CN114910526B - High-sensitivity glucose sensor and preparation method and application thereof - Google Patents
High-sensitivity glucose sensor and preparation method and application thereof Download PDFInfo
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 title claims abstract description 63
- 239000008103 glucose Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 56
- 239000011678 thiamine pyrophosphate Substances 0.000 claims abstract description 44
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 41
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 41
- 239000000661 sodium alginate Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 40
- 229960002363 thiamine pyrophosphate Drugs 0.000 claims abstract description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011889 copper foil Substances 0.000 claims abstract description 20
- 238000000137 annealing Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 12
- 229920001661 Chitosan Polymers 0.000 claims abstract description 11
- 239000002033 PVDF binder Substances 0.000 claims abstract description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 11
- 235000008170 thiamine pyrophosphate Nutrition 0.000 claims abstract description 11
- YXVCLPJQTZXJLH-UHFFFAOYSA-N thiamine(1+) diphosphate chloride Chemical compound [Cl-].CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N YXVCLPJQTZXJLH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims abstract description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims abstract description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 5
- 239000012895 dilution Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000035945 sensitivity Effects 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 108090000790 Enzymes Proteins 0.000 abstract description 4
- 102000004190 Enzymes Human genes 0.000 abstract description 4
- 230000004044 response Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 239000008280 blood Substances 0.000 description 4
- 210000004369 blood Anatomy 0.000 description 4
- 108010050375 Glucose 1-Dehydrogenase Proteins 0.000 description 3
- 108010015776 Glucose oxidase Proteins 0.000 description 3
- 239000004366 Glucose oxidase Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940088598 enzyme Drugs 0.000 description 3
- 229940116332 glucose oxidase Drugs 0.000 description 3
- 235000019420 glucose oxidase Nutrition 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 206010012601 diabetes mellitus Diseases 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- 239000011721 thiamine Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/08—Alloys with open or closed pores
Abstract
The invention provides a high-sensitivity glucose sensor and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing thiamine pyrophosphate solution and chitosan-containing hydrochloric acid solution, stirring and reacting, and adding sodium alginate solution to obtain CS-TPP/SA nanogel solution; to Cu 2+ Dripping CS-TPP/SA nano gel solution into the solution, centrifuging, collecting precipitate, and drying to obtain CS-TPP/SA/Cu 2+ A material; CS-TPP/SA/Cu 2+ Grinding the material, and then annealing to obtain Cu-Cu with porous structure 2+1 An O material; bonding the copper foil with the PDMS substrate, and bonding the porous Cu-Cu 2+1 And coating the mixture of the O material, the conductive carbon black and the polyvinylidene fluoride on the surface of the copper foil, and carrying out vacuum drying to obtain the copper foil. The glucose sensor can effectively solve the problems of poor stability and great influence by external environment of the existing enzyme glucose sensor.
Description
Technical Field
The invention belongs to the technical field of biological sensors, and particularly relates to a high-sensitivity glucose sensor and a preparation method and application thereof.
Background
Effective control of blood glucose can prevent complications of diabetes, but challenges blood glucose sensors for long-term monitoring of blood glucose. Glucose Dehydrogenase (GDH) or glucose oxidase (GOx) in existing marketed blood glucose sensors reacts with glucose in a sample to produce an electrical signal that is related to glucose concentration. The method has the advantages of rapid reaction, high selectivity and good sensitivity, but factors such as a fixing method, temperature, pH (activity loss when the pH is less than 2 or more than 8) and the like obviously influence the enzyme activity.
In order to overcome the disadvantages of short shelf life, harsh storage conditions, limited oxygen and the like, the development of an enzyme-free glucose sensor has become a major trend, but the existing enzyme-free glucose sensor has the disadvantages of narrow detection range, slow glucose oxidation kinetics and low sensitivity, and in addition, the electrochemical potential of glucose oxidation is usually high enough to catalyze physiological substances of a human body, so that the anti-interference capability is poor.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-sensitivity glucose sensor, a preparation method and application thereof, and the glucose sensor can effectively solve the problems of poor stability and great influence by external environment of the existing enzyme glucose sensor.
In order to achieve the above purpose, the technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of a high-sensitivity glucose sensor comprises the following steps:
(1) Mixing a thiamine pyrophosphate solution with a hydrochloric acid solution containing chitosan, adding water for dilution after stirring reaction, and then adding a sodium alginate solution to prepare a chitosan-thiamine pyrophosphate/sodium alginate nanogel solution;
(2) To Cu 2+ Drop-adding chitosan-sulfur into the solutionThe amine pyrophosphates/sodium alginate nanogel solution is centrifuged, and the precipitate is collected and dried to prepare chitosan-thiamine pyrophosphates/sodium alginate/Cu 2+ A material;
(3) Chitosan-thiamine pyrophosphate/sodium alginate/Cu 2+ Grinding the material, and then annealing to obtain Cu-Cu with porous structure 2+1 An O material;
(4) Bonding the copper foil to the PDMS substrate, and then bonding the Cu-Cu of the porous structure 2+1 And coating the mixture of the O material, the conductive carbon black and the polyvinylidene fluoride on the surface of the copper foil, and then carrying out vacuum drying to obtain the copper foil.
Further, in the step (1), the mass ratio of the thiamine pyrophosphate to the chitosan to the sodium alginate is 1-20:9-180:20-400, the pH value of the hydrochloric acid solution is 2.5-4.5, and the stirring reaction time is 0.1-2h.
Further, cu in the step (2) 2+ The molar ratio of the chitosan-thiamine pyrophosphate/sodium alginate nanogel to the chitosan-thiamine pyrophosphate/sodium alginate nanogel is 1-3:0.5-1.5.
Further, in the step (2), the drying temperature is 20-80 ℃ and the drying time is 1-24h.
Further, in the step (3), annealing is performed by adopting a microwave heating mode, wherein the annealing power is 800-1000w, and the annealing time is 1-5min.
Further, cu-Cu of the porous structure in the step (4) 2+1 The mass ratio of the O material to the conductive carbon black to the polyvinylidene fluoride is 60-80:5-30:5-20.
Further, in the step (4), the vacuum drying temperature is 100-140 ℃ and the drying time is 10-14h.
Further, in the step (4), cu-Cu is on the surface of the copper foil 2+1 The dosage of O material is 0.4-0.6mg/cm 2 。
A high-sensitivity glucose sensor is prepared by the method.
The high-sensitivity glucose sensor is applied to qualitative and quantitative detection of glucose.
The beneficial effects of the invention are as follows:
1. the invention adopts the micropore/mesopore metal material to replace glucose oxidase or glucose dehydrogenase for measuring the concentration of glucose, and can effectively solve the problems of poor stability, great influence on the sensing performance by factors such as environmental temperature, pH value, illumination and the like of the glucose sensor based on enzyme.
2. The invention adopts CS and SA materials, utilizes the electrostatic self-assembly technology to prepare the soft template, and has the characteristics of natural sources, simple synthesis, safe and environment-friendly water reaction and the like.
3. The invention uses carboxyl and Cu in SA 2+ Chelation, cu is introduced into the nanogel 2+ The clusters have the characteristics of low cost, no toxicity, high electrochemical activity and the like.
4. The method removes the soft template in the microwave annealing process and simultaneously reduces Cu in situ 2+ Obtaining Cu-Cu 2+1 O porous material. Template removal and Cu 2+ The reduction of the metal oxide porous material is carried out simultaneously, so that the glucose sensor prepared from the metal oxide porous material has the characteristics of high efficiency and convenience, and has high selectivity; the reduced Cu can oxidize glucose, and meanwhile, the unique porous structure can effectively improve the signal-to-noise ratio of the glucose sensor, so that the glucose sensor has high selectivity.
5. The preparation method of the material adopted by the invention is carried out in aqueous solution, does not need to use organic solvent, has green and environment-friendly production process, has no organic solvent residue, and is beneficial to expanding the application range.
6. The invention has cheap raw materials and simple synthesis path, can rapidly prepare a large amount of conductive materials, and is beneficial to mass production and commercial application of novel flexible bioelectronic devices.
Drawings
FIG. 1 is a Cu-Cu porous structure in example 1 2+1 SEM photograph of O material;
FIG. 2 is a CV curve of a working electrode of a glucose sensor;
FIG. 3 is a graph of electrochemical response of a working electrode of a glucose sensor versus glucose concentration;
FIG. 4 is a schematic diagram of the operational stability of a glucose sensor working electrode;
FIG. 5 is a schematic diagram of the operational stability of a working electrode of a glucose sensor.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the particular embodiments described herein are illustrative only and are not intended to limit the invention, i.e., the embodiments described are merely some, but not all, of the embodiments of the invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the invention, as presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present invention.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
A preparation method of the high-sensitivity glucose sensor comprises the following steps:
(1) Mixing a thiamine pyrophosphate solution with a hydrochloric acid solution containing chitosan, stirring for reacting for 1h, adding water for dilution, and then adding a sodium alginate solution, wherein the mass ratio of the thiamine pyrophosphate to the chitosan to the sodium alginate is 10:90:200, and the pH value of the hydrochloric acid solution is 3.5, so as to prepare a chitosan-thiamine pyrophosphate/sodium alginate nanogel solution;
(2) To Cu 2+ Dropwise adding chitosan-thiamine pyrophosphate/sodium alginate nanogel solution and Cu into the solution 2+ The molar ratio of the chitosan-thiamine pyrophosphate/sodium alginate nanogel to the chitosan-thiamine pyrophosphate/sodium alginate nanogel is 2:1, and then the chitosan-thiamine pyrophosphate/sodium alginate/Cu is prepared by centrifuging, collecting the precipitate and drying the precipitate for 12 hours at 60 ℃ 2+ A material;
(3) Chitosan-thiamine pyrophosphate/sodium alginate/Cu 2+ After grinding the material, annealing treatment is carried out by adopting a microwave heating mode, the annealing power is 900w, the annealing time is 1min, and the Cu-Cu with a porous structure is prepared 2+1 An O material;
(4) Bonding the copper foil and the PDMS substrate through a photo-curing adhesive, and then bonding the Cu-Cu with a porous structure 2+1 Coating the mixture of O material, conductive carbon black and polyvinylidene fluoride on the surface of copper foil, and Cu-Cu with porous structure 2+1 The mass ratio of the O material to the conductive carbon black to the polyvinylidene fluoride is 70:20:10, and then vacuum drying is carried out for 12 hours at 120 ℃, wherein Cu-Cu is arranged on the surface of the copper foil 2+1 The dosage of the O material is 0.5mg/cm 2 . Is prepared.
Example 2
A preparation method of the high-sensitivity glucose sensor comprises the following steps:
(1) Mixing a thiamine pyrophosphate solution and a hydrochloric acid solution containing chitosan, stirring for reaction for 1.5 hours, adding water for dilution, and then adding a sodium alginate solution, wherein the mass ratio of the thiamine pyrophosphate to the chitosan to the sodium alginate is 15:100:150, and the pH value of the hydrochloric acid solution is 3.0, so as to prepare a chitosan-thiamine pyrophosphate/sodium alginate nanogel solution;
(2) To Cu 2+ Dropwise adding chitosan-thiamine pyrophosphate/sodium alginate nanogel solution and Cu into the solution 2+ The molar ratio of the chitosan-thiamine pyrophosphate/sodium alginate nanogel to the chitosan-thiamine pyrophosphate/sodium alginate nanogel is 2:1.5, and then the chitosan-thiamine pyrophosphate/sodium alginate/Cu is prepared by centrifuging, collecting the precipitate and drying the precipitate for 24 hours at 20 ℃ 2+ A material;
(3) Chitosan-thiamine pyrophosphate/sodium alginate/Cu 2+ After grinding the material, annealing treatment is carried out by adopting a microwave heating mode, the annealing power is 800w, the annealing time is 4min, and the Cu-Cu with a porous structure is prepared 2+1 An O material;
(4) Bonding the copper foil to the PDMS substrate, and then bonding the Cu-Cu of the porous structure 2+1 Coating the mixture of O material, conductive carbon black and polyvinylidene fluoride on the surface of copper foil, and Cu-Cu with porous structure 2+1 The mass ratio of the O material, the conductive carbon black and the polyvinylidene fluoride is 60:20:20, and thenVacuum drying at 100deg.C for 14 hr, wherein the copper foil surface is Cu-Cu 2+1 The dosage of the O material is 0.4mg/cm 2 . Is prepared.
Example 3
A preparation method of the high-sensitivity glucose sensor comprises the following steps:
(1) Mixing a thiamine pyrophosphate solution with a hydrochloric acid solution containing chitosan, stirring for reacting for 2 hours, adding water for dilution, and then adding a sodium alginate solution, wherein the mass ratio of the thiamine pyrophosphate to the chitosan to the sodium alginate is 10:150:200, and the pH value of the hydrochloric acid solution is 4.5, so as to prepare a chitosan-thiamine pyrophosphate/sodium alginate nanogel solution;
(2) To Cu 2+ Dropwise adding chitosan-thiamine pyrophosphate/sodium alginate nanogel solution and Cu into the solution 2+ The molar ratio of the chitosan-thiamine pyrophosphate/sodium alginate nanogel to the chitosan-thiamine pyrophosphate/sodium alginate nanogel is 2:0.5, and then the chitosan-thiamine pyrophosphate/sodium alginate/Cu is prepared by centrifuging, collecting the precipitate and drying for 1h at 80 ℃ 2+ A material;
(3) Chitosan-thiamine pyrophosphate/sodium alginate/Cu 2+ After grinding the material, annealing treatment is carried out by adopting a microwave heating mode, the annealing power is 1000w, the annealing time is 1min, and the Cu-Cu with a porous structure is prepared 2+1 An O material;
(4) Bonding the copper foil to the PDMS substrate, and then bonding the Cu-Cu of the porous structure 2+1 Coating the mixture of O material, conductive carbon black and polyvinylidene fluoride on the surface of copper foil, and Cu-Cu with porous structure 2+1 The mass ratio of the O material to the conductive carbon black to the polyvinylidene fluoride is 80:10:10, and then vacuum drying is carried out for 10 hours at 140 ℃, wherein Cu-Cu is arranged on the surface of the copper foil 2+1 The dosage of the O material is 0.6mg/cm 2 . Is prepared.
Test examples
Cu-Cu of the porous Structure obtained in example 1 2+1 The microscopic morphology of the O material is observed, and the specific result is shown in figures 1-2. As can be seen from FIG. 1, the CS-TPP/SA/Cu is processed under the condition of the microwave processing time length of 1min by utilizing the time length controllability of the microwave processing 2+ The film is prepared into a film withCu-Cu having porous structure 2+1 O material, the size is uniform, and the aperture is about 53+/-9 nm.
CV test was performed on the working electrode of the glucose sensor prepared in example 1, and the specific test results are shown in FIG. 2. From FIG. 2, it can be seen that the copper substrate is electrochemically active against glucose when Cu-Cu 2+1 The significant electrocatalytic response associated with glucose oxidation occurs at 0.4V when the O-modified electrode is exposed to a 4mM glucose solution.
The electrochemical response of the glucose sensor prepared in example 1 was tested, and the specific test results are shown in fig. 3. As can be seen from FIG. 3, the electrochemical response of the working electrode of the glucose sensor thus obtained was correlated with the glucose concentration, and the electrochemical response was correlated with the glucose concentration in a good linear manner in the range of 0.5 to 20mM in which the applied potential was maintained at 0.6V (R 2 ＝0.0076)。
The stability of the glucose sensor prepared in example 1 was tested, and the specific test results are shown in fig. 4. The operational stability of the working electrode of the glucose sensor can be seen in fig. 4, and the continuous operation of the sensor is proved to have good stability by monitoring the intensity of the operating current when the applied potential is maintained at 0.6V. At operating times as long as 1800s, the current loss was only 9.5%.
The glucose sensor prepared in example 1 was tested for its anti-interference performance, and the specific test results are shown in fig. 5. The tamper resistance of the working electrode of the glucose sensor can be seen in fig. 5. When a glucose solution with a concentration of 1mM was added to the electrolyte, a significant increase in the response current tended to occur. When endogenous interferents AA, UA, DA and AP were added, the current change was weak. In the next experiment, when glucose solution with a concentration of 1mM was continuously added to the electrolyte, a significant increase in response current was observed, which proved that Cu-Cu was 2+1 The O-modified electrode is hardly affected by interfering substances. The material with high selective response provides a new idea for preparing electrode materials of the enzyme-free glucose sensor.
Claims (10)
1. The preparation method of the high-sensitivity glucose sensor is characterized by comprising the following steps of:
(1) Mixing a thiamine pyrophosphate solution with a hydrochloric acid solution containing chitosan, adding water for dilution after stirring reaction, and then adding a sodium alginate solution to prepare a chitosan-thiamine pyrophosphate/sodium alginate nanogel solution;
(2) To Cu 2+ Dripping chitosan-thiamine pyrophosphate/sodium alginate nanogel solution into the solution, centrifuging, collecting precipitate, and drying to obtain chitosan-thiamine pyrophosphate/sodium alginate/Cu 2+ A material;
(3) Chitosan-thiamine pyrophosphate/sodium alginate/Cu 2+ Grinding the material, and then annealing to obtain Cu-Cu with porous structure 2+1 An O material;
(4) Bonding the copper foil to the PDMS substrate, and then bonding the Cu-Cu of the porous structure 2+1 And coating the mixture of the O material, the conductive carbon black and the polyvinylidene fluoride on the surface of the copper foil, and then carrying out vacuum drying to obtain the copper foil.
2. The method for preparing a high-sensitivity glucose sensor according to claim 1, wherein the mass ratio of thiamine pyrophosphate to chitosan to sodium alginate in the step (1) is 1-20:9-180:20-400, the pH value of the hydrochloric acid solution is 2.5-4.5, and the stirring reaction time is 0.1-2h.
3. The method for manufacturing a high-sensitivity glucose sensor according to claim 1, wherein Cu in the step (2) 2+ The molar ratio of the chitosan-thiamine pyrophosphate/sodium alginate nanogel to the chitosan-thiamine pyrophosphate/sodium alginate nanogel is 1-3:0.5-1.5.
4. The method for manufacturing a high-sensitivity glucose sensor according to claim 1, wherein the drying temperature in the step (2) is 20 to 80℃and the drying time is 1 to 24 hours.
5. The method for manufacturing a high-sensitivity glucose sensor according to claim 1, wherein the annealing is performed in the step (3) by microwave heating, the annealing power is 800-1000w, and the annealing time is 1-5min.
6. The method for manufacturing a high-sensitivity glucose sensor according to claim 1, wherein Cu-Cu of the porous structure in the step (4) 2+1 The mass ratio of the O material to the conductive carbon black to the polyvinylidene fluoride is 60-80:5-30:5-20.
7. The method for manufacturing a high-sensitivity glucose sensor according to claim 1, wherein the vacuum drying temperature in the step (4) is 100-140 ℃ and the drying time is 10-14h.
8. The method for manufacturing a high-sensitivity glucose sensor according to claim 1, wherein the copper foil surface in step (4) is Cu-Cu 2+1 The dosage of O material is 0.4-0.6mg/cm 2 。
9. A high sensitivity glucose sensor, characterized in that it is manufactured by the method according to any one of claims 1-8.
10. Use of the high sensitivity glucose sensor of claim 9 for qualitative and quantitative glucose detection.
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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