sensor of measurement Glucose in Blood by Cyclic, which is divided into, to be had enzyme and without two kinds of enzyme, there is enzymatic glucose sensor Due to glucose oxidase itself vulnerable to extraneous factor influence be difficult to store for a long time, and enzyme-free glucose sensor then show it is good Good electro catalytic activity.All in all, have the range of linearity wide, detection limits low, high sensitivity, and the good advantage of selectivity also has Standby good reproducibility and long-time stability.So the exploratory development of enzyme-free glucose sensor receives universal concern.
The metals such as gold, copper, nickel bare electrode can be made into glucose sensor electrode without enzyme, but this kind of electrode is to grape glycosyloxy Change show lower sensitivity and selectivity it is lower.Nanometer material modified electrode has biggish specific surface area and higher Catalytic activity has been widely used in the development of enzyme-free glucose sensor.Some researches show that noble metal nano particles and mistakes It crosses metal nano material and all has the glycoxidative activity of good catalysis grape, be the important material for constructing enzyme-free glucose sensor Material.The electron transmission that there is graphene nano material excellent electric conductivity to promote electrode surface keeps nano particle catalysis active It significantly increases, big specific surface area can load more nanoparticles with catalytic activity, make the detection signal of sensor It greatly enhances.However, since the Van der Waals force between graphene sheet layer is stronger, so that the dispersibility of graphene is poor.
Currently, researcher has developed a kind of graphene oxide/polyaniline composite material.Graphene oxide/the polyphenyl Amine composite material can apply to be built with enzymatic glucose sensor.But due to graphene oxide/polyaniline composite material system Standby to use electrochemical synthesis and chemical synthesis, time-consuming for preparation process, cost is relatively high, technique is cumbersome, and preparation process In need to use Strong oxdiative reagent, such as potassium peroxydisulfate can cause environmental pollution.
Summary of the invention
The purpose of the present invention is provide a kind of Electron Beam Irradiation preparation oxidation stone for the deficiencies in the prior art The method of mertenyl enzyme-free glucose sensor, the oxidation and restore free radical that this method is generated using electron beam irradiation water, together When silver particles and synthesized polyaniline are loaded on graphene oxide, preparation process is simple, mild condition, does not have to toxic chemical and tries Agent, it is environmentally friendly, and glucose sensor obtained has good glucose responding.
The method that Electron Beam Irradiation of the invention prepares graphite oxide alkenyl enzyme-free glucose sensor, it is characterised in that With following preparation process and step:
A. raw material graphene oxide is prepared
Prior art preparation raw material graphene oxide is pressed first, and preparation method is as follows:
By a certain amount of potassium peroxydisulfate (K2S2O8) and phosphorus pentoxide (P2O5) be dissolved in the concentrated sulfuric acid, after being heated to 80 DEG C A certain amount of natural graphite is added, is cooled to room temperature after keeping the temperature 4.5 hours at 80 DEG C;Then it is diluted, is placed with deionized water Overnight;Then it is filtered, washs, gained filter residue is put dry at 60 DEG C in a vacuum drying oven;Filter residue after drying is molten Solution is slowly added to potassium permanganate (KMnO in the concentrated sulfuric acid under condition of ice bath4), constant temperature stirs 2 hours at 35 DEG C;Then it uses Deionized water dilution, and it is slowly added to 30% hydrogen peroxide (H2O2);Then it is filtered, washed, by the product after washing at 60 DEG C Vacuum drying, obtains graphene oxide solid;
B. Electron Beam Irradiation prepares graphite oxide alkenyl enzyme-free glucose sensor
(1), it weighs the resulting graphene oxide of a certain amount of above-mentioned steps (a) to be scattered in deionized water, is placed in ultrasound Ultrasonic disperse 5~15 minutes in oscillator mix them thoroughly uniformly, and obtaining concentration is the g/L graphene oxide of 0.5 g/L~2 Suspension;
(2), a certain amount of soluble silver salt is weighed, is dissolved in suspension obtained by above-mentioned steps (1), then be placed in sonic oscillation Ultrasonic disperse 5~8 minutes in device mix them thoroughly uniformly, obtain the first mixed solution, the silver salt and graphene oxide Mass concentration ratio is 1:1~1:5;
(3), the aniline of the uL of 150 uL~300 is added into resulting first mixed solution of above-mentioned steps (2), is placed in It is stirred 20~30 minutes in magnetic stirring apparatus, is uniformly mixed it, obtains the second mixed solution;
(4), the perchloric acid solution of the mL of 4 mL~15 is added to resulting second mixed solution of above-mentioned steps (3) and is relayed Continuous stirring, is uniformly mixed it, obtains third mixed solution;
(5), the resulting third mixed solution of above-mentioned steps (4) is put into the reaction vessel of sealing, and places it in 2.5 It is irradiated under the electron beam irradiation of the electron accelerator generation of MeV, 40 mA, irradiation dose is 150~300 KGy, is obtained Product after irradiation reaction;
(6), with the product after the above-mentioned irradiated reaction of ethanol washing, then wash with distilled water;Then high speed centrifugation is used Machine centrifuge separation, repeated multiple times, the solids to remove wherein unreacted ion, after being separated;
(7), the solids after above-mentioned steps (6) resulting separation is placed in a vacuum drying oven drying, drying temperature is 50 oC~80oC, drying time are 8~15 hours;Black solid object graphite oxide alkenyl enzyme-free glucose is obtained after drying Sensor, as silver-silver chloride/polyaniline/graphene oxide enzyme-free glucose sensor.
Soluble silver salt described in above-mentioned steps (2) is one of silver nitrate and silver perchlorate.
The invention has the characteristics that generating a variety of oxidations and reproducibility using water under conditions of high-energy electron beam irradiation Living radical, the reaction condition of the accurate control system of energy make the active free radical of a variety of oxidations and reproducibility while playing Effect,Wherein, the aqueous electron of reductive free radical restores silver ion, and oxidative free radical, hydroxyl radical free radical make aniline polymerization Polyaniline is generated, single step reaction prepares silver-silver chloride/polyaniline/graphene oxide enzyme-free glucose sensor.
Compared with prior art, the present invention having following remarkable advantage:
(1) preparation process of the present invention is simple, and production cost is low, is not related to toxic harmful chemical agents, ring in preparation process Border is friendly;
(2) in preparation process of the present invention, silver-silver chloride nano particle and polyaniline energy uniform load are in graphene oxide On, nano particle well-crystallized;Chemical property is good, and glucose sensor obtained has good glucose responding Property, it can be used for detecting glucose under conditions of no enzyme.
Detailed description of the invention
Fig. 1 is X diffraction (XRD) figure of gained graphite oxide alkenyl enzyme-free glucose sensor in the embodiment of the present invention.
Fig. 2 is scanning electron microscope (SEM) figure of gained graphite oxide alkenyl enzyme-free glucose sensor in the embodiment of the present invention.
Fig. 3 be the embodiment of the present invention in gained graphite oxide alkenyl enzyme-free glucose sensor under no glucose condition With there is the cyclic voltammetric under glucose condition to compare figure.
Specific embodiment
After now specific embodiments of the present invention are described in detail.
Embodiment
Producing graphene oxide by existing known technology first, (technical method can refer to document J. Am. Chem. Soc., 2008,130 (18), 5856-5857).
1, the preparation of graphene oxide
By a certain amount of potassium peroxydisulfate (K2S2O8) and phosphorus pentoxide (P2O5) be dissolved in the concentrated sulfuric acid, after being heated to 80 DEG C A certain amount of natural graphite is added, is cooled to room temperature after keeping the temperature 4.5 hours at 80 DEG C;Then it is diluted, is placed with deionized water Overnight;Then it is filtered, washs, gained filter residue is put dry at 60 DEG C in a vacuum drying oven;Filter residue after drying is molten Solution is slowly added to potassium permanganate (KMnO in the concentrated sulfuric acid under condition of ice bath4), constant temperature stirs 2 hours at 35 DEG C;Then it uses Deionized water dilution, and it is slowly added to 30% hydrogen peroxide (H2O2);Then it is filtered, washed, by the product after washing at 60 DEG C Vacuum drying, obtains graphene oxide solid;
2, Electron Beam Irradiation prepares graphite oxide alkenyl enzyme-free glucose sensor
(1), the resulting graphene oxide of above-mentioned steps (a) for weighing 0.9g is scattered in 900 mL deionized waters, is placed in Ultrasonic disperse 8 minutes in ultrasonator mix them thoroughly uniformly, and obtaining concentration is 1 g/L graphene oxide suspension;
(2), the silver nitrate for weighing 0.3 g is dissolved in suspension obtained by above-mentioned steps (1), is placed in ultrasonator Middle ultrasonic disperse 6 minutes mixes them thoroughly uniformly, obtains the first mixed solution, the silver salt and graphene oxide quality Concentration ratio is 1:3;
(3), the aniline of 200 uL is added to resulting first mixed solution of above-mentioned steps (2), is placed in magnetic stirring apparatus Middle stirring 25 minutes, is uniformly mixed it, obtains the second mixed solution;
(4), the perchloric acid solution of 8 mL is added into resulting second mixed solution of above-mentioned steps (3), continues to stir, It is uniformly mixed it, obtains third mixed solution;
(5), the resulting third mixed solution of above-mentioned steps (4) is put into the reaction vessel of sealing, and places it in 2.5 It is irradiated under the electron beam irradiation of the electron accelerator generation of MeV, 40 mA, irradiation dose is 210 KGy, is irradiated Product after reaction;
(6), with the product after the above-mentioned irradiated reaction of ethanol washing, then wash with distilled water;Then high speed centrifugation is used Machine centrifuge separation, repeated multiple times, the solids to remove wherein unreacted ion, after being separated;
(7), the obtained solid object after above-mentioned steps (6) separation is placed in a vacuum drying oven drying, drying temperature 70oC, drying time are 12 hours;Gained black solid object graphite oxide alkenyl enzyme-free glucose sensor after drying, as silver- Silver chlorate/polyaniline/graphene oxide enzyme-free glucose sensor.The performance of graphite oxide alkenyl enzyme-free glucose sensor is surveyed Examination:
The present invention tests the electrochemical sensing performance of graphite oxide alkenyl enzyme-free glucose sensor using cyclic voltammetry. Graphite oxide alkenyl enzyme-free glucose sensor obtained in embodiment is dissolved in dehydrated alcohol, being configured to concentration is 5g/L's Solution;It is successively polished glass-carbon electrode, is cleaned with deionized water, to its natural air drying with the sand paper of 5 μm and 2.7 μm;Take above-mentioned match The solution drop being set to drips the perfluorinated sulfonic acid solution of 20 μ L on glass-carbon electrode, and on its surface again, at room temperature natural air drying;Group Fill three electrode test systems, three electrodes are respectively: working electrode is glass-carbon electrode, and reference electrode is Ag/AgCl electrode, electrode For platinum electrode;Electrolyte is prepared respectively are as follows: the sodium hydroxide of the 50mM without containing glucose and the glucose hydrogen containing 5mM Sodium hydroxide solution;Assembled three electrode tests system is connected on CHI660C electrochemical test and is detected, according to it The variation of response current is to realize the detection to graphite oxide alkenyl enzyme-free glucose sensor to glucose.
Referring to attached drawing, Fig. 1 is the XRD spectra of graphite oxide alkenyl enzyme-free glucose sensor obtained by the embodiment of the present invention. XRD analysis: it is carried out on Japanese RigaKu D/max-2550 type X-ray diffractometer;Using CuK diffraction.As can be known from Fig. 1, this The group of graphite oxide alkenyl enzyme-free glucose sensor becomes silver nano-grain, polyaniline and graphene oxide, wherein silver nanoparticle The well-crystallized of particle.
Referring to attached drawing, Fig. 2 is the SEM figure of graphite oxide alkenyl enzyme-free glucose sensor obtained by the embodiment of the present invention.SEM Analysis: material morphology is observed using Jeol Ltd. JSM-6700F type field emission scanning electron microscope.From Fig. 2 It is found that silver nano-grain and polyaniline are uniformly supported on graphene oxide in this graphite oxide alkenyl enzyme-free glucose sensor On.
Referring to attached drawing, Fig. 3 is graphite oxide alkenyl enzyme-free glucose sensor obtained by the embodiment of the present invention in no glucose Under the conditions of and there is the cyclic voltammetric under glucose condition to compare figure.As can be known from Fig. 3, glucose sensor produced by the present invention exists In the presence of glucose, response current is significantly increased, suitable for the analysis and detection to glucose.

Claims (2)

1. a kind of method that Electron Beam Irradiation prepares graphite oxide alkenyl enzyme-free glucose sensor, it is characterised in that have with Lower preparation process and step:
A. raw material graphene oxide is prepared
Prior art preparation raw material graphene oxide is pressed first, and preparation method is as follows:
By a certain amount of potassium peroxydisulfate (K2S2O8) and phosphorus pentoxide (P2O5) be dissolved in the concentrated sulfuric acid, it is added after being heated to 80 DEG C A certain amount of natural graphite is cooled to room temperature after keeping the temperature 4.5 hours at 80 DEG C;Then it is diluted, is stood overnight with deionized water; Then it is filtered, washs, gained filter residue is put dry at 60 DEG C in a vacuum drying oven;Filter residue after drying is dissolved in dense In sulfuric acid, potassium permanganate (KMnO is slowly added under condition of ice bath4), constant temperature stirs 2 hours at 35 DEG C;Then deionization is used Water dilution, and it is slowly added to 30% hydrogen peroxide (H2O2);Then it is filtered, washed, by the product after washing, vacuum is done at 60 DEG C It is dry, obtain graphene oxide solid;
B. Electron Beam Irradiation prepares graphite oxide alkenyl enzyme-free glucose sensor
(1), it weighs a certain amount of resulting graphene oxide of above-mentioned steps a to be scattered in deionized water, is placed in ultrasonator Middle ultrasonic disperse 5~15 minutes mixes them thoroughly uniformly, and obtaining concentration is 0.5g/L~2g/L graphene oxide suspension;
(2), a certain amount of soluble silver salt is weighed, is dissolved in suspension obtained by above-mentioned steps (1), then be placed in ultrasonator It ultrasonic disperse 5~8 minutes, mixes them thoroughly uniformly, obtains the first mixed solution, the silver salt and graphene oxide quality Concentration ratio is 1:1~1:5;
(3), the aniline of 150 μ of μ L~300 L is added into resulting first mixed solution of above-mentioned steps (2), is placed in magnetic force and stirs It mixes in device and stirs 20~30 minutes, be uniformly mixed it, obtain the second mixed solution;
(4), the perchloric acid solution of 4mL~15mL is added into resulting second mixed solution of above-mentioned steps (3) and continues to stir, It is uniformly mixed it, obtains third mixed solution;
(5), the resulting third mixed solution of above-mentioned steps (4) is put into the reaction vessel of sealing, and place it in 2.5MeV, It is irradiated under the electron beam irradiation that the electron accelerator of 40mA generates, irradiation dose is 150~300KGy, and it is anti-to obtain irradiation Product after answering;
(6), with the product after the above-mentioned irradiated reaction of ethanol washing, then wash with distilled water;Then with supercentrifuge from Heart separation, repeated multiple times, the solids to remove wherein unreacted ion, after being separated;
(7), the solids after above-mentioned steps (6) resulting separation is placed in a vacuum drying oven drying, drying temperature is 50 DEG C ~80 DEG C, drying time is 8~15 hours;It is silver-silver chloride/polyaniline/graphene oxide that black solid object is obtained after drying, And using silver-silver chloride/polyaniline/graphene oxide as modified electrode material, applied to preparing enzyme-free glucose sensor.
2. the side that a kind of Electron Beam Irradiation according to claim 1 prepares graphite oxide alkenyl enzyme-free glucose sensor Method, which is characterized in that soluble silver salt described in above-mentioned steps (2) is one of silver nitrate and silver perchlorate.
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