CN103063720B - Electrode for trans-scale glucose biosensor based on ZnO nanowire and preparation method thereof - Google Patents

Electrode for trans-scale glucose biosensor based on ZnO nanowire and preparation method thereof Download PDF

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CN103063720B
CN103063720B CN201310000633.8A CN201310000633A CN103063720B CN 103063720 B CN103063720 B CN 103063720B CN 201310000633 A CN201310000633 A CN 201310000633A CN 103063720 B CN103063720 B CN 103063720B
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wire
zno nano
helix
bonding gold
electrode
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CN103063720A (en
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景蔚萱
周帆
陈路加
牛玲玲
王兵
齐含
蒋庄德
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Xian Jiaotong University
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Abstract

The invention relates to an electrode for a trans-scale glucose biosensor based on a ZnO nanowire and a preparation method thereof. The electrode comprises an optical fiber core taken as a substrate and a gold bonding wire wound on the optical fiber core in a manner of a spiral line; wherein the gold bonding wire is divided into a spiral line part and a lead part; the ZnO nanowire grows in the direction of a spiral line surface normal of the spiral line part by adopting a hydrothermal method; and glucose oxidase is fixed on the ZnO nanowire. The electrode and the preparation method thereof have the benefits that the gold bonding wire is wound on the cylindrical optical fiber core to form a spiral line array structure; secondly, the ZnO nanowire grows at the spiral line part of the gold bonding wire based on a water bath method to form a micro-nanometer trans-scale structure for increasing the adsorption area of the glucose oxidase; and based on the trans-scale structure, the process parameters of the ZnO nanowire are improved to form a specific random rough surface for enhancing the adsorption of buffer solution on the spiral line-shaped electrode and the fixation of the glucose oxidase on the electrode, thereby greatly improving the catalytic efficiency of the electrode for a glucose sensor.

Description

A kind of based on ZnO nano-wire across yardstick glucose sensor with electrode and preparation method thereof
Technical field
The invention belongs to micro sensing technical field, be mainly used in the fields such as medical science, biology, food processing, galvanochemistry, environmental monitoring, particularly a kind of for blood of human body and urine examination of glucose concentration based on ZnO nano-wire across yardstick glucose sensor with electrode and preparation method thereof.
Background technology
Glucose is the very crucial metabolin of life entity.Concerning diabetic, accurately determine rapidly that the concentration of glucose in blood and urine is very important clinical detection project always.At present be just subject to paying close attention to more and more widely as the third generation glucose sensor of principal character with interelectrode Direct electron transfer taking glucose oxidase and sensor, its research emphasis mainly comprises chemical reaction mechanism between glucose oxidase and tested glucose, directly transports and increase the three aspects: such as material selection, the Fine design of basal electrode structure of enzyme adsorption area for electronics.Aspect above-mentioned material selection, ZnO nano-wire has the following advantages and is applied to gradually glucose sensor with in electrode, and surface volume is than large, nontoxic, has bio-compatibility, and electrochemical properties is stable, and electron transfer capacity is very strong etc.The most important thing is, it has higher isoelectric point (IEP ~ 9.5ev), can adsorb enzyme or protein (as glucose oxidase, IEP ~ 4.2ev) that isoelectric point is lower.Be 7.4 o'clock at pH, the ZnO nano-wire of positively charged not only provides good microenvironment for fixing electronegative glucose oxidase, and has promoted the electronics between glucose oxidase and electrode to shift on a large scale.
Glucose sensor electrode based on ZnO nano-wire, adopt ZnO nano-wire to modify sensor electrode surface, and rely on the ZnO nano-wire of positively charged that electronegative glucose oxidase is fixed on to sensor electrode surface, then utilize the glucose oxidase that is fixed on sensor electrode surface as recognition component, by measuring the electric signal of the redox reaction generation occurring in enzyme catalysis lower electrode surface, realize the detection to concentration of glucose.In order to improve sensitivity, response speed, the serviceable life of such sensor, reduce the performances such as minimum detectability, and prevent that coming off of glucose oxidase from reducing the catalytic efficiency of enzyme with loss, therefore research emphasis mainly concentrates on two aspects such as adsorption area, the reliable absorption of glucose oxidase that increase basal electrode.
Tao Kong deposits ZnO nanorod with electrochemical deposition method on plane gold electrode, then with sodium hydroxide solution, ZnO nanorod is etched into ZnO nano pipe, and on ZnO nano pipe fixing glucose oxidase, finally, at gold electrode surfaces deposition one deck Nafion of sensor film, obtain corresponding glucose sensor electrode; Wei, by first growing ZnO nano-wire on plane gold electrode of hydro-thermal method, then fixes one deck glucose oxidase on ZnO nanorod, has finally prepared the glucose sensor electrode needing.The above-mentioned glucose sensor based on ZnO nano-wire is all increasing the sensor effective active area of electrode in varying degrees with electrode, and has improved the fixed efficiency of glucose oxidase.But because such glucose sensor electrode is planar structure, therefore physical dimension is large, is not easy to microminiaturization, and electrode adsorption area change is not remarkable; In addition also will be in planar substrates sputter layer of gold film as electrode, this is high to process equipment and preparation environmental requirement, therefore unsuitable production control cost.
Summary of the invention
The object of the present invention is to provide a kind of based on ZnO nano-wire across yardstick glucose sensor with electrode and preparation method thereof, the sensor of making by preparation method of the present invention is high with the catalytic efficiency of electrode, fast response time, low to the detection limit of glucose, signal to noise ratio (S/N ratio) is high, manufacturing process is simple, equipment requirement is relatively low, cost compare is cheap, yardstick is little.
For achieving the above object, of the present invention based on ZnO nano-wire across yardstick glucose sensor electrode, comprise the fiber core as substrate, be wound on the bonding gold wire on fiber core in helix mode, wherein bonding gold wire is divided into helix part and lead portion, one deck is along the ZnO nano-wire of the helix surface normal direction growth of helix part, and one deck is fixed on the glucose oxidase on ZnO nano-wire.
The length of described fiber core is 30mm, and diameter is 125 μ m.
The length of described bonding gold wire is 80mm, and diameter is 30 μ m.
Described ZnO nano-wire adopts hydro-thermal method along growing in bonding gold wire helix normal to a surface direction.
Preparation method of the present invention comprises the following steps:
1) get the optical fiber that length is 30mm, soak and peel off fibre cladding with acetone, extracting diameter out is the fiber core of 125 μ m;
2) getting length is that 80mm, diameter are the bonding gold wire of 30 μ m;
3) bonding gold wire is wound on fiber core in helix mode, forms helix assembly, wherein bonding gold wire is divided into helix part and lead portion, and this helix assembly is carried out to standard cleaning;
4) the ZnO nano-wire Seed Layer solution that compound concentration is 1mmol/L;
5) bonding gold wire helix part is immersed to ZnO nano-wire Seed Layer solution, keep taking out after 2 minutes, in bonding gold wire helix part, deposit ZnO nano-wire Seed Layer;
6) the helix assembly that deposits ZnO nano-wire Seed Layer is placed in to the vacuum drier of 150 DEG C and completes annealing in process;
7) the ZnO nano-wire growth-promoting media that compound concentration is 0.025mol/L;
8) employing hydro-thermal method, along growing ZnO nano-wire in the helix surface normal direction of bonding gold wire at 90 DEG C, obtains micro-nano across yardstick structure;
9) ultrasonic cleaning length has the helix assembly of ZnO nano-wire, and at room temperature dry;
10) compound concentration is that 0.01mol/L, pH are 7.4 phosphate buffer;
11) glucose oxidase is joined to the glucose oxidase solution that in above-mentioned phosphate buffer, compound concentration is 10mg/mL;
12) growth is had the bonding gold wire helix part of ZnO nano-wire immerse in glucose oxidase solution and keeps taking out after 15 minutes, and at room temperature dry, obtain one deck be fixed on ZnO nano-wire, for the glucose oxidase of catalytic action;
13) import through plastic suction pipe by fiber core end and bonding gold wire lead portion, and expose from plastic suction pipe end, guarantee the outer face of bonding gold wire helix part in plastic suction pipe import simultaneously, then toward injection ring epoxy resins in plastic suction pipe, and at room temperature make it curing.
The present invention uses the glucose sensor being incorporated into across the thinking of yardstick micro nano structure based on ZnO nano-wire in electrode design, and its remarkable design feature comprises following three aspects::
1, bonding gold wire (electrode material) is wound on column type fiber core, form helix array structure (low frequency space structure, yardstick is at micron order, can extend to other low frequency underlying structure), next helix part at bonding gold wire is based on immersion method growing ZnO nano-wire (high frequency spatial structure, yardstick is at nanoscale), form micro-nanoly across yardstick structure, be used for increasing the adsorption area of glucose oxidase;
2, on the above-mentioned basis across yardstick structure, technological parameter by improving ZnO nano-wire is to form specific random rough surfaces (as Gauss, non-Gauss, from high frequency body structure surfaces such as affine somatotypes), be used for strengthening absorption and the glucose oxidase fixing texts on electrode of damping fluid on spiral yarn shaped electrode, thereby significantly improve the catalytic efficiency of glucose sensor electrode;
3, because bonding gold wire electrode is wound on fiber core, do not need with microfabrication equipments, and fiber core Rigidity and strength is high, size is little, these features not only make this sensor electrode be easy to use, be convenient to detect and are microminiaturized, have also reduced in addition the requirement to preparation technology.
The invention has the beneficial effects as follows, bonding gold wire (electrode material) is wound on column type fiber core, form helix array structure, next helix part at bonding gold wire is based on immersion method growing ZnO nano-wire, form micro-nanoly across yardstick structure, be used for increasing the adsorption area of glucose oxidase; On the above-mentioned basis across yardstick structure, technological parameter by improving ZnO nano-wire is to form specific random rough surfaces, be used for strengthening absorption and the glucose oxidase fixing texts on electrode of damping fluid on spiral yarn shaped electrode, thereby significantly improve the catalytic efficiency of glucose sensor electrode; Because bonding gold wire electrode is wound on fiber core, do not need with microfabrication equipments, and fiber core Rigidity and strength is high, size is little, these features not only make this sensor electricity consumption very easily detect and microminiaturization in using, being convenient to, and have also reduced in addition the requirement to preparation technology.
This invention prepared based on ZnO nano-wire not only can be applied to the detection of concentration of glucose in blood of human body and urine in medical science across yardstick glucose sensor with electrode, and can be applied to the detection of the concentration of glucose in the fields such as biology, food processing, galvanochemistry, environmental monitoring.
Brief description of the drawings
Fig. 1 is the schematic diagram across yardstick glucose biological sensor electrode based on ZnO nano-wire of un-encapsulated of the present invention; Wherein Fig. 1 a is the helix assembly after fixing glucose oxidase, and Fig. 1 b is the partial enlarged drawing of Fig. 1 a;
Fig. 2 is that the present invention is wound on bonding gold wire the helix assembly schematic diagram forming on fiber core in helix mode;
Fig. 3 is the present invention on the helix surface of bonding gold wire along the schematic diagram after normal direction growing ZnO nano-wire; Wherein Fig. 3 a is the long helix assembly that has ZnO nano-wire, and Fig. 3 b is the partial enlarged drawing of Fig. 3 a;
Fig. 4 is the present invention's schematic diagram after fixing glucose oxidase on ZnO nano-wire; Fig. 4 a is the helix assembly after fixing glucose oxidase, and Fig. 4 b is the partial enlarged drawing of Fig. 4 a;
Fig. 5 is the schematic diagram after the present invention goes between, encapsulates.
Embodiment
Below in conjunction with accompanying drawing and case study on implementation, the present invention is described in further detail:
As Fig. 1, the present invention includes as the fiber core 1(length of substrate is 30mm, diameter be 125 μ m), (length is as 80mm to be wound on bonding gold wire on fiber core 1 in helix mode, diameter be 30 μ m), wherein bonding gold wire is divided into helix part 2 and lead portion 3, and one deck is along the ZnO nano-wire 4 of the helix surface normal direction growth of helix part 2, and one deck is fixed on the glucose oxidase 5 on ZnO nano-wire 4.
As shown in Fig. 2, Fig. 3, Fig. 4, Fig. 5, the above-mentioned glucose sensor based on ZnO nano-wire comprises the following steps by the preparation method of electrode:
1) get the optical fiber that length is 30mm, soak and peel off fibre cladding with acetone, extracting diameter out is the fiber core 1 of 125 μ m;
2) getting length is that 80mm, diameter are the bonding gold wire of 30 μ m;
3) standard cleaning fiber core and bonding gold wire, first adopt acetone ultrasonic cleaning 5 minutes, then use deionized water ultrasonic cleaning 2 minutes, then use absolute ethyl alcohol ultrasonic cleaning 2 minutes, use again deionized water ultrasonic cleaning 2 minutes, finally 150 DEG C of oven dry in vacuum drier;
4) bonding gold wire is wound on fiber core 1 in helix mode, form helix assembly, wherein bonding gold wire is divided into helix part 2 and lead portion 3, first use acetone ultrasonic cleaning 3 minutes, then use deionized water ultrasonic cleaning 1 minute, then use absolute ethyl alcohol ultrasonic cleaning 2 minutes, then use deionized water ultrasonic cleaning 1 minute, finally 150 DEG C of oven dry in vacuum drier, as Fig. 2;
5) take 0.06585g zinc acetate (C with electronic scales 4h 6o 4zn2H 2o), put into 50mL beaker, add 24mL absolute ethyl alcohol; Beaker is placed on magnetic stirrer, heats while stirring with the rotating speed of 2000r/min, until dissolve completely, naturally cool to room temperature; Take out 4mL acetic acid zinc solution, add 32mL absolute ethyl alcohol, seal beaker mouth with preservative film, put into 65 DEG C of heating of water bath 5 minutes;
6) take 0.024g NaOH (NaOH) with electronic scales, put into 50mL beaker, add 30mL absolute ethyl alcohol; Beaker is placed on magnetic stirrer, heats while stirring with the rotating speed of 2000r/min, until dissolve completely, naturally cool to room temperature; Get 4mL sodium hydroxide solution, add 10mL absolute ethyl alcohol, seal beaker mouth with preservative film, put into 65 DEG C of heating of water bath 5 minutes;
7) acetic acid zinc solution step 5) and step 6) being obtained respectively and sodium hydroxide solution mix, and seal beaker mouth with preservative film, put into 65 DEG C of heating of water bath 30 minutes; After taking-up, naturally cool to room temperature, just can obtain concentration is the ZnO nano-wire Seed Layer solution of 1mmol/L;
8) clamp the fiber core end of above-mentioned helix assembly with fixture, and bonding gold wire helix part is immersed in ZnO nano-wire Seed Layer solution and kept 2 minutes, and complete annealing in process under 150 DEG C of atmosphere, in triplicate;
9) take respectively 3.71g zinc nitrate (Zn (NO 3) 26H 2o), 1.75g hexamethylenetetramine (C 6h 12n 4), put into 500mL beaker, add 500mL deionized water, on magnetic stirrer, heat while stirring with the rotating speed of 3000r/min, be heated to 90 DEG C, just can obtain concentration is the ZnO nano-wire growth-promoting media of 0.025mol/L;
10) growing ZnO nano-wire, will put into beaker, the ZnO nano-wire growth-promoting media that adds step 9) to prepare with the above-mentioned fiber core of fixture clamping, seal beaker mouth with preservative film, put into 90 DEG C of growths of water-bath 120 minutes, obtain micro-nano across yardstick structure, as Fig. 3;
11) clean the long bonding gold wire that has ZnO nano-wire, have the bonding gold wire 5 minutes of ZnO nano-wire by deionized water ultrasonic cleaning length, under room temperature, be dried;
12) compound concentration is the phosphate buffer that 0.01mol/L, pH value are 7.4, takes 2.9009g sodium hydrogen phosphate (Na 2hPO 412H 2o), 0.2964g sodium dihydrogen phosphate (NaH 2pO 42H 2o), 0.7455g potassium chloride (KCl), adds deionized water dilution, and glass bar stirs, and is then settled to 1000mL;
13) glucose oxidase solution that compound concentration is 10mg/mL, takes 0.05g glucose oxidase, adds the above-mentioned phosphate buffer of 5mL, stirs;
14) (concentration is 0.01M the long bonding gold wire helix part that has a ZnO nano-wire to be immersed to phosphate buffer, pH is 7.4) in, first form hydrophilic surface, immersed again in the glucose oxidase solution that step 13) prepares 15 minutes, after taking-up, under room temperature, be dried 20 minutes, as Fig. 4;
15) import through plastic suction pipe 7 by fiber core end and bonding gold wire lead portion, and expose from plastic suction pipe end, the outer face of the helix part of simultaneously guaranteeing bonding gold wire in plastic suction pipe import, then toward injection ring epoxy resins 6 in plastic suction pipe, and at room temperature make it curing; Finally obtain based on ZnO nano-wire across yardstick glucose sensor electrode, as Fig. 5.

Claims (4)

  1. One kind based on ZnO nano-wire across yardstick glucose sensor electrode, it is characterized in that: comprise the fiber core (1) as substrate, be wound on the bonding gold wire on fiber core (1) in helix mode, wherein bonding gold wire is divided into helix part (2) and lead portion (3), one deck is along the ZnO nano-wire (4) of the helix surface normal direction growth of helix part (2), and one deck is fixed on the glucose oxidase (5) on ZnO nano-wire (4); Described ZnO nano-wire adopts hydro-thermal method along growing in bonding gold wire helix normal to a surface direction.
  2. According to claim 1 based on ZnO nano-wire across yardstick glucose sensor electrode, it is characterized in that: the length of described fiber core (1) is 30mm, diameter is 125 μ m.
  3. According to claim 1 based on ZnO nano-wire across yardstick glucose sensor electrode, it is characterized in that: the length of described bonding gold wire is 80mm, diameter is 30 μ m.
  4. 4. the preparation method with electrode across yardstick glucose sensor based on ZnO nano-wire, is characterized in that comprising the following steps:
    1) get the optical fiber that length is 30mm, soak and peel off fibre cladding with acetone, extracting diameter out is the fiber core (1) of 125 μ m;
    2) getting length is that 80mm, diameter are the bonding gold wire of 30 μ m;
    3) bonding gold wire is wound on fiber core (1) in helix mode, form helix assembly, wherein bonding gold wire is divided into helix part (2) and lead portion (3), and this helix assembly is carried out to standard cleaning;
    4) the ZnO nano-wire Seed Layer solution that compound concentration is 1mmol/L;
    5) bonding gold wire helix part (2) is immersed to ZnO nano-wire Seed Layer solution, keep taking out after 2 minutes, in the upper deposition of bonding gold wire helix part (2) ZnO nano-wire Seed Layer;
    6) the helix assembly that deposits ZnO nano-wire Seed Layer is placed in to the vacuum drier of 150 DEG C and completes annealing in process;
    7) the ZnO nano-wire growth-promoting media that compound concentration is 0.025mol/L;
    8) employing hydro-thermal method, along growing ZnO nano-wire in the helix surface normal direction of bonding gold wire at 90 DEG C, obtains micro-nano across yardstick structure;
    9) ultrasonic cleaning length has the helix assembly of ZnO nano-wire, and at room temperature dry;
    10) compound concentration is that 0.01mol/L, pH are 7.4 phosphate buffer;
    11) glucose oxidase is joined to the glucose oxidase solution that in above-mentioned phosphate buffer, compound concentration is 10mg/mL;
    12) growth is had the bonding gold wire helix part of ZnO nano-wire immerse in glucose oxidase solution and keeps taking out after 15 minutes, and at room temperature dry, obtain one deck be fixed on ZnO nano-wire, for the glucose oxidase of catalytic action;
    13) import through plastic suction pipe by fiber core end and bonding gold wire lead portion, and expose from plastic suction pipe end, guarantee the outer face of bonding gold wire helix part in plastic suction pipe import simultaneously, then toward injection ring epoxy resins in plastic suction pipe, and at room temperature make it curing.
CN201310000633.8A 2013-01-05 2013-01-05 Electrode for trans-scale glucose biosensor based on ZnO nanowire and preparation method thereof Expired - Fee Related CN103063720B (en)

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CN103344688A (en) * 2013-06-24 2013-10-09 西安交通大学 Working electrode for cylindrical array cross-scale glucose sensor and preparation method of working electrode
CN103983678B (en) * 2014-05-09 2016-06-29 西安交通大学 A kind of based on spherical glucose enzyme electrode across mesostructure array and preparation method thereof
CN106128769A (en) * 2016-07-04 2016-11-16 西安交通大学 A kind of three-dimensional dye-sensitized solar cell working electrode and preparation method thereof
CN111208184B (en) * 2020-02-03 2020-11-27 徐州融创达电子科技有限公司 Preparation process of non-enzymatic glucose sensing detection system
CN112525963B (en) * 2020-11-30 2023-01-13 南通市疾病预防控制中心 Electrochemical biosensor based on ZnO nano material and method for detecting glucose concentration by using electrochemical biosensor
CN113358725A (en) * 2021-05-17 2021-09-07 西安交通大学 Flexible electrochemical glucose sensor electrode and preparation method thereof

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