CN110455894A - A kind of nano-porous gold of sweat detection glucose is without enzyme flexible sensing electrode and the preparation method and application thereof - Google Patents
A kind of nano-porous gold of sweat detection glucose is without enzyme flexible sensing electrode and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention provides a kind of nano-porous golds of sweat detection glucose without enzyme flexible sensing electrode and the preparation method and application thereof.The present invention provides a kind of coplanar integrated enzyme-free glucose sensing electrode of three electrodes, by electro-deposition by the nano-porous gold of high catalytic activity in conjunction with fine interdigital electrode, to provide a kind of feasible method in microelectrode region electro-deposition nano material.The flexible sensing electrode sensitivity with higher of nano-porous gold modification provided by the invention, extremely low detection limit, wider inspection range and excellent stability and interference free performance, its detection is limited to 0.55 μM, possesses 1297 μ A/mMcm respectively in the inspection range of 0.001~2.50mM and 2.50~10.0mM2With 854.7 μ A/mMcm2High sensitivity.
Description
Technical field
The invention belongs to glucose detection sensor fields, are related to a kind of nano-porous gold of no enzyme detection glucose
(NPG) application of the preparation method of flexible sensing electrode, especially sensing electrode in glucose quickly detects.
Background technique
Diabetes are the insufficient insulins secreted due to human pancreas or cannot efficiently use disease caused by insulin.Closely
In decades, the disease incidence of diabetes constantly rises, and has been cited as one of four big non-communicable diseases.Diabetes are a kind of chronic
Disease can cause multiple complications such as hypopsia, renal failure, retinopathy and apoplexy etc., therefore to diabetes
Effectively extensive concern of the detection with treatment by society.
Studies have shown that strict glycemic control can ensure the life and health of diabetic, it effectively prevent complication.In order to
The intracorporal metaboilic level of people and blood-sugar content are understood in time, and this field needs a kind of with highly sensitive, high reliability grape
Sugar detection electrode for persistently detecting the content of glucose in human body, and is easy to use.
Detecting the main method of glucose at this stage includes electrochemical method, colorimetric method, conductance method, optical means and fluorescence
Spectroscopic methodology, wherein electrochemical process has many advantages, such as that detection limit is low, the response time is short, stability is good and cost is relatively low, therefore obtains
It is widely used.
Glucose is detected using electrochemical sensing technology, maximum limitation is that enzyme is extremely sensitive to external environment, is held
Easy in inactivation causes the electrochemical sensor containing enzyme to be difficult to reuse.Therefore, exploitation high-performance without enzyme electrochemical sensor especially
It is important.
Electrode is the core component of electrochemical sensor, wherein three-electrode system is using relatively broad.Three electrodes include
Working electrode, reference electrode and to electrode.Three electrodes of traditional three-electrode system are not in one plane integrated,
Between each electrode distance farther out, in working electrode in Electrochemical Test Procedure and to being easy to appear concentration polarization, shadow between electrode
Ring measuring accuracy.In addition, traditional three electrode sizes are big, it is not easy to the design and processing of microsensor, limits three electrode bodies
The application of system is also unfavorable for the universal and application of fast inspection type sensing electrode.
Patent CN109019572A discloses a kind of enzyme-free glucose electrochemical sensing electrode, main technical schemes be with
Foam Ni is template, using vapour deposition process (CVD) batch synthesis three-dimensional grapheme material 3D-G-Ni.Directly made with 3D-G-Ni
For electrode material and sensing interface, highly sensitive glucose is established without enzyme electrochemical sensing electrode, in human serum
The measurement of concentration of glucose.Its detection limit can reach 1 μM.However, this method needs to prepare at high temperature, and process conditions are complicated,
Preparation cost is higher, and by blood testing mode, more cumbersome than vitro detection.
And the labyrinth of interdigital electrode carrys out very big challenge to active material load-strap, prepares active material slurry at present
Material, preparing interdigital electrode by screen printing mode is common method, however this method limits slurry, and is difficult to
The line width line-spacing for regulating and controlling interdigital electrode, is also easy to cause electrode damage, thus how in tiny area electro-deposition active material
It is a problem urgently to be resolved.
In conclusion this field needs, a kind of preparation process is simple, reusable enzyme-free glucose quickly detects
Sensing electrode simplifies detecting step, and realize and detect glucose in vitro, so that glucose detection is more to reduce preparation cost
Add safe and simple.
Summary of the invention
The object of the present invention is to provide a kind of sweat that can be used for without enzyme detection glucose, nanoporous that three electrodes are coplanar
Golden flexible sensing electrode.
The electrode is made of polyimide flex substrate, conductive layer, conversion zone；Polyimide flex substrate surface is equipped with and leads
Electric layer, conductive layer surface are equipped with conversion zone；The conductive layer is at least two alloy-layers formed in Ti, Mo, W；It is described anti-
Layer surface is answered to be equipped with nanoporous layer gold；The electrode by three electrodes integrate it is coplanar form, wherein working electrode surface modification receive
Meter Duo Kong gold, to electrode face finish platinum, reference electrode surface modification silver-silver chloride.
The electrode front is provided with a pair of screw type interdigital electrode, respectively as working electrode and to electrode；Electrode is just
Face is provided with the semicircle electrode wires of outer ring as reference electrode；Working electrode and be 100 μm to the distance of electrode.
The electrode solve the problems, such as three-electrode system can not be applied to microsensor, and interdigital electrode obtained due to
It working electrode and is closer between electrode, the concentration polarization in Electrochemical Test Procedure can be substantially eliminated.By in electrode
The porous gold of surface finish nano also solves the technical issues of small electrode zone modifies nano-porous gold.
Electrode provided by the invention uses flexible polyimide substrate material, can fit closely human skin, bent, electricity
The nanoporous layer gold of pole surface modification does not generate situations such as falling off, being broken when electrode is bent, and illustrates electrode face finish
Nanoporous layer gold fit closely in electrode surface, it is not easily to fall off with failure, it is ensured that reliability in actual use.
The nano-porous gold layer surface of sensing electrode surface modification provided by the invention is the through-hole that diameter is 20~55nm
With continuous ligament structure, is conducive to the transmission of electronics conduction and electrolyte, provides a large amount of active sites for electrocatalytic reaction；It uses
The surface porosity factor of the nanoporous layer gold for the chemical corrosion method preparation that this patent provides is 70~80%, nanoporous gold surface
What low-light hole configurations played catalytic action mainly by forming less than the nanometer micropore of 50nm, to substance is work in nanometer micropore
Property site.
The surface porosity factor of the nanoporous layer gold of the electrochemical erosion method preparation provided using this patent is 60~75%,
Pore size is 5~25nm, this is because tin atom slowly aoxidizes precipitation in chemical corrosion process, golden ligament slowly deforms receipts
Contracting, forms relatively large hole, and electrochemical corrosion is comparatively quick, and the hole configurations that the gold of reservation is formed is smaller.
It can be used for nanometer that sweat quickly detects glucose, that three electrodes are coplanar it is a further object of the present invention to provide a kind of
Porous preparation method of the gold without enzyme flexible sensing electrode.
The nano-porous gold of sweat detection glucose provided by the invention is without the preparation method of enzyme flexible sensing electrode, specifically
The following steps are included:
(1) at least two alloy-layers formed in the sputtering of polyimide flex substrate surface Ti, Mo, W, then in alloy
Layer surface copper facing；
(2) polyimide-based bottom surface layers of copper is roughened through persulfuric acid microetch, one layer of dry film of hot pressing, through overexposure, development
And etching process, it will be in designed figure line transitions to substrate；
(3) chemical nickel plating and gold is soaked on the copper wire of polyimide-based bottom surface, it is saved in dry environments；
(4) thick layer gold is plated in polyimide flex electrode surface；
(5) platinum plating in the interdigital electrode of the positive right side of face of polyimide flex electrode；
(6) in polyimide flex electrode front deposited Au tin alloy, removal metallic tin is carried, obtains modification nanoporous
The electrode of gold；
(7) in the front disk electrode surface modification silver-silver chloride of polyimide flex electrode.
In step (1)~(3) of the present invention, titanium-tungsten is sputtered on polyimide substrate, surface conductance is used for, after copper facing
Fine-line is processed, in order to which protection circuit is not oxidized, chemical nickel plating is carried out and soaks golden processing.
Sensing electrode prepared by the present invention have multi-layer metal structure, electrode lower layer be oxidizable, not corrosion resistant copper and
Nickel, in order to ensure modification nano material on the electrode and carry out electro-chemical test during layers of copper and nickel layer it is unaffected, it is first
One layer of thicker layer gold is first electroplated on the line.
In step (4) of the present invention, gold plating solution composition are as follows: citric acid gold potassium 12g/L；Gold-plated temperature is 55 DEG C, and electric current is close
Degree is 1.0A/dm2, time 5min.
Sensing electrode prepared by the present invention uses three-electrode system, in order to need to platinum plating to electrode face finish platinum
Solution carries out experiment sieving, this is strong acid or alkali corrosion electrode in electroplating process in order to prevent, and circuit is caused to fall off or coating
Displacement reaction occurs.
In step (5) of the present invention, the preferred neutral soluble salt of the supporting electrolyte of plating solution can increase the ionic conductance of plating solution
Rate.Platinum plating bath group becomes H2PtCl61mM and KCl 0.1M.
The nanoporous gold electrode that can be used for glucose detection in the present invention in order to obtain, needs the electroplate liquid to electro-deposition
A large amount of experiment screening is carried out, this is because the electroplate liquid for gold-tin alloy deposition cannot be in entire available current density range
Interior deposit alloy, it is therefore desirable to the composition of sophisticated design electroplate liquid.For example, using gluconic acid, ethylenediaminetetraacetic acid etc.
The electroplate liquid in the prior art of complexant, it will usually obtain the conjunction under different current densities with the region Fu Xi or Fu Jin
Gold leads to the uneven of deposition.
The proportion of golden tin is also required to experiment determination in plating solution, with the increase of gold content in plating solution, the hole of nano-porous gold
Diameter reduces, and when gold content is too low, cracking phenomena occurs in porous layer gold, and influences to plate the binding force of interlayer, leads to nanoporous
Layer gold falls off from base, therefore the proportion general control of golden tin is 1: 1 or so.
In step (6) of the present invention, the composition of gold-tin alloy plating solution used in electro-deposition are as follows: potassium citrate 50g/L~55g/L,
Sodium citrate 5g/L~10g/L, ascorbic acid 15g/L~20g/L, p-methyl benzenesulfonic acid 15g/L~20g/L, potassium antimony tartrate
0.5g/L~1.0g/L, 90 μ L of μ L~110 of magnesium acetate, 90 μ L of μ L~110 of L-64 additive, 3,5- dihydroxybenzyl alcohol, 90 μ L~
110 μ L, stannous sulfate 15g/L~20g/L, citric acid gold potassium 10g/L~15g/L.
In step (6) of the present invention, electrodeposition temperature is 40 DEG C~60 DEG C, preferably 45 DEG C；Current density is 0.5A/dm2
~0.8A/dm2, current density 0.8A/dm2；Time is 10min~30min, preferably 10min.
In step (6) of the present invention, removal metallic tin is using electrochemical erosion method or chemical corrosion method；Wherein chemical attack
Corrosive liquid used in method is lye, and the concentration of lye is 5M~15M, and the alkali is alkali metal hydroxide, alkali metal
At least one of carbonate, alkali metal hydrogencarbonate, alkali metal alcoholates.
Sensing electrode prepared by the present invention uses three-electrode system, in order in reference electrode surface modification silver-silver chloride.
In step (7) of the present invention, the solution composition of silver-silver chloride is plated are as follows: silver nitrate 40g/L~45g/L, sodium thiosulfate
200g/L~250g/L, potassium metabisulfite 40g/L~45g/L, ammonium acetate 20g/L~30g/L, thiosemicarbazide 0.6g/L~
0.8g/L。
In step (7) of the present invention, electroplating temperature is 25 DEG C, current density 0.3A/dm2, time 15min.
It is a further object of the present invention to provide a kind of nano-porous golds of sweat detection glucose without enzyme flexible sensing electrode
Application method.
High performance nano-porous gold in conjunction with interdigital electrode, is passed through the interdigitated electrode structure of small spacing, drop by the present invention
Low ohm drop slows down concentration polarization, enhances signal-to-noise ratio, greatly improves the performance of enzyme-free glucose sensing electrode.
Flexible sensing electrode prepared by the present invention can be closely adhered to human skin, be examined by the sweat that human skin is secreted
Survey concentration of glucose, and it can be used repeatedly, electrode circuit it is not easy to break with fall off, be also easy to clean.
Glucose is as follows in the reaction process of electrode surface:
Anode reaction: Au+OH-→Au(OH)ads+e-；2Au(OH)ads+C6H12O6→2Au+C6H10O6+2H2O
Negative reaction: O2+2H2O+4e-→4OH-
Overall reaction: C6H12O6+1/2 O2→C6H10O6+H2O
Nano-porous gold is to OH-Absorption generates hydroxyl radical free radical, forms the Au (OH) of a large amount of high activitiesads, can quickly by
Glucose catalyticing oxidation is gluconic acid lactone, and glucolactone further aoxidizes, and Au is oxidized to Au under high potential2O3, account for
According to active site, make the Au (OH) of high activityadsIt reduces.Detecting without enzyme for glucose is realized with this.
The flexible sensing electrode sensitivity with higher of nano-porous gold modification provided by the invention, extremely low detection
Limit, wider inspection range and excellent stability and interference free performance, detection are limited to 0.55 μM, 0.001~
Possess 1297 μ A/mMcm in the inspection range of 2.50mM and 2.50~10.0mM respectively2With 854.7 μ A/mM.cm2It is highly sensitive
Degree.
The beneficial effects of the present invention are:
(1) three electrode coplanar structure: the copolymerization of three electrodes is integrated in same electrode plane, and constant distance, passes through fork
Refer to the design of electrode structure, effectively reduces the spacing between electrode, reduce solution itself ohmmic drop, slow down concentration polarization, favorably
In the conduction of electronics, the sensitivity of electrode is enhanced.
(2) flexible wearable electrode: polyimide flex material is used, human skin can be fitted closely, electrode is bent
And not will lead to circuit fracture, it can be used as wearable electrode and use, it is mostly disposable to solve glucose detection electrode now
The problem of, and detected by external sweat, electrode uses safer simplicity.
(3) without enzyme stable detection: modifying working electrode using nano-porous gold, by penetrating through the addition of pore structure, not only
Electrode specific surface area and porosity can be improved by multiple equally distributed holes, so that electrode catalyst performance is stronger and performance is steady
It is fixed, while nano-porous gold can be directly used for glucose assays, and there is high conductivity, the superiority such as anticorrosive, practicability is high
Can, the deactivation prob of the sensor of enzyme is overcome, can be saved in general room environment, it is with good stability.
Detailed description of the invention
Invention is described further using attached drawing, but the embodiments in the accompanying drawings do not constitute any limitation to the present invention,
For those of ordinary skill in the art, without creative efforts, it can also be obtained according to the following drawings
Its attached drawing.
Fig. 1 is the nano-porous gold of sweat detection glucose prepared by the present invention without the schematic diagram of enzyme flexible sensing electrode
(a) and bent electrode schematic diagram (b)；
Fig. 2 is that the scanning electron microscope (SEM) photograph (a) for the nano-porous gold that chemical corrosion method goes alloy to prepare and electrochemical erosion method are gone
The scanning electron microscope (SEM) photograph (b) of the nano-porous gold of alloy preparation；
Fig. 3 is cyclic voltammetric of the interdigital electrode modification nano-porous gold front and back in 0.1M KOH+0.01M KCl buffer
Curve graph, scanning speed 20mV/s；
Fig. 4 is that the flexible interdigital electrode of nano-porous gold modification prepared by the present invention is buffered in 0.1M KOH+0.01M KCl
Cyclic voltammetry curve figure after the glucose (0~30mM) of various concentration is added in liquid, scanning speed 20mV/s；
Fig. 5 is the chronoa mperometric plot of the anti-interference test of flexible interdigital electrode of nano-porous gold modification prepared by the present invention
Figure；
Current density when Fig. 6 is the flexible interdigital electrode detection glucose of nano-porous gold prepared by the present invention modification with
The staircase curve figure of concentration of glucose variation；
Fig. 7 is the interdigital stability test of the flexibility of nano-porous gold modification prepared by the present invention.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
A kind of nano-porous gold of sweat detection glucose specifically includes following without the preparation method of enzyme flexible sensing electrode
Step:
(1) at least two alloy-layers formed in the sputtering of polyimide flex substrate surface Ti, Mo, W, then in alloy
Layer surface copper facing；
(2) polyimide-based bottom surface layers of copper is roughened through persulfuric acid microetch, one layer of dry film of hot pressing, through overexposure, development
And etching process, it will be in designed figure line transitions to substrate；
(3) chemical nickel plating and gold is soaked on the copper wire of polyimide-based bottom surface, it is saved in dry environments；
(4) thick layer gold is plated in polyimide flex electrode surface；
(5) platinum plating in the interdigital electrode of the positive right side of face of polyimide flex electrode；
(6) in polyimide flex electrode front deposited Au tin alloy, removal metallic tin is carried, obtains modification nanoporous
The electrode of gold；
(7) in the front disk electrode surface modification silver-silver chloride of polyimide flex electrode.
Further, in step (4), gold plating solution composition are as follows: citric acid gold potassium 12g/L；Gold-plated temperature is 55 DEG C, and electric current is close
Degree is 1.0A/dm2, time 5min.
Further, in step (5), platinum plating bath group becomes H2PtCl61mM and KCl 0.1M.
Further, in step (6), the composition of gold-tin alloy plating solution used in electro-deposition are as follows: potassium citrate 50g/L~55g/L,
Sodium citrate 5g/L~10g/L, ascorbic acid 15g/L~20g/L, p-methyl benzenesulfonic acid 15g/L~20g/L, potassium antimony tartrate
0.5g/L~1.0g/L, 90 μ L of μ L~110 of magnesium acetate, 90 μ L of μ L~110 of L-64 additive, 3,5- dihydroxybenzyl alcohol, 90 μ L~
110 μ L, stannous sulfate 15g/L~20g/L, citric acid gold potassium 10g/L~15g/L.
Further, in step (6), electrodeposition temperature is 40 DEG C~60 DEG C, preferably 45 DEG C；Current density is 0.5A/dm2
~0.8A/dm2, current density 0.8A/dm2；Time is 10min~30min, preferably 10min.
Further, in step (6), removal metallic tin is using electrochemical erosion method or chemical corrosion method；Wherein chemistry is rotten
Corrosive liquid used in erosion method is lye, and the concentration of lye is 5M~15M, and the alkali is alkali metal hydroxide, alkali gold
Belong at least one of carbonate, alkali metal hydrogencarbonate, alkali metal alcoholates.
Further, in step (7), the solution composition of silver-silver chloride is plated are as follows: silver nitrate 40g/L~45g/L, thiosulfuric acid
Sodium 200g/L~250g/L, potassium metabisulfite 40g/L~45g/L, ammonium acetate 20g/L~30g/L, thiosemicarbazide 0.6g/L~
0.8g/L。
Further, in step (7), electroplating temperature is 25 DEG C, current density 0.3A/dm2, time 15min.
The contents of the present invention are described in further detail below by way of specific embodiment.
Embodiment 1
Preparation of the nano-porous gold without enzyme flexible sensing electrode:
(1) polyimide flex substrate surface sputter Ti, it is W-shaped at alloy-layer, then in alloyed layer copper facing.
(2) polyimide-based bottom surface layers of copper is roughened through persulfuric acid microetch, one layer of dry film of hot pressing, through overexposure, development
And etching process, it will be in designed figure line transitions to substrate.
(3) chemical nickel plating and gold is soaked on the copper wire of polyimide-based bottom surface, the polyimide flex prepared
Electrode.
(4) polyimide flex electrode is put into acetone ultrasonic oil removing, is washed with deionized water and dries after taking-up, it will
Electrode is fixed on copper sheet, is connected to positive three pins of interdigital electrode with copper sheet with conductive silver paste, and conductive silver paste is dry solidifying
Gu after, the copper sheet above pin is sealed with adhesive waterproof tape；Interdigital electrode is immersed and contains citric acid gold potassium 12g/L, AURUNA
5100 open in the plating solution of cylinder liquid (volume ratio 1: 2), and water bath heating temperature is 55 DEG C, in 1.0A/dm2It is electric under current density condition
Plate 5min.
(5) H is configured2PtCl6Interdigital electrode is immersed plating solution by the platinum plating bath of 1mM and KCl 0.1M, is to electricity with platinized platinum
Pole, control electrochemical workstation current potential are -0.4V, and 15min is electroplated at normal temperature.
(6) at 45 DEG C, current density 0.8A/dm2Under the conditions of electro-deposition 10min, gold-tin alloy plating solution used in electro-deposition
Composition are as follows: potassium citrate 55g/L, sodium citrate 5g/L, ascorbic acid 20g/L, p-methyl benzenesulfonic acid 20g/L, potassium antimony tartrate
0.5g/L, 100 μ L of magnesium acetate, 100 μ L of L-64 additive, 3,5- dihydroxybenzyl alcohol, 100 μ L, stannous sulfate 18.1g/L, lemon
Sour gold potassium 12g/L.
Electrode is taken out after plating, is cleaned with deionized water, is then dried in air, then electrode in 4M KOH+1M
H2O2It is impregnated in corrosive liquid and removes tin, placed 4 days, and be optionally added into appropriate 30%H2O2, go to take out electrode after alloy, use
Deionized water is cleaned and is dried.
(7) at 25 DEG C, current density 0.3A/dm2Under the conditions of be electroplated 15min, electroplating solution composition are as follows: silver nitrate 40g/
L~45g/L, sodium thiosulfate 200g/L~250g/L, potassium metabisulfite 40g/L~45g/L, ammonium acetate 20g/L~30g/L,
Thiosemicarbazide 0.6g/L~0.8g/L；Electrode is taken out after plating, is cleaned with deionized water, is then dried in air, then
Electrode is placed in 0.1M KCl+0.01M HCl solution, using silver-plated semicircle disc electrode as working electrode, platinum plate electrode
For to electrode, commercial silver-silver chloride is as reference electrode, the cyclic voltammetry scan in the section -0.15~1.05V, scanning speed
The coplanar sensing electrode of three electrode of flexibility of nano-porous gold has been modified after scanning 5 is enclosed for 50mV/s.
Embodiment 2
Preparation of the nano-porous gold without enzyme flexible sensing electrode:
(1) polyimide flex substrate surface sputter Ti, it is W-shaped at alloy-layer, then in alloyed layer copper facing.
(2) polyimide-based bottom surface layers of copper is roughened through persulfuric acid microetch, one layer of dry film of hot pressing, through overexposure, development
And etching process, it will be in designed figure line transitions to substrate.
(3) chemical nickel plating and gold is soaked on the copper wire of polyimide-based bottom surface, the polyimide flex prepared
Electrode.
(4) polyimide flex electrode is put into acetone ultrasonic oil removing, is washed with deionized water and dries after taking-up, it will
Electrode is fixed on copper sheet, is connected to positive three pins of interdigital electrode with copper sheet with conductive silver paste, and conductive silver paste is dry solidifying
Gu after, the copper sheet above pin is sealed with adhesive waterproof tape；Interdigital electrode is immersed and contains citric acid gold potassium 12g/L, AURUNA
5100 open in the plating solution of cylinder liquid (volume ratio 1: 2), and water bath heating temperature is 55 DEG C, in 1.0A/dm2It is electric under current density condition
Plate 5min.
(5) H is configured2PtCl6Interdigital electrode is immersed plating solution by the platinum plating bath of 1mM and KCl 0.1M, is to electricity with platinized platinum
Pole, control electrochemical workstation current potential are -0.4V, and 15min is electroplated at normal temperature.
(6) at 45 DEG C, current density 0.8A/dm2Under the conditions of electro-deposition 10min, gold-tin alloy plating solution used in electro-deposition
Composition are as follows: potassium citrate 55g/L, sodium citrate 5g/L, ascorbic acid 20g/L, p-methyl benzenesulfonic acid 20g/L, potassium antimony tartrate
0.5g/L, 100 μ L of magnesium acetate, 100 μ L of L-64 additive, 3,5- dihydroxybenzyl alcohol, 100 μ L, stannous sulfate 18.1g/L, lemon
Sour gold potassium 12g/L.
Electrode is taken out after plating, is cleaned with deionized water, is then dried in air, it is then that electrode merging 2M KOH is molten
In liquid, using interdigital electrode as anode, gauze platinum electrode applies constant potential 1.0V as cathode, corrodes 5 hours, remove alloy knot
Electrode is taken out after beam, is washed with deionized water and is dried.
(7) at 25 DEG C, current density 0.3A/dm2Under the conditions of be electroplated 15min, electroplating solution composition are as follows: silver nitrate 40g/
L~45g/L, sodium thiosulfate 200g/L~250g/L, potassium metabisulfite 40g/L~45g/L, ammonium acetate 20g/L~30g/L,
Thiosemicarbazide 0.6g/L~0.8g/L；Electrode is taken out after plating, is cleaned with deionized water, is then dried in air, then
Electrode is placed in 0.1M KCl+0.01M HCl solution, using silver-plated semicircle disc electrode as working electrode, platinum plate electrode
For to electrode, commercial silver-silver chloride is as reference electrode, the cyclic voltammetry scan in the section -0.15~1.05V, scanning speed
The coplanar sensing electrode of three electrode of flexibility of nano-porous gold has been modified after scanning 5 is enclosed for 50mV/s.
Embodiment 3
Nano-porous gold is tested without the detection performance of enzyme flexible sensing electrode:
The flexible interdigital electrode merging 0.1M KOH+0.01M KCl buffering of nano-porous gold modification prepared by embodiment 1
In liquid, and the glucose (0~30mM) of various concentration is added, is -0.8~-0.6V, scanning speed 20mV/s in sweep interval
In the case where carry out cyclic voltammetry curve test, obtain result such as attached drawing 4.It is from figure it may be concluded that prepared by the present invention
Nano-porous gold can be with quantitative detection glucose without enzyme flexible sensing electrode.
Embodiment 4
Anti-interference test of the nano-porous gold without enzyme flexible sensing electrode:
The flexible interdigital electrode merging 0.1M KOH+0.01M KCl electrolysis of nano-porous gold modification prepared by embodiment 1
In liquid, and 0.01mM ascorbic acid (AA) successively is added dropwise wherein, 0.01mM uric acid (UA), 0.01mM acetaminophenol (AP)
With 0.1mM glucose (Glu), chrono-amperometric test is carried out under conditions of test potential is 0.1V, obtains result such as attached drawing 5.
It may be concluded that the flexible interdigital electrode of nano-porous gold prepared by the present invention modification has good anti-interference from figure
Can, glucose can be detected under complicated test environment.
Embodiment 5
Quantitative test of the nano-porous gold without enzyme flexible sensing electrode detection glucose:
The flexible interdigital electrode merging 0.1M KOH+0.01M KCl buffering of nano-porous gold modification prepared by embodiment 1
In liquid, and certain density glucose concentrate is added dropwise every 50s, carries out current density in the case where test potential is 0.1V
Test., obtain result such as attached drawing 6.It may be concluded that the flexibility of nano-porous gold prepared by the present invention modification is interdigital from figure
Electrode minimum detectability is 0.55 μM, and is possessed respectively in the inspection range of 0.001~2.50mM and 2.50~10.0mM
1297μA/mM·cm2With 854.7 μ A/mMcm2High sensitivity.
Embodiment 6
Stability test of the nano-porous gold without enzyme flexible sensing electrode:
Chrono-amperometric will be carried out after the repeated multiple times bending of flexible interdigital electrode of nano-porous gold modification prepared by embodiment 1
Test, records its current density change, obtains result such as attached drawing 7.It may be concluded that nanometer prepared by the present invention is more from figure
The flexible interdigital electrode of hole gold modification has good flexibility, not will lead to coating in bending process and falls off or route damage, tool
There is outstanding stability.
Comparative example 1
The preparation of normal flexible sensing electrode:
(1) polyimide flex substrate surface sputter Ti, it is W-shaped at alloy-layer, then in alloyed layer copper facing.
(2) polyimide-based bottom surface layers of copper is roughened through persulfuric acid microetch, one layer of dry film of hot pressing, through overexposure, development
And etching process, it will be in designed figure line transitions to substrate.
(3) chemical nickel plating and gold is soaked on the copper wire of polyimide-based bottom surface, the polyimide flex prepared
Electrode.
(4) polyimide flex electrode is put into acetone ultrasonic oil removing, is washed with deionized water and dries after taking-up, it will
Electrode is fixed on copper sheet, is connected to positive three pins of interdigital electrode with copper sheet with conductive silver paste, and conductive silver paste is dry solidifying
Gu after, the copper sheet above pin is sealed with adhesive waterproof tape；Interdigital electrode is immersed and contains citric acid gold potassium 12g/L, AURUNA
5100 open in the plating solution of cylinder liquid (volume ratio 1: 2), and water bath heating temperature is 55 DEG C, in 1.0A/dm2It is electric under current density condition
Plate 5min, after take out electrode, be washed with deionized water and dry, obtain normal flexible sensing electrode.
Electrode basement used in above step is identical as embodiment 1 and embodiment 2.
Comparative example 2
The test of nano-porous gold electrode detection glucose responding:
The normal flexible sensing that nano-porous gold prepared by embodiment 1 is prepared without enzyme flexible sensing electrode and comparative example 1
Electrode is placed in 0.1M KOH+0.01M KCl buffer, is -0.8~-0.6V in sweep interval, scanning speed is 20mV/s's
In the case of test its cyclic voltammetry curve figure respectively, be separately added into 5mM glucose later, its cyclic voltammetry curve of re-test obtains
To result such as attached drawing 3.It may be concluded that nano-porous gold prepared by the present invention is without enzyme flexible sensing electrode ratio tradition from figure
Electrode has stronger detection performance and response characteristic.
In conclusion nano-porous gold prepared by the present invention has extremely low detection limit, superelevation without enzyme flexible sensing electrode
Detection sensitivity and wider detection range, while there is outstanding stability and interference free performance.
Phenetic analysis
Attached drawing 1 is the nano-porous gold of the preparation of embodiment 1 without enzyme flexible sensing electrode schematic diagram (a) and bent schematic diagram
(b).Sensing electrode prepared by the present invention uses polyimide flex material, can fit closely human skin, electrode it is bent and
It not will lead to circuit fracture, can be used as wearable electrode and use.
Attached drawing 2 is the scanning electron microscope (SEM) photograph (a) for the nano-porous gold that the chemical corrosion method of embodiment 1 goes alloy to prepare and implements
The scanning electron microscope (SEM) photograph (b) for the nano-porous gold that the electrochemical erosion method of example 2 goes alloy to prepare.It can be seen that, implement from Fig. 2 (a)
The through-hole and continuous ligament of 20~50nm are uniformly distributed in nanoporous layer gold prepared by example 1, this structure is conducive to electronics biography
It leads and electrolyte transport, can be reacted for electrode catalyst and a large amount of active sites are provided, while ligament structure can safeguard nano material
Stability.
It can be seen that from Fig. 2 (b), nano-porous gold layer surface prepared by embodiment 2 is uniformly distributed a large amount of aperture, hole
Size is generally less than the hole in Fig. 2 (a).The surface porosity factor of nanoporous layer gold be 60~75%, pore size be 5~
25nm, this is because tin atom slowly aoxidizes precipitation in chemical corrosion process, the golden slow deformation retract of ligament is formed relatively large
Hole, and electrochemical corrosion is comparatively quick, and the hole configurations that the gold of reservation is formed is smaller.
Attached drawing 3 is the normal flexible that nano-porous gold prepared by embodiment 1 is prepared without enzyme flexible sensing electrode and comparative example 1
Cyclic voltammetry curve figure of the sensing electrode in 0.1M KOH+0.01M KCl buffer, sweep interval are -0.8~-0.6V, are swept
Retouching speed is 20mV/s.It can be seen from the figure that interdigital electrode prepared by comparative example 1 is not obvious when glucose is not added
Current-responsive, and embodiment 1 prepare interdigital electrode occur an oxidation peak at 0.3V, show nano-porous gold to OH-
Absorption generates hydroxyl radical free radical, and when toward positive electricity bit scan, electric current continues to increase and second oxidation peak of appearance 0.5V at, shows
Au is oxidized to Au under high potential2O3, when toward negative electricity bit scan, one reduction peak of appearance, shows Au 0.1V at2O3It is reduced to
Au, and a small reduction peak at -0.2V then shows OH-Desorption.
When 5mM glucose is added, interdigital electrode prepared by comparative example 1 generates oxidation peak current, is because thick metal plated
Interdigital electrode surface exposure after layer has the active site of gold, can promote the catalysis oxidation of glucose, but its active area is far small
In nano-porous gold；And interdigital electrode prepared by embodiment 1 produces three oxidation peaks, first peak is in -0.6V, and peak current is very
It is small, it is direct absorption of the nano-porous gold to glucose, as current potential increases, occurs second oxidation peak at 0.2V, this is
Nano-porous gold is to OH-Absorption generates hydroxyl radical free radical, forms the Au (OH) of a large amount of high activitiesads, quickly glucose can be urged
Change is oxidized to glucose lactones, occurs third oxidation peak at 0.4V, shows the further of reaction product glucolactone
Oxidation.
To sum up it may be concluded that nano-porous gold prepared by embodiment 1 is made without enzyme flexible sensing electrode than comparative example 1
Standby normal flexible sensing electrode possesses more electrochemical surface areas and active site, on the basis of common interdigital electrode
On, the detection performance of nano-porous gold modified electrode prepared by the present invention obtains very big enhancing.
Attached drawing 4 is the flexible interdigital electrode of nano-porous gold modification prepared by embodiment 1 in 0.1M KOH+0.01M KCl
In buffer be added various concentration glucose (0~30mM) after cyclic voltammetry curve figure, sweep interval be -0.8~-
0.6V, scanning speed 20mV/s.It can be seen from the figure that oxidation current increases with it with the increase of concentration of glucose, lead to
Cross cyclic voltammetry can qualitative test glucose concentration, so it may be concluded that, embodiment 1 prepare nano-porous gold modification
Flexible interdigital electrode can be used for detecting glucose, and quantitative detection can be further realized.
Attached drawing 5 is the chrono-amperometric of the anti-interference test of flexible interdigital electrode of nano-porous gold modification prepared by embodiment 1
Curve graph, electrolyte are 0.1M KOH+0.01M KCl, test potential 0.1V, and it is anti-bad that 0.01mM is successively added dropwise in buffer
Hematic acid (AA), 0.01mM uric acid (UA), 0.01mM acetaminophenol (AP) and 0.1mM glucose (Glu).It can from figure
Out, the curent change for after glucose being added, producing apparent current-responsive, and chaff interferent being added is much smaller than the electric current of glucose
Response, so it may be concluded that, the flexible interdigital electrode of nano-porous gold modification prepared by embodiment 1 has good anti-interference
Performance can detect glucose under complicated test environment.
Electric current when attached drawing 6 is the flexible interdigital electrode detection glucose of nano-porous gold modification prepared by embodiment 1 is close
Spend the staircase curve figure that changes with concentration of glucose, test potential 0.1V, in 0.1M KOH+0.01M KCl solution every
Certain density glucose concentrate is added dropwise in 50s.It can be seen from the figure that with concentration of glucose be incremented by, response current by
Step increases, it can be seen that flexible interdigital electrode can detect glucose at much lower concentrations, and the minimum inspection of interdigital electrode is calculated
Rising limit is 0.55 μM (S/N=3)；And it is carried out in the interval range of 0.001~0.250mM and 2.50~10.0mM respectively linear
Fitting, related coefficient is respectively 0.9994 and 0.9968, and the sensitivity that can calculate interdigital electrode is respectively 1297 μ A/mM
cm2With 854.7 μ A/mMcm2。
Attached drawing 7 be embodiment 1 prepare nano-porous gold modification the repeated multiple times bending of flexible interdigital electrode after counted
When testing current, record its current density change, obtained current density change histogram.It can be seen from the figure that by
The performance of 8000 bendings, flexible interdigital electrode does not significantly decrease, so it may be concluded that, prepared by embodiment 1 receives
The flexible interdigital electrode of meter Duo Kong gold modification shows good flexible characteristic, not will lead to coating in bending process and falls off or line
Path loss is bad, has outstanding stability.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power
Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims
Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the embodiments can also be by appropriately combined, formation those skilled in the art
The other embodiments that member is understood that.The technical detail being not described in detail in the present invention can pass through appointing in this field
One prior art is realized.Particularly, all technical characterstics being not described in detail can pass through any prior art reality in the present invention
It is existing.
Claims (13)
1. a kind of nano-porous gold of sweat detection glucose is without enzyme flexible sensing electrode, which is characterized in that the electrode is by gathering
Acid imide flexible substrates, conductive layer, conversion zone composition；The polyimide flex substrate surface is equipped with the conductive layer, described
Conductive layer surface is equipped with the conversion zone；The conductive layer is at least two alloy-layers formed in Ti, Mo, W；The reaction
Layer surface is equipped with nanoporous layer gold；The electrode by three electrodes integrate it is coplanar form, wherein working electrode surface modify nanometer
Porous gold, to electrode face finish platinum, reference electrode surface modification silver-silver chloride.
2. a kind of nano-porous gold of sweat detection glucose according to claim 1 is without enzyme flexible sensing electrode, special
Sign is that the electrode front is provided with a pair of screw type interdigital electrode, respectively as working electrode and to electrode；The electricity
Extremely front is provided with the semicircle electrode wires of outer ring as reference electrode；The working electrode and the distance to electrode are 100 μ
m。
3. a kind of nano-porous gold of sweat detection glucose according to claim 1 is without enzyme flexible sensing electrode, special
Sign is that the reaction bore dia of the nanoporous layer gold is 5~55nm, and the surface porosity factor of the nanoporous layer gold is 60
~80%.
4. a kind of nano-porous gold of sweat detection glucose is without the preparation method of enzyme flexible sensing electrode, which is characterized in that packet
Include following steps:
(1) at least two alloy-layers formed in the sputtering of polyimide flex substrate surface Ti, Mo, W, then in alloy-layer table
Face copper facing；
(2) polyimide-based bottom surface layers of copper is roughened through persulfuric acid microetch, one layer of dry film of hot pressing, through overexposure, development and erosion
Quarter processing, will be in designed figure line transitions to substrate；
(3) chemical nickel plating and gold is soaked on the copper wire of polyimide-based bottom surface, it is saved in dry environments；
(4) thick layer gold is plated in polyimide flex electrode surface；
(5) platinum plating in the interdigital electrode of the positive right side of face of polyimide flex electrode；
(6) in polyimide flex electrode front deposited Au tin alloy, removal metallic tin is carried, obtains modification nano-porous gold
Electrode；
(7) in the front disk electrode surface modification silver-silver chloride of polyimide flex electrode.
5. a kind of nano-porous gold of sweat detection glucose according to claim 4 is without the preparation of enzyme flexible sensing electrode
Method, it is characterised in that: in the step (4), gold plating solution composition are as follows: citric acid gold potassium 12g/L；Gold-plated temperature is 55 DEG C,
Current density is 1.0A/dm2, time 5min.
6. a kind of nano-porous gold of sweat detection glucose according to claim 4 is without the preparation of enzyme flexible sensing electrode
Method, it is characterised in that: in the step (5), platinum plating bath group becomes H2PtCl61mM and KCl 0.1M.
7. a kind of nano-porous gold of sweat detection glucose according to claim 4 is without the preparation of enzyme flexible sensing electrode
Method, it is characterised in that: in the step (6), the composition of gold-tin alloy plating solution used in electro-deposition are as follows: potassium citrate 50g/L~
55g/L, sodium citrate 5g/L~10g/L, ascorbic acid 15g/L~20g/L, p-methyl benzenesulfonic acid 15g/L~20g/L, tartaric acid
Antimony potassium 0.5g/L~1.0g/L, 90 μ L of μ L~110 of magnesium acetate, 90 μ L of μ L~110 of L-64 additive, 3,5- dihydroxybenzyl alcohol 90
μ L of μ L~110, stannous sulfate 15g/L~20g/L, citric acid gold potassium 10g/L~15g/L.
8. a kind of nano-porous gold of sweat detection glucose according to claim 4 is without the preparation of enzyme flexible sensing electrode
Method, it is characterised in that: in the step (6), electrodeposition temperature is 40 DEG C~60 DEG C, current density 0.5A/dm2~
0.8A/dm2, the time is 10min~30min.
9. a kind of nano-porous gold of sweat detection glucose according to claim 4 is without the preparation of enzyme flexible sensing electrode
Method, it is characterised in that: in the step (6), removal metallic tin is using electrochemical erosion method or chemical corrosion method.
10. a kind of nano-porous gold of sweat detection glucose according to claim 4 is without the system of enzyme flexible sensing electrode
Preparation Method, it is characterised in that: in the step (6), corrosive liquid used in chemical corrosion method is lye, and the concentration of lye is
5M~15M, the alkali be alkali metal hydroxide, alkali carbonate, alkali metal hydrogencarbonate, in alkali metal alcoholates extremely
Few one kind.
11. a kind of nano-porous gold of sweat detection glucose according to claim 4 is without the system of enzyme flexible sensing electrode
Preparation Method, it is characterised in that: in the step (7), plate the solution composition of silver-silver chloride are as follows: silver nitrate 40g/L~45g/L, sulphur
Sodium thiosulfate 200g/L~250g/L, potassium metabisulfite 40g/L~45g/L, ammonium acetate 20g/L~30g/L, thiosemicarbazide
0.6g/L~0.8g/L.
12. a kind of nano-porous gold of sweat detection glucose according to claim 4 is without the system of enzyme flexible sensing electrode
Preparation Method, it is characterised in that: in the step (7), electroplating temperature is 25 DEG C, current density 0.3A/dm2, the time is
15min。
13. a kind of nano-porous gold the answering without enzyme flexible sensing electrode of sweat detection glucose according to claim 1
With, which is characterized in that the electrode can be bonded human skin, detect concentration of glucose by sweat.
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