阅读说明：本技术 无酶葡萄糖传感元件及制备方法与应用 (Enzyme-free glucose sensing element and preparation method and application ) 是由 刘晨晨 崔光亮 张品华 王晓丽 李建福 于 2019-08-15 设计创作，主要内容包括：本发明公开了一种无酶葡萄糖传感元件及制备方法与应用,属于生物检测技术领域。解决了现有传感器传感能力低、耗时长、检测性能低等问题,所述的无酶葡萄糖传感元件,是基于氧化亚铜二维阵列的葡萄糖传感元件。步骤：取沉积在绝缘基底上的Cu<Sub>2</Sub>O基有序纳微结构阵列样品材料,用掩膜板Ⅰ盖住靠近绝缘基底中心的样品材料的一端,再用掩膜板Ⅱ盖住掩膜板Ⅰ,使掩膜板Ⅰ和掩膜板Ⅱ中心轴重合,其中掩膜板Ⅱ的宽度大于掩膜板Ⅰ；通过溅射方法在绝缘基底和掩膜板Ⅱ表面溅射金导电膜；取下掩膜板Ⅱ,在暴露出来的样品材料上涂抹疏水绝缘层；取下掩膜板Ⅰ,在两侧金导电膜上连接导电电极即可。本发明可用于制备无酶葡萄糖传感元件。(The invention discloses a kind of enzyme-free glucose sensing element and preparation method and applications, belong to technical field of biological.Solves the problems such as existing sensor senses ability is low, time-consuming, detection performance is low, the enzyme-free glucose sensing element is the glucose sensing element based on cuprous oxide two-dimensional array.Step: the Cu of deposition on a dielectric base is taken 2 The orderly nano-micro structure array sample material of O base, one end of the specimen material close to dielectric base center is covered with mask plate I, mask plate I is covered with mask plate II again, makes II center overlapping of axles of mask plate I and mask plate, wherein the width of mask plate II is greater than mask plate I；Golden conductive film is sputtered in dielectric base and II surface of mask plate by sputtering method；Mask plate II is removed, smears drain insulating layer on the specimen material being exposed；Mask plate I is removed, conductive electrode is connected on the gold conductive film of two sides.The present invention can be used for preparing enzyme-free glucose sensing element.)

1. a kind of enzyme-free glucose sensing element, it is characterised in that: be the glucose sensing member based on cuprous oxide two-dimensional array Part.

2. enzyme-free glucose sensing element according to claim 1, it is characterised in that: the cuprous oxide two-dimensional array It is Cu₂The orderly nano-micro structure array material of O base.

3. a kind of preparation method of enzyme-free glucose sensing element of any of claims 1 or 2, it is characterised in that including following step It is rapid:

(1) Cu of deposition on a dielectric base is taken₂The orderly nano-micro structure array sample material of O base is covered with mask plate I close to absolutely One end of the specimen material of edge base center, then mask plate I is covered with mask plate II, make II central axis of mask plate I and mask plate It is overlapped, wherein the width of mask plate II is greater than mask plate I；

(2) golden conductive film is sputtered in dielectric base and II surface of mask plate by sputtering method；

(3) mask plate II is removed, smears drain insulating layer on the specimen material being exposed；

(4) mask plate I is removed, connects conductive electrode on the gold conductive film of two sides to get the enzyme-free glucose sensing element is arrived Part.

4. the preparation method of enzyme-free glucose sensing element according to claim 3, it is characterised in that: the Cu₂O base The preparation method of orderly nano-micro structure array sample material the following steps are included:

A, electric depositing solution is configured using copper nitrate, nitric acid, ultrapure water as raw material, the concentration of copper nitrate is 50mM/L, 20 μ L of nitric acid；

B, the anode and cathode of electro-deposition, electrode long 2-2.5cm, wide 1-2mm are with the ultrapure copper foil of 30 μ m-thicks；

C, two copper electrodes are connected with power positive cathode respectively, then the parallel width in electrochemical growth room that is put into is 10- 20mm, length are in the dielectric base of 15-25mm；

D, electrolyte is added dropwise between spacing is two electrodes of 6-10mm, covered simultaneously guarantees between coverslip without generating gas Bubble；

E, indoor temperature control will be grown at -1.7 to -2.0 DEG C, placed 10-20 minutes；Electrolyte keeps constant temperature shape after freezing State is placed 20 minutes；First apply DC voltage on the electrode, object to be deposited changes semisinusoidal deposition potential, sample into after starting growth It gradually deposits on a dielectric base, dielectric base is taken out after deposition, clean 3--5 times with ultrapure water to get exhausted to being deposited on Cu in edge substrate₂The orderly nano-micro structure array sample material of O base.

5. the preparation method of enzyme-free glucose sensing element according to claim 4, it is characterised in that: the Cu₂O base Orderly nano-micro structure array sample material width is greater than 5mm.

6. the preparation method of enzyme-free glucose sensing element according to claim 5, it is characterised in that: the mask plate I width is 0.5-1mm, and II width of mask plate is 2-3mm.

7. the preparation method of enzyme-free glucose sensing element according to claim 6, it is characterised in that: the gold is conductive The resistance of film is less than 20 Ω/cm.

8. the preparation method of enzyme-free glucose sensing element according to claim 7, it is characterised in that: described in step e DC voltage is 0.5-0.6V.

9. the preparation method of enzyme-free glucose sensing element according to claim 8, it is characterised in that: described in step e Semisinusoidal deposition potential voltage is 0.2-0.7V, frequency 0.5-1Hz.

10. a kind of application of enzyme-free glucose sensing element described in claim 1-2 or 4-9, it is characterised in that: described Enzyme-free glucose sensing element is connected on matched four probe conductions tester the detection acquisition that can carry out electric signal.

Technical field

The present invention relates to a kind of enzyme-free glucose sensing element and preparation method and applications, belong to Measurement for Biotechnique neck Domain.

Background technique

Currently, glucose sensor mainly includes enzyme (based on glucose oxidase) and without enzyme (based on electrochemical oxidation) Two kinds, wherein oxidizing ferment base glucose sensor higher cost, and the structure based on enzyme itself and there are many problems, it is such as steady It is qualitative it is poor, reproducibility is lower, is easy to be affected by the ambient, enzyme-free glucose sensor overcomes these well It is insufficient.But the selectivity of no enzyme sensor is bad, poor anti jamming capability etc. is also a problem to be solved.Noble metal and its mixing Object such as gold, platinum, nickel, Jin-silver, gold-platinum enzyme-free glucose sensor is widely studied, but these materials that there are sensibility is low, The disadvantages of poor selectivity, lead to that sensor senses ability is low, time-consuming, detection performance is low.And since cost of manufacture is high, It cannot be widely applied to commodity production.

Summary of the invention

The technical problem to be solved by the present invention is overcoming the deficiencies of the prior art and provide, a kind of transmission speed is fast, electric conductivity Good, high sensitivity enzyme-free glucose sensing element；The present invention additionally provides the system of this enzyme-free glucose sensing element simultaneously Preparation Method and application.

The enzyme-free glucose sensing element is the glucose sensing element based on cuprous oxide two-dimensional array.

Utilize electric signal before and after enzyme-free glucose sensing element and glucose exposure based on cuprous oxide two-dimensional array Change to react concentration of glucose, the present invention utilizes four Probe-detection methods, passes through systematic characterization test, and detection oxidation is sub- Curent change of the copper two-dimensional material before and after contacting glucose, obtains the linear relationship of current-responsive and concentration of glucose, that is, builds The corresponding relationship of vertical current detection value and concentration of glucose, the detection of concentration of glucose, such as Fig. 3 are realized with this.

Preferred enzyme-free glucose sensing element, the cuprous oxide two-dimensional array is Cu₂The orderly nano-micro structure battle array of O base Column material.

The preparation method of the enzyme-free glucose sensing element, comprising the following steps:

(1) Cu of deposition on a dielectric base is taken₂The orderly nano-micro structure array sample material of O base, is covered with mask plate I and is leaned on One end of the specimen material at nearly dielectric base center, then mask plate I is covered with mask plate II, make in mask plate I and mask plate II Mandrel is overlapped, and wherein the width of mask plate II is greater than mask plate I；

(2) golden conductive film is sputtered in dielectric base and II surface of mask plate by sputtering method；

(3) mask plate II is removed, smears drain insulating layer on the specimen material being exposed；

(4) mask plate I is removed, conductive electrode is connected on the gold conductive film of two sides and is passed to get to the enzyme-free glucose Sensing unit.

The present invention utilizes the two-dimensional structure array material of electrochemical deposition experimental method building, has low manufacture cost, inspection Survey the advantages such as performance is good, using its two-dimensional nanostructure, cyclic array, large specific surface area, electron-transport speed fastly, electric conductivity The features such as good, high sensitivity, good selectivity, realize the detection to concentration of glucose.And what the present invention constructed receive microsensor Part has the characteristics that manufacturing technology requirement is low, at low cost, is easy to scale commodity production.The present invention provides a kind of new spirits Quick, fast and accurately enzyme-free glucose detecting element and application method.

The Cu₂The preparation method of the orderly nano-micro structure array sample material of O base the following steps are included:

A, electric depositing solution is configured using copper nitrate, nitric acid, ultrapure water as raw material, the concentration of copper nitrate is 50mM/L, nitric acid 20μL；

B, the anode and cathode of electro-deposition, electrode long 2-2.5cm, wide 1-2mm are with the ultrapure copper foil of 30 μ m-thicks；

C, two copper electrodes are connected with power positive cathode respectively, then the parallel width in electrochemical growth room that is put into is 10-20mm, length are in the dielectric base of 15-25mm；

D, electrolyte is added dropwise between spacing is two electrodes of 6-10mm, covered simultaneously guarantees not produce between coverslip Anger bubble；

E, indoor temperature control will be grown at -1.7 to -2.0 DEG C, placed 10-20 minutes；Electrolyte keeps permanent after freezing Temperature state is placed 20 minutes；First applying DC voltage on the electrode, object to be deposited changes semisinusoidal deposition potential into after starting growth, Sample gradually deposits on a dielectric base, and dielectric base is taken out after deposition, cleans 3--5 times with ultrapure water to get deposition is arrived Cu on a dielectric base₂The orderly nano-micro structure array sample material of O base.

Preferably, the Cu₂The orderly nano-micro structure array sample material width of O base is greater than 5mm.

Preferably, I width of mask plate is 0.5-1mm, and II width of mask plate is 2-3mm.

Preferably, the resistance of the golden conductive film is less than 20 Ω/cm.

Preferably, DC voltage described in step e is 0.5-0.6V.

Preferably, semisinusoidal deposition potential voltage described in step e be 0.2-0.7V, frequency 0.5-1Hz.

Preferably, the enzyme-free glucose sensing element is connected on matched four probe conductions tester can be into The detection of horizontal electrical signal acquires.

Compared with prior art the beneficial effects of the present invention are:

(1) Cu prepared by the present invention₂The orderly nano-micro structure array material of O base is two-dimensional structure material and long-range order, steady Qualitative height.State modulator when for building enzyme-free glucose sensing element is highly beneficial.Based on conductance preferential growth principle, material The electric conductivity of material has very strong advantage.

(2) enzyme-free glucose sensing element preparation method of the invention is simple, easy to store, and testing cost is low, as a result can be straight Reading is connect, is a kind of sensitive, fast and accurately clinical and family disease detection method.

(3) enzyme-free glucose sensing element high sensitivity (detection accuracy can achieve 0.1mM) of the invention, detection range (0.1-15mM) greatly.Detection electric current and the linear relationship that concentration of glucose is met are as shown in Figure 3.The nano effect of material, week Phase property structure provides big specific surface area, improves the contact area of device and glucose, to promote the electric oxygen of glucose Change catalysis, while to ascorbic acid present in blood of human body, urea, the different kinds of ions such as cysteine have very strong anti-interference Property.

Detailed description of the invention

Fig. 1 is the preparation flow figure of enzyme-free glucose sensing element of the present invention；

Fig. 2 is the Cu₂The orderly nano-micro structure array material scanning electron microscope diagram of O base；

Fig. 3 is based on Cu₂The linear relationship chart of O base orderly nano-micro structure array material concentration of glucose and electric current.

Specific embodiment

The present invention will be further described combined with specific embodiments below.