CN113533469A - Lactate ion sensor based on graphene/polypyrrole and preparation method and application thereof - Google Patents
Lactate ion sensor based on graphene/polypyrrole and preparation method and application thereof Download PDFInfo
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- CN113533469A CN113533469A CN202110788990.XA CN202110788990A CN113533469A CN 113533469 A CN113533469 A CN 113533469A CN 202110788990 A CN202110788990 A CN 202110788990A CN 113533469 A CN113533469 A CN 113533469A
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- graphene
- polypyrrole
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- ion sensor
- lactate ion
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Images
Classifications
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- 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/307—Disposable laminated or multilayered electrodes
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- 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
-
- 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The invention discloses a lactate ion sensor based on graphene/polypyrrole and a preparation method and application thereof. The method has simple process, compounds two sensitive materials of graphene and polypyrrole in a layered/layered form, does not relate to the problems of fixation and inactivation of biological enzyme, and has the advantages of high ionic responsiveness, wide detection range, high surface flatness, adjustable material thickness and performance, stable chemical property and the like, long service life and good material durability.
Description
Technical Field
The invention relates to the field of ion sensors, in particular to a lactate ion sensor and a preparation method thereof.
Background
In recent years, the significance of wearable electronic sensors for monitoring endocrine and metabolic products in human sweat in health detection is increasingly prominent. For example, the content of lactic acid, a key product of carbohydrate anaerobic metabolism in the human body, in sweat is an important parameter in sports medicine and clinical analysis. At present, most lactate sensors are based on the catalytic reaction of lactate oxidase, and although the selectivity is high, the activity of the enzyme is easily influenced by the environment, so the use condition of the sensors is limited and the service life of the sensors is short. While enzyme-free sensors represent an important research direction, their related research is limited and immature. The search for enzyme-free sensors with wide detection range and high sensitivity is imminent.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide an enzyme-free lactate ion sensor based on a two-dimensional material graphene/polypyrrole composite film, and the enzyme-free lactate ion sensor can simultaneously realize high ion responsiveness, wide detection range and long service life.
The technical scheme is as follows: the lactate ion sensor based on graphene/polypyrrole comprises a substrate, a spiral interdigital electrode and a composite film, wherein the composite film comprises layered graphene and a polypyrrole film covering the upper surface of the graphene. Namely: different from most of existing enzyme-containing lactic acid sensors, the substrate is provided with a graphene/polypyrrole composite lactate ion sensitive functional material, the graphene/polypyrrole composite functional material comprises layered graphene, and layered polypyrrole is electrochemically polymerized on the surface of the layered graphene in situ; the lactate ion sensor is provided with a spiral interdigital electrode, and the electrode is connected with the graphene/polypyrrole composite ion sensitive material.
The substrate is at least one of a silicon wafer with an oxide layer, a polyimide sheet and a polydimethylsiloxane sheet, and the thickness of the substrate is 0.3-0.5 mm.
The transparency of the graphene is more than 95% so as to ensure that the graphene is pure and has no covering; the number of layers of the graphene is less than three, and the thickness of the polypyrrole layer is 20-200 nm, so that sufficient surface area and adsorption sites are guaranteed.
The spiral interdigital electrode is in a double-spiral line shape, the width of the electrode fingers is 10-30 mu m, the interdigital distance is 20-60 mu m, and the number of turns of a single electrode is 2-10.
And the graphene/polypyrrole composite film is only filled in the interdigital electrode channel and is in contact with the electrodes on the two sides. The spiral interdigital electrode is composed of a Ti film and an Au film covered on the Ti film.
The invention also provides a preparation method of the lactate ion sensor based on graphene/polypyrrole, which comprises the following steps:
(1) patterning the surface of the pretreated substrate by a patterning process;
(2) sequentially depositing Ti and Au on the patterned substrate by a physical vapor deposition method, and stripping redundant Ti/Au from the substrate by a stripping process to obtain the interdigital electrode with a spiral shape.
(3) Graphene is prepared by a chemical vapor deposition method and transferred to the surface of a substrate with electrodes using wet transfer.
(4) Polymerizing polypyrrole on the graphene film in situ by an electrochemical polymerization method to obtain a graphene/polypyrrole composite film;
(5) and carrying out etching and channeling treatment on the graphene/polypyrrole composite film, and connecting two ends of the composite film with electrodes to obtain the lactate ion sensor.
In the step (1), the patterning method includes: at least one of electron beam lithography, ultraviolet lithography, extreme ultraviolet lithography, and nanoimprint techniques;
in the step (2), the physical vapor deposition method includes: at least one of electron beam evaporation, magnetron sputtering or thermal evaporation; the titanium gold electrode comprises the following components: the thickness of the titanium is 5-20 nm, and the thickness of the gold is 40-60 nm.
In the step (2), the wet transfer is an electrochemical stripping method.
In the step (3), the preparation method of the single-layer graphene film is chemical vapor deposition with a copper foil as a substrate. The transparency of the prepared graphene is more than 95%, and the number of layers of the graphene is less than 3.
In the step (3), the wet transfer method is an electrochemical stripping method, so that the transfer speed is increased, the impurity pollution is reduced, and the sensing performance is improved;
in the step (3), the graphene is transferred to the surface of the substrate with the electrode by using wet transfer; the method comprises the following specific steps:
(a) coating polymethyl methacrylate (PMMA) on the surface of a substrate (copper foil) on which single-layer graphene grows, and heating and drying; the coating can adopt at least one of spin coating, spray coating, blade coating or dip coating;
(b) the peripheral edge of the copper foil is cut off and a sharp object is used to scribe a straight line through the edge. And (3) clamping the copper foil by using a lead with an alligator clip, wherein the clamping position is the narrower side of the straight line.
(c) Using copper foil as cathode, platinum electrode or carbon electrode as anode, NaOH solution or Na with concentration of 0.1-5 mol/L2S2O8The solution is an electrolyte, and a voltage of 1-5V is applied. And placing the anode in the electrolyte, slowly extending the cathode copper foil into the electrolyte, and keeping the separation interface of the PMMA and the copper foil at the liquid level position all the time. And finally, separating PMMA from the copper foil to complete stripping.
(d) Transferring the P MMA/graphene onto a substrate, cleaning and drying the P MMA/graphene with deionized water before transfer, heating to soften the P MMA at 150-180 ℃, removing PMMA with an organic solvent, and drying.
The electrochemical polymerization method in the step (4) comprises the following steps:
(a) preparing sodium p-toluenesulfonate with the concentration of 0.01-0.10 mol/L, adding pyrrole liquid to the concentration of 0.1-0.3 mol/L, adding hydrochloric acid to adjust the pH value to 1.5-2.5, and carrying out ultrasonic treatment for 5-20 min to completely emulsify and uniformly disperse the sodium p-toluenesulfonate;
(b) using an electrochemical workstation, the working electrode was connected to an electrode contact on the substrate using a saturated calomel electrode with an electrolyte of saturated potassium chloride solution as a reference electrode and a platinum sheet electrode as an auxiliary electrode.
(c) In-situ polymerizing polypyrrole on the surface of the graphene film by using a constant-pressure polymerization method: setting the polarization voltage to 0.7-0.9V. The low-pressure low-speed polymerization is adopted, the order of polypyrrole is improved, electrons on the outer layer of the polypyrrole can be better delocalized, and the sensing sensitivity can be obviously improved. The thickness of polypyrrole is determined by polymerization, and is generally set to be 20-60 min, if the thickness is too short, the sensitivity and selectivity of the sensor are reduced, and if the thickness is too long, the response speed becomes slow.
And (5) adopting plasma etching, using high-purity oxygen or high-purity argon as a gas source, wherein the pressure in the gas cavity is 1-50 Pa, and the flow rate is 1-2 sccm. Because the film is thin, the etching time does not need to be too long and is 5-10 min.
The invention also provides application of the lactate ion sensor based on graphene/polypyrrole in detection of lactate concentration in a liquid environment.
The invention principle is as follows: although the traditional detection method of oxidase + electrochemical electrode has the advantages of high selectivity and molecular recognition in the aspect of detection, the problems of difficulty in development of lactate ion sensors due to the difficulties in maintaining the activity of biological enzymes, narrow detection range, low detection sensitivity and the like in continuous work are generated. Graphene is expected to solve the above-mentioned difficulties due to its various excellent electrical, mechanical, physical and chemical properties. In addition, the electrical property and the surface chemical potential of the graphene can be regulated and controlled through doping, and the sensitivity and the selectivity are further improved. According to the invention, the high carrier concentration and the mobility of graphene are utilized, the specificity of polypyrrole for the lactate group is combined, and a physical adsorption and charge transfer method is adopted, so that the high sensitivity, the wide detection range and the simple device manufacturing of the lactate ion sensor are realized, and the concentration detection of the lactate ions can be realized without the participation of lactic acid biological oxidase. Meanwhile, the use of the interdigital electrode further enlarges the detection area and the anti-interference performance of the sensor, compared with the traditional double-electrode (or three-electrode) system, the liquid quantity required by detection is less, and micro detection can be realized.
Compared with the common parallel double electrodes, the electrode in the shape has the advantages of high detection sensitivity, strong anti-interference performance, large coverage area and the like. The lactate example sensor has the widest detection range of 10-110mM and the sensitivity of 0.309% mM-1(2.609μA mM-1) (ii) a In a narrow detection range (10-40mM), the sensitivity is as high as 0.936 percent mM-1(10.923μA mM-1) And the response time (55 s) and the recovery time (43 s) are shorter, which is obviously superior to the sensor in the prior invention.
Has the advantages that:
(1) the lactate ion sensing device of the graphene/polypyrrole layered composite ion sensitive material provided by the invention has a sensing area of only 3mm2Compared with the traditional huge electrochemical detection instrument, the electrochemical detection instrument can realize high sensitivity under a very small volume and can meet the requirements of wearable equipment and microelectronic devices.
The method has simple process, compounds two sensitive materials of graphene and polypyrrole in a layered/layered form, does not relate to the problems of activity and fixation of biological enzyme, and ensures that the composite material has the advantages of high ionic responsiveness, low detection limit, high surface flatness, adjustable material thickness, stable chemical property and the like, and has long service life and good material durability.
(2) Due to the high chemical stability of the graphene, the graphene/polypyrrole layered composite material disclosed by the invention can maintain the stability of the sensing performance for a long time in a room-temperature atmospheric environment.
(3) Compared with the common parallel double electrodes, the spiral interdigital electrode has the advantages of high detection sensitivity, strong anti-interference performance, large coverage area and the like.
(4) According to the invention, the graphene is transferred by adopting an electrochemical bubbling method, the transfer speed is high, copper residue caused by insufficient etching in the etching process is avoided, and the purity and the flatness of the large-area graphene are increased.
(5) According to the invention, due to the spherical cluster surface morphology of the graphene/polypyrrole composite material, the graphene/polypyrrole composite material has a large specific surface area, and lactate adsorption sites are increased to a great extent, so that the sensor has a higher linear interval compared with most commercial sensors, and has good response linearity within 10 mM-100 mM, and a step of diluting most sensors is omitted.
Drawings
Fig. 1 is a schematic diagram of a preparation process of a graphene/polypyrrole lactate ion sensor.
Fig. 2 is a schematic diagram of a transfer process of electrochemical exfoliation of graphene.
FIG. 3 is an AFM microscopic image of a graphene/polypyrrole layered composite ion sensitive material; FIG. 1 (a) shows example 1, and FIG. 1 (b) shows comparative example 1.
Fig. 4 is a raman characterization graph of the graphene/polypyrrole layered composite ion-sensitive material.
FIG. 5 shows the mask layout (top: first lithography; bottom: second lithography).
FIG. 6 is a detailed view of the sensing area of the reticle; FIG. (a) is a photolithography; FIG. b shows a second photolithography.
Fig. 7 is a microscopic image of a channel material of the graphene/polypyrrole lactate ion sensing device according to the present invention.
Fig. 8 is a current response curve of the ion sensor manufactured in example 1 at an operating voltage of 0.1V.
Fig. 9 is a sensor structure view.
Detailed Description
The present invention will be described in further detail with reference to examples.
The following examples and comparative examples are all commercially available with respect to starting materials and reagents.
Example 1:
a preparation method of a lactate ion sensor based on graphene/polypyrrole comprises the following steps, and a specific manufacturing flow chart is shown in figure 1:
(1) the single-layer graphene film is prepared by using a chemical vapor deposition method, and the prepared graphene is a single layer.
(2) Using ultraviolet lithography technology to construct an electrode pattern on a silicon wafer with a 300nm oxide layer, wherein the size parameters of the electrode pattern are as follows: the width of the fingers is 30 μm, the distance between the fingers is 60 μm, and the number of turns of a single finger is 5. And then depositing a titanium-gold electrode layer on the silicon substrate by using an electron beam evaporation method, wherein the thickness of titanium is 5nm, and the thickness of gold is 45 nm. And finally, preparing the silicon wafer with the spiral interdigital electrode on the surface by a stripping process, wherein the specific electrode shape design is shown in figures 5 and 6.
(3) Electrochemical wet transfer of graphene thin films onto a silicon substrate with electrodes: the method comprises the steps of heating and drying PMMA on the surface of a copper foil with single-layer graphene, cutting off the peripheral edge of the copper foil, and marking a straight line which penetrates through the PMMA at a position close to a measured edge by using a sharp object. And (3) clamping the copper foil by using a lead with an alligator clip, wherein the clamping position is the narrower side of the straight line. A voltage of 3.5V was applied to a copper foil as a cathode, a platinum electrode or a carbon electrode as an anode, and a NaOH solution having a concentration of 1mol/L as an electrolyte. And placing the anode in the electrolyte, slowly extending the cathode copper foil into the electrolyte, and keeping the separation line of the PMMA and the copper foil at the liquid level position all the time. And finally, separating PMMA from the copper foil to complete stripping. Obtaining the PMMA film with the single-layer graphene on the lower surface. Cleaning and drying the P MMA sheet with the single-layer graphene by using deionized water, transferring the single-layer graphene onto a silicon substrate with an electrode, heating to 160 ℃ to soften PMMA, removing the PMMA by using acetone, cleaning residual PMMA and acetone by using isopropanol, and drying (as shown in figure 2).
(4) In-situ polymerization of a thin polypyrrole layer on a single-layer graphene film using an electrochemical polymerization process: preparing an electrolytic cell solution: 0.971g of sodium p-toluenesulfonate is dissolved in 49mL of deionized water, 1mL of 1mol/L hydrochloric acid and 350. mu.L of pyrrole are added, and ultrasonic treatment is carried out for 10min after uniform stirring. And connecting the working electrode to an electrode contact on a silicon wafer, and using a platinum sheet electrode as an auxiliary electrode to build an electrolytic cell. The working mode of the electrochemical workstation is set to be a constant voltage test mode, the voltage is set to be 0.9V, and the polymerization time is 20 min. And after the polymerization is finished, taking down the silicon wafer, and sequentially cleaning the silicon wafer by using acetone, isopropanol and deionized water. And naturally drying to avoid damaging the composite film. The raman spectrum characterization of the prepared graphene polypyrrole composite film is shown in fig. 4.
(5) And preparing a device channel region protective layer by using an ultraviolet photoetching technology. Setting the air cavity pressure to be 50Pa by using an argon plasma etching technology, introducing 2sccm argon, and etching for 5min to remove the unprotected graphene/polypyrrole composite film, thereby finally obtaining the lactate ion sensing device (shown in figure 7) with the channel material being a single-layer graphene/polypyrrole composite film;
in the embodiment, the lactate ion sensing device of the single-layer graphene/polypyrrole layered composite ion sensitive material prepared by the method has the average polypyrrole cluster size of 50nm and is uniformly distributed (as shown in the left figure of fig. 3). As shown in FIG. 8, the detection range is the widest 10-110mM, and the sensitivity can reach 0.309% mM-1(2.609μA mM-1) (ii) a In a narrow detection range (10-40mM), the sensitivity is as high as 0.936 percent mM-1(10.923μA mM-1) And the response time (≈ 55s) and recovery time (≈ 43s) are short.
Example 2:
a preparation method of a lactate ion sensor based on graphene/polypyrrole comprises the following steps:
(1) the single-layer graphene film is prepared by using a chemical vapor deposition method, and the prepared graphene is a single layer.
(2) Using ultraviolet lithography technology to construct an electrode pattern on a silicon wafer with a 300nm oxide layer, wherein the size parameters of the electrode pattern are as follows: the width of the fingers is 30 μm, the distance between the fingers is 60 μm, and the number of turns of a single finger is 5. And then depositing a titanium-gold electrode layer on the silicon substrate by using an electron beam evaporation method, wherein the thickness of titanium is 5nm, and the thickness of gold is 45 nm. And finally, preparing the silicon wafer with the spiral interdigital electrode on the surface by a stripping process.
(3) Electrochemical wet transfer of graphene thin films onto a silicon substrate with electrodes: the method comprises the steps of heating and drying PMMA on the surface of a copper foil with single-layer graphene, cutting off the peripheral edge of the copper foil, and marking a straight line which penetrates through the PMMA at a position close to a measured edge by using a sharp object. And (3) clamping the copper foil by using a lead with an alligator clip, wherein the clamping position is the narrower side of the straight line. A voltage of 3.5V was applied to a copper foil as a cathode, a platinum electrode or a carbon electrode as an anode, and a NaOH solution having a concentration of 1mol/L as an electrolyte. And placing the anode in the electrolyte, slowly extending the cathode copper foil into the electrolyte, and keeping the separation line of the PMMA and the copper foil at the liquid level position all the time. And finally, separating PMMA from the copper foil to complete stripping. Obtaining the PMMA film with the single-layer graphene on the lower surface. Washing and drying the PMMA sheet with the single-layer graphene by using deionized water, transferring the single-layer graphene onto a silicon substrate with an electrode, heating to 160 ℃ to soften PMMA, removing PMMA by using acetone, washing residual PMMA and acetone by using isopropanol, and drying.
(4) In-situ polymerization of a thin polypyrrole layer on a single-layer graphene film using an electrochemical polymerization process: preparing an electrolytic cell solution: 0.971g of sodium p-toluenesulfonate is dissolved in 49mL of deionized water, 1mL of 1mol/L hydrochloric acid and 350. mu.L of pyrrole are added, and ultrasonic treatment is carried out for 10min after uniform stirring. And connecting the working electrode to an electrode contact on a silicon wafer, and using a platinum sheet electrode as an auxiliary electrode to build an electrolytic cell. The working mode of the electrochemical workstation is set to be a constant voltage test mode, the voltage is set to be 0.7V, and the polymerization time is 30 min. And after the polymerization is finished, taking down the silicon wafer, and sequentially cleaning the silicon wafer by using acetone, isopropanol and deionized water. And naturally drying to avoid damaging the composite film.
(5) And preparing a device channel region protective layer by using an ultraviolet photoetching technology. Setting the air pressure of an air cavity to be 50Pa by using an argon plasma etching technology, introducing 2sccm argon, and etching for 5min to remove the unprotected graphene/polypyrrole composite film, thereby finally obtaining the lactate ion sensor with the channel material being the single-layer graphene/polypyrrole composite film;
in this example, the polymerization voltage was lowered and the polymerization time was increased. The lactate ion sensing device of the single-layer graphene/polypyrrole layered composite ion sensitive material prepared by the method has the advantages that the average size of polypyrrole spheres is 50nm, the distribution is uniform, and the sensitivity and the detection range are basically consistent with those of the lactate ion sensing device in the embodiment 1.
Comparative example 1:
a preparation method of a lactate ion sensor based on graphene/polypyrrole comprises the following steps:
(1) the single-layer graphene film is prepared by using a chemical vapor deposition method, and the prepared graphene is a single layer.
(2) Using ultraviolet lithography technology to construct an electrode pattern on a silicon wafer with a 300nm oxide layer, wherein the size parameters of the electrode pattern are as follows: the width of the fingers is 30 μm, the distance between the fingers is 60 μm, and the number of turns of a single finger is 5. And then depositing a titanium-gold electrode layer on the silicon substrate by using an electron beam evaporation method, wherein the thickness of titanium is 5nm, and the thickness of gold is 45 nm. And finally, preparing the silicon wafer with the spiral interdigital electrode on the surface by a stripping process.
(3) Electrochemical wet transfer of graphene thin films onto a silicon substrate with electrodes: the method comprises the steps of heating and drying a surface P MMA with single-layer graphene growing on a copper foil, then cutting off the peripheral edge of the copper foil, and marking a straight line passing through the edge by using a sharp object at a position close to the edge. And (3) clamping the copper foil by using a lead with an alligator clip, wherein the clamping position is the narrower side of the straight line. A voltage of 3.5V was applied to a copper foil as a cathode, a platinum electrode or a carbon electrode as an anode, and a NaOH solution having a concentration of 1mol/L as an electrolyte. And placing the anode in the electrolyte, slowly extending the cathode copper foil into the electrolyte, and keeping the separation line of the PMMA and the copper foil at the liquid level position all the time. And finally, separating PMMA from the copper foil to complete stripping. Obtaining the PMMA film with the single-layer graphene on the lower surface. Washing and drying the PMMA sheet with the single-layer graphene by using deionized water, transferring the single-layer graphene onto a silicon substrate with an electrode, heating to 160 ℃ to soften PMMA, removing PMMA by using acetone, washing residual PMMA and acetone by using isopropanol, and drying.
(4) In-situ polymerization of a thin polypyrrole layer on a single-layer graphene film using an electrochemical polymerization process: preparing an electrolytic cell solution: 50mL of 1mol/L sodium lactate solution is prepared, 1mL of 1mol/L hydrochloric acid and 350 mu L of pyrrole are added, and ultrasonic treatment is carried out for 10min after uniform stirring. And connecting the working electrode to an electrode contact on a silicon wafer, and using a platinum sheet electrode as an auxiliary electrode to build an electrolytic cell. The working mode of the electrochemical workstation is set to be a constant voltage test mode, the voltage is set to be 0.9V, and the polymerization time is 20 min. And after the polymerization is finished, taking down the silicon wafer, and sequentially cleaning the silicon wafer by using acetone, isopropanol and deionized water. And naturally drying to avoid damaging the composite film.
(5) And preparing a device channel region protective layer by using an ultraviolet photoetching technology. Setting the air pressure of an air cavity to be 50Pa by using an argon plasma etching technology, introducing 2sccm argon, and etching for 5min to remove the unprotected graphene/polypyrrole composite film, thereby finally obtaining the lactate ion sensor with the channel material being the single-layer graphene/polypyrrole composite film;
in the comparative example, the lactate ion sensing device of the single-layer graphene/polypyrrole layered composite ion-sensitive material prepared by the method has an average polypyrrole spherical cluster size of 90nm, and spherical cluster aggregation is generated (as shown in the right figure of fig. 3).
The test result comparison can be used for obtaining the conclusion that: the response degree of the sensor prepared in the electrolyte environment with sodium p-toluenesulfonate as the emulsifier is about three times that of the sensor prepared in the comparative example with sodium lactate as the emulsifier, and the sensitivity is the top of the sensors reported in the prior art. And the current change can be rapidly generated under the condition of multiple liquid environment changes, and the stability and the repeatability of the sensor are strong. And as can be shown in the attached figure 3, the sodium p-toluenesulfonate can enable the polypyrrole ball clusters to be distributed more uniformly, so that the sensing sensitivity is remarkably improved.
Comparative example 2:
a preparation method of a lactate ion sensor based on graphene/polypyrrole comprises the following steps:
(1) the single-layer graphene film is prepared by using a chemical vapor deposition method, and the prepared graphene is a single layer.
(2) Using ultraviolet lithography technology to construct an electrode pattern on a silicon wafer with a 300nm oxide layer, wherein the size parameters of the electrode pattern are as follows: the width of the fingers is 30 μm, the distance between the fingers is 60 μm, and the number of turns of a single finger is 5. And then depositing a titanium-gold electrode layer on the silicon substrate by using an electron beam evaporation method, wherein the thickness of titanium is 5nm, and the thickness of gold is 45 nm. And finally, preparing the silicon wafer with the spiral interdigital electrode on the surface by a stripping process.
(3) Transferring the graphene film to a silicon substrate with an electrode by using a substrate etching method: and spin-coating PMMA on the surface of the copper foil with the single-layer graphene, heating and drying, and then immersing the surface of the copper foil without the PMMA into 0.5mol/L ammonium persulfate solution for corrosion to obtain the PMMA film with the single-layer graphene on the lower surface. Washing and drying the PMMA sheet with the single-layer graphene by using deionized water, transferring the single-layer graphene onto a silicon substrate with an electrode, heating to soften PMMA at 165 ℃, removing PMMA by using acetone, washing residual PMMA and acetone by using isopropanol, and drying.
(4) In-situ polymerization of a thin polypyrrole layer on a single-layer graphene film using an electrochemical polymerization process: preparing an electrolytic cell solution: 0.971g of sodium p-toluenesulfonate is dissolved in 49mL of deionized water, 1mL of 1mol/L hydrochloric acid and 350. mu.L of pyrrole are added, and ultrasonic treatment is carried out for 10min after uniform stirring. And connecting the working electrode to an electrode contact on a silicon wafer, and using a platinum sheet electrode as an auxiliary electrode to build an electrolytic cell. The working mode of the electrochemical workstation is set to be a constant voltage test mode, the voltage is set to be 0.9V, and the polymerization time is 20 min. And after the polymerization is finished, taking down the silicon wafer, and sequentially cleaning the silicon wafer by using acetone, isopropanol and deionized water. And naturally drying to avoid damaging the composite film.
(5) And preparing a device channel region protective layer by using an ultraviolet photoetching technology. Setting the air pressure of an air cavity to be 50Pa by using an argon plasma etching technology, introducing 2sccm argon, and etching for 5min to remove the unprotected graphene/polypyrrole composite film, thereby finally obtaining the lactate ion sensor with the channel material being the single-layer graphene/polypyrrole composite film;
in the comparative example, the single-layer graphene obtained by the method in (3) has copper residues, and is particularly obvious at the edge position. The residue reduces the purity and flatness of the graphene, influences the subsequent polymerization process in step (4), reduces the thickness controllability of polypyrrole polymerization, and reduces the performance of the sensor. Also, such residue results in impurities in the overall sensing material, which also adversely affects sensor performance. Therefore, the electrochemical stripping method in wet transfer can ensure the stability of the manufacturing quality of the sensor and the performance of the sensor.
Comparative example 3:
a preparation method of a lactate ion sensor based on graphene/polypyrrole comprises the following steps:
(1) the single-layer graphene film is prepared by using a chemical vapor deposition method, and the prepared graphene is a single layer.
(2) Using ultraviolet lithography technology to construct an electrode pattern on a silicon wafer with a 300nm oxide layer, wherein the size parameters of the electrode pattern are as follows: the width of the fingers is 30 μm, the distance between the fingers is 60 μm, and the number of turns of a single finger is 5. And then depositing a titanium-gold electrode layer on the silicon substrate by using an electron beam evaporation method, wherein the thickness of titanium is 5nm, and the thickness of gold is 45 nm. And finally, preparing the silicon wafer with the spiral interdigital electrode on the surface by a stripping process.
(3) Electrochemical wet transfer of graphene thin films onto a silicon substrate with electrodes: the method comprises the steps of heating and drying PMMA on the surface of a copper foil with single-layer graphene, cutting off the peripheral edge of the copper foil, and marking a straight line which penetrates through the PMMA at a position close to a measured edge by using a sharp object. And (3) clamping the copper foil by using a lead with an alligator clip, wherein the clamping position is the narrower side of the straight line. A voltage of 3.5V was applied to a copper foil as a cathode, a platinum electrode or a carbon electrode as an anode, and a NaOH solution having a concentration of 1mol/L as an electrolyte. And placing the anode in the electrolyte, slowly extending the cathode copper foil into the electrolyte, and keeping the separation line of the PMMA and the copper foil at the liquid level position all the time. And finally, separating PMMA from the copper foil to complete stripping. Obtaining the PMMA film with the single-layer graphene on the lower surface. Washing and drying the PMMA sheet with the single-layer graphene by using deionized water, transferring the single-layer graphene onto a silicon substrate with an electrode, heating to 160 ℃ to soften PMMA, removing PMMA by using acetone, washing residual PMMA and acetone by using isopropanol, and drying.
(4) Polymerizing a thin layer of polypyrrole in situ on a single layer graphene film using cyclic voltammetric mode polymerization: preparing an electrolytic cell solution: 0.971g of sodium p-toluenesulfonate is dissolved in 49mL of deionized water, 1mL of 1mol/L hydrochloric acid and 350. mu.L of pyrrole are added, and ultrasonic treatment is carried out for 10min after uniform stirring. And connecting the working electrode to an electrode contact on a silicon wafer, and using a platinum sheet electrode as an auxiliary electrode to build an electrolytic cell. Setting the working mode of the electrochemical workstation as a cyclic voltammetry mode, setting the first potential to be 0V, the second potential to be 0.65V, the scanning step length to be 1mV, the scanning rate to be 5mV and the number of cyclic cycles to be 5 circles. And after the polymerization is finished, taking down the silicon wafer, and sequentially cleaning the silicon wafer by using acetone, isopropanol and deionized water. And naturally drying to avoid damaging the composite film.
(5) And preparing a device channel region protective layer by using an ultraviolet photoetching technology. Setting the air pressure of an air cavity to be 50Pa by using an argon plasma etching technology, introducing 2sccm argon, and etching for 5min to remove the unprotected graphene/polypyrrole composite film, thereby finally obtaining the lactate ion sensor with the channel material being the single-layer graphene/polypyrrole composite film;
in this comparative example, the polypyrrole film obtained by the cyclic voltammetry mode polymerization in (4) was significantly less uniform (compared to example 1), and particularly the thickness of the portion of the polypyrrole film near the electrode was significantly increased. Such non-uniformity causes non-uniformity of the entire sensing material, adversely affecting the stability of the sensor manufacturing quality and its performance.
Comparative example 4:
this comparative example is based on a carbon nanotube/polypyrrole composite fiber based transistor sensor:
(1) preparing a carbon nano tube dispersion liquid: mixing 5g of carbon nano tube, 10g of sodium dodecyl sulfate and 100g of deionized water, and performing ultrasonic treatment for 1 hour to obtain a carbon nano tube dispersion liquid;
(2) preparing the flexible fiber with the surface coated with the carbon nanotube layer: placing acrylic fibers with the surfaces subjected to ultrasonic cleaning by ethanol into the carbon nanotube dispersion liquid obtained in the step 1) for repeated soaking for 2 hours, taking out, washing and drying to obtain flexible fibers with the surfaces coated with the carbon nanotube layer;
(3) preparing a mixed solution A: dissolving 2.5g of anthraquinone-2, 7-disulfonic acid disodium salt and 8.0g of pyrrole monomer into deionized water to obtain 250mL of mixed solution A;
(4) preparing a mixed solution B: dissolving 45g of 9-ferric nitrate hydrate and 30g of 5-sulfosalicylic acid into deionized water to obtain 150mL of mixed solution B;
(5) preparing carbon nano tube/polypyrrole composite fibers: taking the flexible fiber with the length and the width of 20cm coated with the carbon nanotube layer on the surface in the step (2), placing the flexible fiber in 250mL of mixed solution A, stirring for 10 minutes at room temperature, then dropwise adding 150mL of mixed solution B, controlling the stirring speed to be 800r/min under the water bath condition of 0 ℃, stirring for reaction for 4 hours, taking out, washing with ethanol and deionized water, and air-drying at normal temperature to obtain the carbon nanotube/polypyrrole composite fiber;
(6) preparing an electrolyte: mixing 1g of polyvinyl alcohol, 1g of phosphoric acid and 10mL of deionized water, and stirring and dissolving at the temperature of 60 ℃ to obtain electrolyte;
(7) preparing a carbon nano tube/polypyrrole composite fiber-based transistor sensor:
(8) preparing a source drain electrode of the transistor sensor: taking the carbon nanotube/polypyrrole composite fiber with the length of 2cm prepared in the step (5), coating conductive silver paste at two ends along the length, leaving the length of 2mm in the middle without coating, and fixing the fiber coated with the conductive silver paste on a PVC plastic plate to be used as a source electrode and a drain electrode of a transistor sensor;
(9) preparing a gate electrode of the transistor sensor: taking the carbon nano tube/polypyrrole composite fiber with the length of 2cm, prepared in the step (5), soaking the carbon nano tube/polypyrrole composite fiber in a lactate oxidase solution with the concentration of 10mg/mL for 24 hours under an ice bath condition, taking out the carbon nano tube/polypyrrole composite fiber, continuing to soak the carbon nano tube/polypyrrole composite fiber in a perfluorosulfonic acid solution with the mass percentage concentration of 2% under the ice bath condition for 24 hours, taking out the carbon nano tube/polypyrrole composite fiber, and air-drying the carbon nano tube/polypyrrole composite fiber under the ice bath condition to prepare a gate electrode of the transistor sensor;
(10) assembling the transistor sensor: and (3) crosswise arranging the source drain electrode and the gate electrode in the step (7), and smearing the electrolyte which is used for blocking the two electrodes from directly contacting and is configured in the step (6) at the intersection point of the crosswise arrangement, so as to assemble the carbon nano tube/polypyrrole composite fiber-based transistor sensor.
This comparative example requires immobilization of oxidase and is complicated to manufacture. Meanwhile, the detection range of the lactic acid sensor prepared by the method of the comparative example is as follows: 1nM to 1mM, and the detection range is far less than 10mM to 110mM of the invention. The invention has obvious improvement on the detection range.
Comparative example 5:
in this comparison example, to detect the lactic acid in the artificial sweat, the annular is dressed the model and is printed out the cavity ring that outer radius is 15mm, and the inner radius is 10mm, and the height is 5mm epoxy by 3D printing technique. Sputtering a graphite electrode with the length and width of 15mm and 2mm and the thickness of 1mm on the inner surface of the annular wearing model by utilizing a photoetching technology, wherein the graphite electrode is used as a working electrode; then evaporating a silver metal electrode with the same size characteristic as the working electrode at a position 2mm away from the working electrode, and carrying out electrolytic treatment by using the electrode to form a silver/silver chloride electrode as a counter electrode. The AD conversion circuit, the current acquisition and microprocessor and the 1.5V button battery are installed and fixed in a cavity of the ring of the wearable model, and a 4-bit LED display nixie tube with the width of 1cm and the length of 2cm is fixed on the outer surface of the annular wearable model to serve as a display screen and be connected with the microprocessor through a display circuit. The positive pole of the battery is connected with the working electrode, and the counter electrode is sequentially connected with the current acquisition circuit, the A/D conversion circuit and the microprocessor in series and is connected to the negative pole of the battery, so that the homeotropic voltage of the electrochemical reaction is ensured. Thereafter, 1. mu.l of 1% glutaraldehyde and 1. mu.l of a 10U/. mu.l solution of lactase were mixed with a shaker, and then dropped into the working electrode to wait until drying and solidification.
The detection limit of the sensor prepared by the method of the comparative example is 0.00771mM, the accurate detection concentration range is 0.00771-4 mM, the relative average error is about 2%, and the detection time is about 2 minutes. The detection range is far smaller than 10 mM-110 mM of the invention, and the detection time is longer than 64s of the invention, so that the detection range and the detection time are obviously improved compared with the comparative example.
Comparative example 6:
the comparative example is based on a sensing electrode of a high-efficiency lactic acid sensor, and the preparation method comprises the steps of preparing LOX protease and preparing an electrode material;
(1) the preparation process of the electrode material comprises the preparation process of the graphene oxide and graphene quantum dot composite material and the treatment process of a glassy carbon electrode;
(2) the graphene oxide and graphene quantum dot composite material is prepared by dissolving graphene oxide and graphene quantum dots in ultrapure water, wherein the concentration is 1.3mg/mL, and performing ultrasonic treatment for 2 hours; then reacting the obtained solution at 180 ℃ for 14 h; centrifuging the solution obtained by the reaction at 8000rpm for 6 h; then drying the mixture in a vacuum oven at 60 ℃ for 14 h;
(3) the particle size of the graphene quantum dots is 5nm, the flake size of the graphene oxide is 250nm, and the weight ratio of the graphene oxide to the graphene quantum dots is 1: 1;
(4) the treatment process of the glassy carbon electrode comprises the following steps:
A. polishing the glassy carbon electrode by using aluminum oxide to obtain a glassy carbon electrode with a mirror surface, performing ultrasonic treatment on the glassy carbon electrode by using a treatment solution for 3 hours, and drying the glassy carbon electrode under the condition of nitrogen;
B. dissolving the graphene and graphene quantum dot composite material in ultrapure water, wherein the concentration of the graphene and graphene quantum dot composite material is 1.0mg/mL, carrying out ultrasonic treatment for 3h, pouring 25 mu L of the graphene and graphene quantum dot composite material on the surface of the material obtained in the step A, and drying at room temperature;
C. dropwise adding 5 mu LLOX protease on the surface of the material obtained in the step B, standing and drying at 4 ℃ for 2.5 h;
the treatment solution comprises 50% (v/v) nitric acid solution, absolute ethyl alcohol and water, wherein the volume ratio of the nitric acid solution to the absolute ethyl alcohol to the water is 1: 1: 1;
(5) the diameter of the glassy carbon electrode is 2mm, and the diameter of the alumina is 0.25 μm;
(6) the preparation of the LOX protease comprises the following steps:
A. carrying out whole-gene extraction on aerococcus viridis, and designing a pair of primers 5' -GCGCGGCAGCCATATGATGAATA
PCR amplification of target gene LOX by ACAATGACATT-3 ' and 5'-GGTGGTGGTGCTCGAGCTAGTATTCATAACCG-3' to obtain target gene sequence;
C. utilizing a homologous recombination method, utilizing a one-step cloning kit, carrying out water bath at 37 ℃ for 30min on the obtained target in the step (1)
The gene of (a) is connected with a starting vector to construct an expression vector;
D. constructing gene engineering bacteria containing LOX gene by using host bacteria, inoculating the constructed LOX strain into an LB shake flask, culturing at 37 ℃ for 3.5h, adding 50mM lactose solution for 25ul, and culturing at 20 ℃ for 24 h. Expressing a lactate oxidase gene;
E. purifying the recombinant expressed lactate oxidase by using a nickel ion column, and concentrating to obtain LOX protease;
the starting vector is pET-28a (+), and the expression vector is pET-LOX; the host strain is E.coli BL21(DE3), and the genetically engineered strain is E.coli BL21(DE 3-pET-LOX).
The detection range of the comparative example is 0.1 mM-0.8 mM, and the sensitivity is 0.98667 mu AmM-1The present invention is significantly lower than the present invention, and the method using oxidase still lacks stability for long-term use and ease of preparation. The invention has obvious improvement on the sensitivity and the detection range.
Claims (10)
1. A lactate ion sensor based on graphene/polypyrrole is characterized in that: the composite film comprises layered graphene and a polypyrrole film coated on the upper surface of the graphene.
2. The graphene/polypyrrole-based lactate ion sensor according to claim 1, wherein: the transparency of the graphene is more than 95%, the number of layers of the graphene is less than three, and the thickness of the polypyrrole layer is 20-200 nm.
3. The graphene/polypyrrole-based lactate ion sensor according to claim 1, wherein: the spiral interdigital electrode is in a double-spiral line shape, the width of the electrode fingers is 10-30 mu m, the interdigital distance is 20-60 mu m, and the number of turns of a single electrode is 2-10.
4. The graphene/polypyrrole-based lactate ion sensor according to claim 1, wherein: the spiral interdigital electrode is composed of a Ti film and an Au film covered on the Ti film.
5. The graphene/polypyrrole-based lactate ion sensor according to claim 1, wherein: the graphene/polypyrrole composite film is filled in the interdigital electrode channel and is in contact with the electrodes on the two sides.
6. The method for preparing a graphene/polypyrrole-based lactate ion sensor according to claim 1, characterized by comprising the steps of:
(1) patterning the surface of the pretreated substrate by a photoetching process;
(2) depositing Ti and Au on the patterned substrate by a physical vapor deposition method, and stripping redundant Ti/Au from the substrate by a stripping process to obtain an interdigital electrode with a spiral shape;
(3) graphene is prepared by a chemical vapor deposition method and transferred to the surface of a substrate with electrodes using wet transfer.
(4) Polymerizing polypyrrole on the graphene film in situ by an electrochemical polymerization method to obtain a graphene/polypyrrole composite film;
(5) and carrying out etching and channeling treatment on the graphene/polypyrrole composite film, and connecting two ends of the composite film with electrodes to obtain the lactate ion sensor.
7. The method for preparing a graphene/polypyrrole-based lactate ion sensor according to claim 6, wherein the step (4) includes the steps of:
(a) preparing sodium p-toluenesulfonate with the concentration of 0.01-0.10 mol/L, adding pyrrole liquid to the concentration of 0.1-0.3 mol/L, adding hydrochloric acid to adjust the pH value to 1.5-2.5, and carrying out ultrasonic treatment for 5-20 min to completely emulsify and uniformly disperse the sodium p-toluenesulfonate;
(b) the electrochemical workstation uses a saturated calomel electrode of which the electrolyte is saturated potassium chloride solution as a reference electrode and a platinum sheet electrode as an auxiliary electrode, and the working electrode is connected to an electrode contact on the substrate;
(c) in-situ polymerizing polypyrrole on the surface of the graphene film by using a constant-pressure polymerization method: setting the polarization voltage to be 0.7-0.9V and the polarization time to be 20-60 min.
8. The method for preparing a lactate ion sensor based on graphene/polypyrrole according to claim 6, wherein: in the step (1), the substrate is one of polyethylene terephthalate, polyimide and a silicon wafer with an oxide layer.
9. The method for preparing a lactate ion sensor based on graphene/polypyrrole according to claim 6, wherein: in the step (2), the wet transfer is an electrochemical stripping method.
10. Use of the graphene/polypyrrole based lactate ion sensor of claim 1 as a sensor for detecting lactate concentration in a liquid environment.
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