Dry film self-calibration sensing device and method for measuring concentration of analyte by dry film self-calibration sensing device

Abstract

The present application relates to a dry film self-calibration sensing device and a method for measuring the concentration of an analyte by the dry film self-calibration sensing device. The dry film self-calibration sensing device comprises a first electrode and a second electrode; a detection portion of the first electrode and a detection portion of the second electrode are coated and connected by means of a sensing film, the sensing film comprises a first area and a second area, the first area coats the detection portion of the first electrode, and the second area coats the detection portion of the second electrode. When the dry film self-calibration sensing device measures the concentration of the analyte, calibration is not needed, and a measurement method is simple, thereby remarkably reducing measurement costs.

Description

A dry film self-calibration sensing device and a method for detecting analyte concentration thereof TECHNICAL FIELD

[0001] The present application belongs to the technical field of analyte concentration sensor, and relates to a self-calibration sensing device, in particular to a dry film self-calibration sensing device and a method for detecting analyte concentration thereof. BACKGROUND

[0002] The method for determining analyte concentration in the prior art includes using an electrolyte analyzer to determine the analyte concentration. In the process of determining the analyte concentration, an electrode needs to be selected for calibration according to the analyte to be measured, and a plurality of calibration solutions are needed to calibrate the slope of the analyte selection electrode, and then the sample to be measured is determined, and the analyte concentration in the sample to be measured is determined according to the previously established coordinates.

[0003] The analyte concentration includes electrolyte concentration, metabolite concentration, etc., wherein the electrolyte concentration includes sodium ion (Na + ) concentration, potassium ion (K + ) concentration, chloride ion (Cl-) concentration, calcium ion (Ca 2+ ) concentration and magnesium ion concentration (Mg 2+ ) and the like; the metabolite concentration includes glucose concentration, urea nitrogen concentration, creatinine concentration and uric acid concentration.

[0004] For example, CN102866197A discloses a method for rapidly detecting multiple electrolyte concentrations in a solution by using ion selective electrodes, which includes the following steps: (1) K / Na / Cl / Ca / pH / Li / Mg uses ion selective electrodes, first absorbs A / B liquid for calibration, calculates the slope and other parameters of each electrode, applies the Nernst equation, establishes the coordinate curve of each electrode item, and then tests the unknown solution sample; (2) determines the ion concentration of the position solution sample according to the previously established coordinates.

[0005] The ion selective electrode method is one of the most commonly used methods for determining ion concentration. In addition, there is a colorimetric detection method for the quantitative detection of urea nitrogen (BUN) in serum or plasma samples. At present, the most commonly used ion concentration detection method is wet ion selective electrode, but the wet ion selective electrode has the disadvantages of complex operation, high use and maintenance cost, slow response, not easy to carry, high storage condition requirement, poor stability, easy pollution and interference, etc.; and the colorimetric detection method is not suitable for whole blood samples, and all are in the form of large packaging reagents. Compared with the wet ion selective electrode method and the colorimetric detection method, the solid-state ion selective electrode has the characteristics of accurate measurement, convenient storage and transportation, good stability, low cost and simple operation, etc., can maintain the measurement accuracy for a long time, and can be widely used in various environments.

[0006] Meanwhile, the use of the calibration solution requires a complex instrument and pipeline, and there is a risk of liquid leakage. In addition, the calibration solution has a short shelf life, which not only increases the use cost but also increases the calibration time when the number of test objects is small. Therefore, it is necessary to provide a dry film self-calibration sensing device without calibration and convenient detection, and a preparation method and application thereof. SUMMARY

[0007] The present application provides a dry film self-calibration sensing device and a method for detecting the concentration of an analyte, which does not need to be calibrated when determining the concentration of the analyte, and the preparation method and determination method are simple, which significantly reduces the detection cost.

[0008] In a first aspect, the present application provides a dry film self-calibration sensing device, which comprises at least one first electrode and at least one second electrode.

[0009] The detection part of the at least one first electrode and the detection part of the at least one second electrode are connected by a sensing film.

[0010] Preferably, the first electrode can correspond to at least one second electrode.

[0011] Preferably, the sensing film comprises at least one first region and at least one second region, the first region covers the detection part of the first electrode, and the second region covers the detection part of the second electrode.

[0012] Preferably, the sensing films of the first region and the second region are the same or different.

[0013] Preferably, the sensing film of the first region is a polymer macromolecular film, and the sensing film of the second region is a polymer macromolecular film or an electrolyte film.

[0014] Preferably, the material of the first electrode comprises any one or a combination of at least two of gold, platinum, silver, copper or carbon, and typical but non-limiting combinations include a combination of gold and platinum, a combination of silver and copper, a combination of platinum and carbon, a combination of gold, platinum and silver, or a combination of gold, platinum, silver, copper and carbon.

[0015] In the present application, the first electrode is a material such as gold, platinum, silver, copper or carbon itself, or an electrode comprising the above-mentioned materials after screen printing, or a conductive thin film electrode obtained by magnetron sputtering or electroplating, chemical deposition.

[0016] Preferably, the material of the second electrode comprises any one or a combination of at least two of gold, platinum, silver, copper or carbon, and typical but non-limiting combinations include a combination of gold and platinum, a combination of silver and copper, a combination of platinum and carbon, a combination of gold, platinum and silver, or a combination of gold, platinum, silver, copper and carbon.

[0017] In the present application, the second electrode is a material itself such as gold, platinum, silver, copper or carbon, or an electrode including the above-mentioned material after screen printing, or a conductive thin film electrode obtained by magnetron sputtering or electroplating, chemical deposition.

[0018] Preferably, a conductive medium is arranged between the first region sensing film and the detection part of the first electrode, and between the second region sensing film and the detection part of the second electrode.

[0019] A conductive medium is arranged between the detection part of the first electrode and the detection part of the second electrode, and the conductive medium is not connected to the first electrode and the second electrode at the same time, and the sensing film covers the conductive medium.

[0020] The conductive medium can improve the electronic transmission efficiency between the sensing film and the electrode and / or between the electrodes under different environments or detection conditions, and the conductive medium has good conductivity, and materials such as metals, non-metals, organic salts or inorganic salts can be used as the conductive medium in the present application.

[0021] Preferably, the material of the conductive medium includes poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT-PSS) and / or reduced graphene (RGO).

[0022] Preferably, the conductive medium can be a material itself, or a conductive medium including the above-mentioned material after screen printing, or a conductive medium obtained by magnetron sputtering.

[0023] Preferably, the sensing film of the first region and / or the second region is a polymer macromolecular film.

[0024] The preparation raw material of the first region sensing film includes a first ion carrier.

[0025] The preparation raw material of the second region sensing film includes a second ion carrier and / or a lipophilic electrolyte.

[0026] Preferably, the first ion carrier and the second ion carrier are the same or different.

[0027] As one of the preferred schemes of the dry film self-calibration sensing device provided in the present application, when the sensing film of the second region is a polymer macromolecular film:

[0028] The sensing film of the first region is a polymer macromolecular film, the preparation raw material of the sensing film of the first region includes a first ion carrier and an adjuvant, and the preparation raw material of the sensing film of the second region includes a second ion carrier and an adjuvant.

[0029] The first ion carrier and the second ion carrier are the same or different.

[0030] The first ion carrier is selected from any one or a combination of at least two of a lithium ion carrier, a sodium ion carrier, a potassium ion carrier, a calcium ion carrier, a magnesium ion carrier, a lead ion carrier, a mercury ion carrier, a silver ion carrier, a copper ion carrier, a hydrogen ion carrier, an ammonium ion carrier, a fluoride ion carrier, a chloride ion carrier, a bromide ion carrier, an iodide ion carrier, a nitrate ion carrier, a perchlorate ion carrier, a sulfide ion carrier, or a carbonate ion carrier.

[0031] Preferably, the first ion carrier comprises any one or a combination of at least two of a sodium ion carrier X, valinomycin, a calcium ion carrier I, a lithium ion carrier VI, a magnesium ion carrier VI, a hydrogen ion carrier I, a nonactin, a lead ion carrier IV, a carbonate ion carrier VII, or a nitrate ion carrier VI.

[0032] wherein the sodium ion carrier X has a CAS number of 111633-81-3; the valinomycin has a CAS number of 2001-95-8; the calcium ion carrier I has a CAS number of 54957-22-7; the lithium ion carrier VI has a CAS number of 175765-23-2; the magnesium ion carrier VI has a CAS number of 151285-37-3; the hydrogen ion carrier I has a CAS number of 25344-49-2; the nonactin has a CAS number of 6833-84-7; the lead ion carrier IV has a CAS number of 151874-99-0; the carbonate ion carrier VII has a CAS number of 222310-82-9; and the nitrate ion carrier VI has a CAS number of 110547-28-1.

[0033] Preferably, the mass concentration of the first ion carrier is 0.1% to 20%.

[0034] The second ion carrier is selected from any one or a combination of at least two of a lithium ion carrier, a sodium ion carrier, a potassium ion carrier, a calcium ion carrier, a magnesium ion carrier, a lead ion carrier, a mercury ion carrier, a silver ion carrier, a copper ion carrier, a hydrogen ion carrier, an ammonium ion carrier, a fluoride ion carrier, a chloride ion carrier, a bromide ion carrier, an iodide ion carrier, a nitrate ion carrier, a perchlorate ion carrier, a sulfide ion carrier, or a carbonate ion carrier.

[0035] Preferably, the second ion carrier comprises any one or a combination of at least two of a sodium ion carrier X, valinomycin, a calcium ion carrier I, a lithium ion carrier VI, a magnesium ion carrier VI, a hydrogen ion carrier I, a nonactin, a lead ion carrier IV, a carbonate ion carrier VII, or a nitrate ion carrier VI.

[0036] wherein the sodium ionophore X has a CAS number of 111633-81-3; the valinomycin has a CAS number of 2001-95-8; the calcium ionophore I has a CAS number of 54957-22-7; the lithium ionophore VI has a CAS number of 175765-23-2; the magnesium ionophore VI has a CAS number of 151285-37-3; the hydrogen ionophore I has a CAS number of 25344-49-2; the gramicidin has a CAS number of 6833-84-7; the lead ionophore IV has a CAS number of 151874-99-0; the carbonate ionophore VII has a CAS number of 222310-82-9; and the nitrate ionophore VI has a CAS number of 110547-28-1.

[0037] Preferably, the second ionophore has a mass concentration of 0.1% to 20%.

[0038] Preferably, the adjuvant includes an ion additive, a plasticizer, a neutral polymer, and a solvent.

[0039] The ion additive includes any one or a combination of at least two of tetra(4-fluorophenyl)borate, tetra[3,5-bis(trifluoromethyl)phenyl]borate, tetra[3,5-bis(trifluoromethyl)phenyl]borate, tetra(4-chlorophenyl)borate, or tridodecylmethylammonium chloride.

[0040] Preferably, the ion additive includes any one or a combination of at least two of tetra(4-fluorophenyl)borate, tetra[3,5-bis(trifluoromethyl)phenyl]borate, tetra[3,5-bis(trifluoromethyl)phenyl]borate, tetra(4-chlorophenyl)borate, or tridodecylmethylammonium chloride.

[0041] Preferably, the ion additive is tetra[3,5-bis(trifluoromethyl)phenyl]borate sodium (NaTFPB).

[0042] Preferably, the ion additive has a mass concentration of 0.1% to 20%.

[0043] Preferably, the plasticizer includes any one or a combination of at least two of dinonyl phenyl ether, di(2-ethylhexyl) adipate, di(2-ethylhexyl) sebacate, or o-nitrophenyl dodecyl ether.

[0044] Preferably, the plasticizer includes any one or a combination of at least two of dinonyl phenyl ether and / or di(2-ethylhexyl) adipate.

[0045] Preferably, the plasticizer has a mass concentration of 99% or less, preferably 20% to 80%.

[0046] Preferably, the neutral polymer comprises any one or a combination of at least two of carboxyl polyvinyl chloride, polyvinyl chloride, silicone-based rubber or polyurethane.

[0047] Preferably, the neutral polymer comprises polyvinyl chloride (PVC) and / or silicone-based rubber.

[0048] Preferably, the mass concentration of the neutral polymer is 99% or less, preferably 20% to 60%.

[0049] Preferably, the solvent comprises an ether-based solvent and / or a carbonate-based solvent.

[0050] Preferably, the solvent comprises tetrahydrofuran.

[0051] As the second preferred scheme of the dry film self-calibration sensing device provided in the present application, when the sensing film of the second region is an electrolyte film:

[0052] The sensing film of the first region is a polymer macromolecular film, and the preparation raw material thereof comprises a first ion carrier and an adjuvant.

[0053] The sensing film of the second region is an electrolyte film, and the preparation raw material thereof comprises a lipophilic electrolyte.

[0054] The first ion carrier is selected from any one or a combination of at least two of lithium ion carrier, sodium ion carrier, potassium ion carrier, calcium ion carrier, magnesium ion carrier, lead ion carrier, mercury ion carrier, silver ion carrier, copper ion carrier, hydrogen ion carrier, ammonium ion carrier, fluoride ion carrier, chloride ion carrier, bromide ion carrier, iodide ion carrier, nitrate ion carrier, perchlorate ion carrier, sulphide ion carrier or carbonate ion carrier.

[0055] Preferably, the first ion carrier comprises any one or a combination of at least two of sodium ion carrier X, valinomycin, calcium ion carrier I, lithium ion carrier VI, magnesium ion carrier VI, hydrogen ion carrier I, nonactin, lead ion carrier IV, carbonate ion carrier VII or nitrate ion carrier VI.

[0056] The CAS number of the sodium ion carrier X is 111633-81-3; the CAS number of the valinomycin is 2001-95-8; the CAS number of the calcium ion carrier I is 54957-22-7; the CAS number of the lithium ion carrier VI is 175765-23-2; the CAS number of the magnesium ion carrier VI is 151285-37-3; the CAS number of the hydrogen ion carrier I is 25344-49-2; the CAS number of the apurimycin is 6833-84-7; the CAS number of the lead ion carrier IV is 151874-99-0; the CAS number of the carbonate ion carrier VII is 222310-82-9; and the CAS number of the nitrate ion carrier VI is 110547-28-1.

[0057] Preferably, the lipophilic electrolyte comprises any one or a combination of at least two of pyridine-based ionic liquid, quaternary ammonium salt-based ionic liquid, quaternary phosphonium salt-based ionic liquid, imidazole-based ionic liquid, pyrrolidine-based ionic liquid, piperidine-based ionic liquid, or tetra(4-chlorophenyl)phosphonium tetradecylammonium.

[0058] Preferably, the lipophilic electrolyte is quaternary ammonium salt-based ionic liquid.

[0059] Preferably, the quaternary ammonium salt-based ionic liquid is propyltributylphosphonium bis(trifluoromethanesulfonyl)imide.

[0060] Preferably, the mass concentration of the lipophilic electrolyte is 1% to 100%.

[0061] Preferably, the auxiliary agent for preparing the sensing membrane of the first region comprises an ionic additive, a plasticizer, a neutral polymer, and a solvent.

[0062] The ionic additive comprises any one or a combination of at least two of tetra(4-fluorophenyl)borate, tetra[3,5-bis(trifluoromethyl)phenyl]borate, tetra[3,5-bis(trifluoromethyl)phenyl]borate, tetra(4-chlorophenyl)borate, or dodecylmethylammonium chloride.

[0063] Preferably, the ionic additive comprises any one or a combination of at least two of tetra(4-fluorophenyl)borate sodium hydrate, tetra[3,5-bis(trifluoromethyl)phenyl]borate sodium, tetra[3,5-bis(trifluoromethyl)phenyl]borate potassium, tetra(4-chlorophenyl)borate potassium, or dodecylmethylammonium chloride.

[0064] Preferably, the ionic additive is tetra[3,5-bis(trifluoromethyl)phenyl]borate sodium (NaTFPB).

[0065] Preferably, the mass concentration of the ionic additive is 0.1% to 20%.

[0066] Preferably, the plasticizer comprises any one or a combination of at least two of dinonyl phenyl ether, di(2-ethylhexyl) adipate, di(2-ethylhexyl) sebacate, or o-nitrophenyl dodecyl ether.

[0067] Preferably, the plasticizer is dinonyl phenyl ether and / or di(2-ethylhexyl) adipate.

[0068] Preferably, the plasticizer has a mass concentration of 99% or less, preferably 20% to 80%.

[0069] Preferably, the neutral polymer comprises any one or a combination of at least two of carboxylated polyvinyl chloride, polyvinyl chloride, silicone-based rubber, or polyurethane.

[0070] Preferably, the neutral polymer comprises polyvinyl chloride (PVC) and / or silicone-based rubber.

[0071] Preferably, the neutral polymer has a mass concentration of 99% or less, preferably 20% to 60%.

[0072] Preferably, the solvent is selected from the group consisting of an ether solvent and / or a carbonate solvent.

[0073] Preferably, the solvent comprises tetrahydrofuran.

[0074] Preferably, the preparation of the sensing membrane of the second region further comprises an aid, the aid comprising a neutral polymer and a plasticizer.

[0075] Preferably, the neutral polymer comprises any one or a combination of at least two of carboxylated polyvinyl chloride, polyvinyl chloride, silicone-based rubber, or polyurethane.

[0076] Preferably, the neutral polymer of the aid comprises polyvinyl chloride (PVC) and / or silicone-based rubber.

[0077] Preferably, the neutral polymer has a mass concentration of 99% or less, preferably 20% to 60%.

[0078] Preferably, the plasticizer of the aid comprises any one or a combination of at least two of dinonyl phenyl ether, di(2-ethylhexyl) adipate, di(2-ethylhexyl) sebacate, or o-nitrophenyl dodecyl ether.

[0079] Preferably, the plasticizer is dinonyl phenyl ether and / or di(2-ethylhexyl) adipate.

[0080] Preferably, the plasticizer has a mass concentration of 99% or less, preferably 20% to 80%.

[0081] According to the dry film self-calibration sensing device of the present application, when the second area sensing film is an electrolyte film, the dry film self-calibration sensing device can be used to measure the concentration of a single ion.

[0082] When the second area sensing film is a polymer macromolecular film, and the first ion carrier and the second ion carrier are the same, the dry film self-calibration sensing device can be used to measure the concentration of a single ion or a metabolite.

[0083] When the second area sensing film is a polymer macromolecular film, and the first ion carrier and the second ion carrier are different, the dry film self-calibration sensing device can be used to measure the concentration ratio of two ions or the concentration of a metabolite in the system.

[0084] In a second aspect, the present application provides a preparation method of the dry film self-calibration sensing device according to the first aspect, the preparation method comprising the following steps:

[0085] S1: covering the detection part of the first electrode and the detection part of the second electrode with a sensing film, respectively;

[0086] S2: connecting the detection part of the first electrode and the detection part of the second electrode with a sensing film;

[0087] S3: obtaining the dry film self-calibration sensing device after the sensing film is formed.

[0088] In the present application, the method for covering the first area of the sensing film on the detection part of the first electrode includes any one or a combination of at least two of dispensing, coating or dropping.

[0089] The method for covering the second area of the sensing film on the detection part of the second electrode includes any one or a combination of at least two of dispensing, coating or dropping.

[0090] The method for connecting the detection part of the first electrode and the detection part of the second electrode can be adding sensing film to the detection part of the first electrode and the detection part of the second electrode until the two areas are connected after covering the detection part of the first electrode and the detection part of the second electrode with a sensing film, respectively; or adding sensing film to the gap between the detection part of the first electrode and the detection part of the second electrode after covering the detection part of the first electrode and the detection part of the second electrode with a sensing film, respectively.

[0091] The first area of the sensing film of the present application is mixed from the preparation raw materials of the first area.

[0092] The second area of the sensing film of the present application is mixed from the preparation raw materials of the second area.

[0093] Preferably, a conductive medium is arranged between the first area and the detection part of the first electrode and / or between the second area and the detection part of the second electrode, respectively.

[0094] Preferably, an electrically conductive medium is arranged between the first electrode detection part and the second electrode detection part, the electrically conductive medium is not connected with the first electrode and the second electrode at the same time, and the sensing film covers the electrically conductive medium.

[0095] Preferably, the material of the electrically conductive medium includes poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT-PSS) and / or reduced graphene oxide (RGO).

[0096] The electrically conductive medium can be a material itself, a screen-printed electrically conductive medium including the above-mentioned material, or a magnetron sputtering obtained electrically conductive medium.

[0097] In a third aspect, the application further provides a method for detecting an analyte concentration by using the dry film self-calibration sensing device of the first aspect, and the method comprises the following steps:

[0098] The potential values of the sample detection state and the dry film state are respectively measured and recorded as E 样本 and E 干膜 , to obtain the concentration ratio C1 / C2 of the detection objects of the first electrode and the second electrode, and the corresponding relationship is: E 样本 -E 干膜 =Sxlg(C1 / C2)+A.

[0099] Wherein, C1 corresponds to the concentration of the detection object of the first electrode, C2 corresponds to the concentration of the detection object of the second electrode, S is the Nernst slope of the dry film self-calibration sensing device, and A is the inherent constant of the dry film self-calibration sensing device.

[0100] In the method provided by the application, E 样本 is the potential value when detecting the sample to be measured, and E 干膜 is the potential value detected by the dry film self-calibration sensing device in the dry state.

[0101] The analyte concentration includes ion concentration and metabolite concentration, wherein the ion concentration includes metal ions or non-metal ions, and the metabolite concentration includes glucose concentration, urea nitrogen concentration, creatinine concentration, uric acid concentration or lactic acid concentration.

[0102] When the detection concentration is ion concentration:

[0103] When the sensing film of the second region is a polymer macromolecular film, and the first ion carrier and the second ion carrier are the same, the detection objects of the first electrode and the second electrode are the same. A known amount of auxiliary salt is introduced into the detection part of the second electrode, and at this time, the concentration of the detection object of the second electrode is C1+C x， to obtain the concentration ratio C1 / (C1+C x), the corresponding relationship is: E 样本 -E 干膜 =S x lg (C1 / (C1+C x ))+A;

[0104] wherein C x is the concentration of the ion to be detected corresponding to the auxiliary salt;

[0105] The ion to be detected corresponding to the auxiliary salt is the same as the ion of the determination object, and the auxiliary salt includes an inorganic salt containing the ion to be detected. For example, when the determination object of the first electrode and the second electrode is potassium ion, the first ion carrier in the first region sensing membrane is valinomycin, and the second ion carrier in the second region sensing membrane is valinomycin. During detection, a known amount of auxiliary salt is introduced into the detection part of the second electrode, and then the detection part of the first electrode and the second electrode is soaked with the sample to be detected, so that E 样本 , the concentration C1 can be obtained by the relationship of E 样本 -E 干膜 =S x lg (C1 / (C1+C x ))+A.

[0106] For example, the setting method of the auxiliary salt includes directly placing the auxiliary salt solid on the detection part of the corresponding electrode, or dissolving the auxiliary salt and then directly adding the solution to the corresponding sensing membrane or dropping the solution on the medium, and then covering the medium on the detection part of the corresponding electrode.

[0107] For example, the medium includes but is not limited to any one of filter paper, glass fiber or cellulose membrane.

[0108] Preferably, when the second region sensing membrane is a polymer high molecular film, and the first ion carrier and the second ion carrier are the same, the determination objects of the first electrode and the second electrode are the same. A substance containing a co-extracted anion is introduced into the detection part of the second electrode, and at this time the concentration of the determination object of the second electrode is C 2， , the concentration ratio C1 / C2 of the determination objects of the first electrode and the second electrode is obtained, and the corresponding relationship is: E 样本 -E 干膜 =S x lg (C1 / C2)+A.

[0109] wherein C2 is the concentration value of the potential signal generated by the co-extracted anion on the second electrode.

[0110] Preferably, the co-extracted anion includes but is not limited to any one of trifluoromethyl sulfonic acid ion, perfluoroethyl sulfonic acid ion, perfluoropropyl sulfonic acid ion, perfluorobutyl sulfonic acid ion, 4-octyl benzene sulfonic acid ion or dodecyl benzene sulfonic acid, or a combination of at least two of them.

[0111] The mass concentration of the co-extracted anion is 0.1% to 100%.

[0112] Exemplarily, when the determination object of the first electrode is potassium ion, the first ion carrier in the first region sensing membrane is valinomycin, and the co-extraction anion in the second region sensing membrane is trifluoromethyl sulfonic acid ion. The detection part of the first electrode and the second electrode is infiltrated by the sample to be measured, so that E 样本 , and the concentration C1 can be obtained by the relationship E 样本 -E 干膜 = S x lg (C1 / C2) + A.

[0113] Preferably, when the second region sensing membrane is an electrolyte membrane, the concentration of the determination object of the second electrode is the ion concentration C2 of the known concentration in the electrolyte membrane, and the concentration ratio C1 / C2 of the determination object of the first electrode and the second electrode is obtained, and the corresponding relationship is E 样本 -E 干膜 = S x lg (C1 / C2) + A.

[0114] Wherein, C1 corresponds to the concentration of the determination object of the first electrode, and C2 is the ion concentration of the known concentration in the electrolyte membrane.

[0115] The membrane potential of the electrolyte membrane after sample infiltration is a stable fixed value, so the value of C2 is a fixed value.

[0116] Exemplarily, when the determination object is potassium ion, the first ion carrier in the first region sensing membrane is valinomycin, and when detection is performed, the detection part of the first electrode and the second electrode is infiltrated by the sample to be measured, so that E 样本 , and the concentration C1 can be obtained by the relationship E 样本 -E 干 膜 = S x lg (C1 / C2) + A.

[0117] Preferably, when the second region sensing membrane is a polymer high molecular membrane, and the first ion carrier and the second ion carrier are different, the determination objects of the first electrode and the second electrode are different.

[0118] Exemplarily, when the determination object of the first electrode is sodium ion and the determination object of the second electrode is potassium ion, the first ion carrier in the first region sensing membrane is sodium ion carrier X, and the second ion carrier in the second region sensing membrane is valinomycin. When detection is performed, the detection part of the first electrode and the second electrode is infiltrated by the sample to be measured, so that E 样本 , and the ratio of the concentration C1 and the concentration C2 can be obtained by the relationship E 样本 -E 干膜 = S x lg (C1 / C2) + A.

[0119] Wherein C1 corresponds to the concentration of sodium ions in the sample to be measured, C2 corresponds to the concentration of potassium ions in the sample to be measured, S is the Nernst slope of the dry film self-calibrating sensing device, and A is the inherent constant of the dry film self-calibrating sensing device.

[0120] Preferably, the measurement object of the first electrode includes metal ions or non-metal ions; and the measurement object of the second electrode includes metal ions or non-metal ions.

[0121] The metal ions include any one of Li + , Na + , K + , Ca 2+ , Mg 2+ , Pb 2+ , Hg 2+ , Ag + , or Cu 2+ ; and the non-metal ions include any one of H + , NH4 + , F - , Cl - , Br - , I - , NO3 - , ClO4 - , S 2- , or CO3 2- .

[0122] When the concentration to be detected is the concentration of metabolites, the following applies:

[0123] When the sensing film of the second region is a polymer high molecular film, and the first ion carrier is the same as the second ion carrier, the measurement objects of the first electrode and the second electrode are the same. A reaction reagent is introduced into the detection part of the first electrode, and the concentration of the measurement object of the first electrode is represented as C0+C M , and the concentration ratio of the measurement objects of the first electrode and the second electrode (C0+C M ) / C2 is obtained, and the corresponding relationship is: E 样本 -E 干膜 = S x lg ((C0+C M ) / C2) + A.

[0124] Wherein C0+C M corresponds to the concentration of the measurement object of the first electrode, C2 corresponds to the concentration of the measurement object of the second electrode, C0 is the concentration of the ion detected by the first electrode in the sample, and C M is the concentration of metabolites in the sample, wherein C0=C2.

[0125] The metabolites include urea nitrogen or creatinine.

[0126] The reaction reagent includes at least one of urease, carbonic anhydrase, creatinine hydrolase or creatine hydrolase.

[0127] Preferably, the activity of the reaction reagent is 0.01U-20U, preferably 1U-10U.

[0128] Preferably, the polymer membrane is any one of an ammonium ion sensing membrane or a carbonate ion sensing membrane.

[0129] Preferably, the first ion carrier of the first region sensing membrane includes an ammonium ion carrier or a carbonate ion carrier; the second ion carrier of the second region sensing membrane includes an ammonium ion carrier or a carbonate ion carrier;

[0130] The reaction reagent is at least one of urease, carbonic anhydrase, creatinine hydrolase or creatine hydrolase;

[0131] The metabolite is urea nitrogen or creatinine.

[0132] For example, the reaction reagent is urease, and the metabolite is urea nitrogen. The urease can decompose urea into ammonia and carbon dioxide, and the ammonia and carbon dioxide are dissolved in the sample to be tested and converted into ammonium ions and carbonate ions.

[0133] When the first electrode and the second electrode are both measuring carbonate ions, the first ion carrier in the first region of the sensing membrane is a carbonate ion carrier, and the second ion carrier in the second region of the sensing membrane is a carbonate ion carrier. During the detection, urease is introduced into the detection part of the first electrode, and then the detection parts of the first and second electrodes are infiltrated with the sample to be tested. The urease converts the urea in the sample to be tested into ammonium ions, carbonate ions, and hydrogen ions, thereby obtaining E 样本 , so according to the relationship E 样本 -E 干膜 =S×lg((C0+C M ) / C2)+A, the concentration ratio of the first electrode and the second electrode to be measured is obtained (C0+C M ) / C2.

[0134] The concentration of ammonium ions or carbonate ions in general whole blood, serum, and plasma samples is very low. Therefore, the relationship E 样本 -E 干膜 =S×lg((C0+C M ) / C2)+A can be simplified to E 样本 -E 干膜 =S×lg(C M )+A.

[0135] Exemplarily, the setting method of the reaction reagent comprises directly placing on the detection part of the corresponding electrode; or dissolving the reaction reagent, then directly adding the solution on the corresponding sensing film or dropping on the mediator, and then covering the mediator on the detection part of the corresponding electrode.

[0136] Exemplarily, the mediator comprises any one of filter paper, glass fiber or cellulose membrane.

[0137] In a fourth aspect, the application further provides a method for detecting concentration by using the dry film self-calibration sensing device of the first aspect, and the method comprises the following steps:

[0138] The potential values of the sample determination state and the dry film state are respectively measured and recorded as E 样本 and E 干膜 , and the concentration product of the determination objects of the first electrode and the second electrode is obtained, and the corresponding relationship is: E 样本 -E 干膜 =S×lg(C1×C2)+A.

[0139] The charges of the determination objects of the first electrode and the second electrode are opposite charges, for example, the first electrode is an ammonium ion selective electrode, and the second electrode is a carbonate ion selective electrode, or vice versa.

[0140] Wherein, C1 corresponds to the concentration of the determination object of the first electrode, C2 corresponds to the concentration of the determination object of the second electrode, S is the Nernst slope of the dry film self-calibration sensing device, and A is the inherent constant of the dry film self-calibration sensing device.

[0141] Preferably, when the sensing film of the second region is a polymer macromolecular film, and the first ion carrier and the second ion carrier are different, the determination objects of the first electrode and the second electrode are different. Reaction reagents are introduced into the detection parts of the first electrode and the second electrode, and at this time, the concentration of the determination object of the first electrode is represented as C0+C M , the concentration of the determination object of the second electrode is represented as C3+C M , and the concentration product of the determination objects of the first electrode and the second electrode is obtained (C0+C M )×(C3+C M ), and the corresponding relationship is: E 样本 -E 干膜 =S×lg((C0+C M )×(C3+C M ))+A.

[0142] Wherein, C0+C M corresponds to the concentration C1 of the determination object of the first electrode, C3+C M corresponds to the concentration C2 of the determination object of the second electrode, C0 is the concentration of the detected ion of the first electrode in the sample, and C MC3 is the concentration of the ion detected by the second electrode in the sample.

[0143] The polymer macromolecular film is an ammonium ion sensing film or a carbonate ion sensing film.

[0144] The first ion carrier of the first region sensing film comprises an ammonium ion carrier or a carbonate ion carrier; the second ion carrier of the second region sensing film comprises an ammonium ion carrier or a carbonate ion carrier.

[0145] The reaction reagent is at least one of urease, carbonic anhydrase, creatinine hydrolase or creatine hydrolase.

[0146] The metabolic product is urea nitrogen or creatinine.

[0147] Exemplarily, the reaction reagent is urease, which can decompose urea into ammonia and carbon dioxide, and the ammonia and carbon dioxide are dissolved in the sample to be measured to become ammonium ions and carbonate ions. When the measurement objects of the first electrode and the second electrode are carbonate ions and ammonium ions respectively, the first ion carrier in the first region sensing film is a carbonate ion carrier, and the second ion carrier in the second region sensing film is an ammonium ion carrier. During detection, urease is introduced into the detection part of the first electrode and the second electrode, and then the sample to be measured is used to soak the detection part of the first electrode and the second electrode. The urease converts the urea in the sample to be measured into ammonium ions, carbonate ions and hydrogen ions, so that E 样本 , and the concentration product of the measurement objects of the first electrode and the second electrode (C0+C M )×(C3+C M ) is obtained.

[0148] The concentration of ammonium ions or carbonate ions in general whole blood, serum and plasma samples is very low, so the relationship E 样本 -E 干膜 =S×lg((C0+C M )×(C3+C M ))+A can be simplified to E 样本 -E 干膜 =S×lg(C M 2 )+A, and the concentration C M of urea nitrogen is obtained.

[0149] Exemplarily, the setting method of the reaction reagent comprises directly placing the reaction reagent on the detection part of the corresponding electrode; or dissolving the reaction reagent, and then directly adding the solution to the corresponding sensing film, or adding the solution dropwise on the mediator, and then covering the mediator on the detection part of the corresponding electrode.

[0150] Exemplarily, the mediator comprises but is not limited to any one of filter paper, glass fiber or cellulose membrane.

[0151] Compared with the prior art, the application has the following beneficial effects:

[0152] (1) The dry film self-calibration sensing device prepared by using the application does not need to use a calibration solution for calibration when measuring the concentration of an analyte, so there is no liquid substance in the test system, which can prevent the risk of equipment leakage from causing damage to life and property, and the measurement method is simple. In a complex and variable detection environment, accurate measurement data can be continuously provided without calibration and calibration, which reduces errors caused by the performance degradation or drift of the sensor, significantly improves the stability and reliability of the sensor, and reduces the detection cost.

[0153] (2) The dry film self-calibration sensing device prepared according to the embodiments of the application can simultaneously measure a plurality of different analyte concentrations or concentration ratios. Compared with the detection method in the prior art, which requires at least three electrodes to measure the concentration ratio, the application only needs two electrodes to measure the concentration ratio, which reduces the complexity and cost of the electrodes and the detection equipment, and improves the detection efficiency and accuracy.

[0154] (3) The dry film self-calibration sensing device prepared according to the embodiments of the application has excellent stability in a dry state, which ensures that the sensor has strong resistance to environmental interference factors during long-term use or storage, such as temperature and humidity changes, so that the performance of the sensor is less affected. The sensing device can work stably under complex environmental conditions and maintain its performance unchanged, which improves the accuracy and reliability of the measurement. In addition, the dry-state sensing device has low power consumption during operation, which helps to prolong the service life of the sensor and reduce the operating cost.

[0155] (4) The application uses a potential method to detect the interface potential to determine the concentration of the analyte to be measured. When the measured substance is an ion, the sample does not participate in the reaction during the measurement, and the concentration of the sample background substance is not destroyed, so the sample can be repeatedly used. In addition, the dry film self-calibration sensing device prepared by the application has high selectivity to the ion to be measured, and the electrode detection limit is low, which can detect very low concentrations. Therefore, in the presence of a plurality of analytes, interference can be effectively reduced, and the electrode has more significant accuracy in measuring complex system samples. BRIEF DESCRIPTION OF DRAWINGS

[0156] FIG. 1 is a structural schematic diagram of the dry film self-calibration sensing device in Examples 1-5;

[0157] FIG. 2 is a structural schematic diagram of the dry film self-calibration sensing device in Examples 6-9;

[0158] FIG. 3 is a structural schematic diagram of the dry film self-calibration sensing device in Example 10;

[0159] Fig. 4 is a structural schematic diagram of the dry film self-calibration sensing device in Example 11;

[0160] Fig. 5 is a standard curve in the case of Application Example 1-1;

[0161] Fig. 6 is a standard curve in the case of Application Example 1-2;

[0162] Fig. 7 is a standard curve in the case of Application Example 1-3;

[0163] Fig. 8 is a standard curve in the case of Application Example 2-1;

[0164] Fig. 9 is a standard curve in the case of Application Example 2-2;

[0165] Fig. 10 is a standard curve in the case of Application Example 3-1;

[0166] Fig. 11 is a standard curve in the case of Application Example 3-2;

[0167] Fig. 12 is a standard curve in the case of Application Example 3-3;

[0168] Fig. 13 is a standard curve for measuring the concentration of carbonate ions in the case of Application Example 4-1;

[0169] Fig. 14 is a standard curve for measuring the concentration of sodium ions in the case of Application Example 5;

[0170] Fig. 15 is a standard curve for measuring the concentration of potassium ions in the case of Application Example 5;

[0171] Fig. 16 is a standard curve for measuring the concentration of calcium ions in the case of Application Example 5;

[0172] Fig. 17 is a standard curve for measuring the concentration of sodium ions in the case of Application Example 6;

[0173] Fig. 18 is a standard curve for measuring the concentration of potassium ions in the case of Application Example 6;

[0174] Fig. 19 is a standard curve for measuring the concentration of calcium ions in the case of Application Example 6;

[0175] BRIEF DESCRIPTION OF DRAWINGS DETAILED DESCRIPTION

[0176] The technical solutions of the present application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.

[0177] The examples in this part further illustrate the content of the present application, but should not be understood as limiting the present application. Modifications or replacements of the methods, steps or conditions of the present application, without departing from the spirit and essence of the present application, all belong to the scope of the present application.

[0178] If not specifically indicated, the technical means used in the examples are conventional means known to those skilled in the art. In the examples, each reagent added, etc. is commercially available unless otherwise specified.

[0179] The operation of setting the insulating layer in the examples is not a further limitation of the technical solutions of the present application, but only to form a dry film self-calibration sensing device that meets the actual application.

[0180] Example 1

[0181] The present example provides a dry film self-calibration sensing device as shown in Figure 1, wherein the sensing film 5 of the first region 8 and the sensing film 5 of the second region 9 are both polymer macromolecular films, and the first ion carrier and the second ion carrier are different;

[0182] The dry film self-calibration sensing device provided in the present example is obtained by using the following preparation method, which comprises the following steps:

[0183] (1) Take the insulating substrate 1, and then use the silk screen printing method to attach the ink as the electrode layer on the insulating substrate 1, to independently obtain the first electrode 3 and the second electrode 4 which are both carbon electrodes;

[0184] (2) The sensing film 5 of the first region 8 is coated on the detection part 6 of the first electrode by coating, and the sensing film 5 of the second region 9 is coated on the detection part 7 of the second electrode by coating; continue to add the sensing film 5 to the detection part 6 of the first electrode and the detection part 7 of the second electrode until the two regions are connected, so that the sensing film 5 connects the detection part 6 of the first electrode and the detection part 7 of the second electrode; after the sensing film 5 of the first region 8 and the sensing film 5 of the second region 9 are formed, an insulating layer 2 is arranged on the first electrode 3 and the second electrode 4 to obtain a dry film self-calibration sensing device.

[0185] The sensing film 5 of the first region 8 is mixed from its corresponding preparation raw materials, including 0.2% sodium ion carrier X, 0.2% NaTFPB, 13.0% NPOE, 6.6% PVC and 80.0% tetrahydrofuran;

[0186] The sensing film 5 of the second region 9 is mixed from its corresponding preparation raw materials, including 0.4% valinomycin, 0.3% NaTFPB, 12.8% NPOE, 6.5% PVC and 80.0% tetrahydrofuran.

[0187] Example 2:

[0188] The embodiment provides a dry film self-calibration sensing device, as shown in Figure 1, wherein the sensing film 5 of the first area 8 and the sensing film 5 of the second area 9 are polymer high molecular films, and the first ion carrier and the second ion carrier are the same;

[0189] The dry film self-calibration sensing device provided by the embodiment is obtained by using the following preparation method, and the preparation method comprises the following steps.

[0190] (1) Take the insulating substrate 1, and then use a magnetron sputtering mode to attach a gold thin film on the insulating substrate 1 as an electrode layer, so that the first electrode 3 and the second electrode 4, which are both gold electrodes, are independently obtained.

[0191] (2) The point gluing mode is used to attach poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT-PSS) on the detection part 6 of the first electrode and the detection part 7 of the second electrode respectively, so that the detection part 6 of the first electrode and the detection part 7 of the second electrode covered by the conductive medium are independently obtained.

[0192] (3) The point gluing mode is used to coat the sensing film 5 of the first area 8 on the detection part 6 of the first electrode and the sensing film 5 of the second area 9 on the detection part 7 of the second electrode; the sensing film 5 is continuously added to the detection part 6 of the first electrode and the detection part 7 of the second electrode until the two areas are connected, so that the sensing film 5 connects the detection part 6 of the first electrode and the detection part 7 of the second electrode; after the sensing film 5 of the first area 8 and the sensing film 5 of the second area 9 are formed, the insulating layer 2 is arranged on the first electrode 3 and the second electrode 4, so that the dry film self-calibration sensing device is obtained.

[0193] The sensing film 5 of the first area 8 is mixed by corresponding raw materials, and comprises 0.4% valinomycin, 0.3% NaTFPB, 12.8% NPOE, 6.5% PVC and 80.0% tetrahydrofuran.

[0194] The sensing film 5 of the second area 9 is mixed by corresponding raw materials, and comprises 0.4% valinomycin, 0.3% NaTFPB, 12.8% NPOE, 6.5% PVC and 80.0% tetrahydrofuran.

[0195] Embodiment 3

[0196] The embodiment provides a dry film self-calibration sensing device, as shown in Figure 1, wherein the sensing film 5 of the first area 8 is a polymer high molecular film, and the sensing film 5 of the second area 9 is an electrolyte film.

[0197] The dry film self-calibration sensing device provided by the embodiment is obtained by using the following preparation method, and the preparation method comprises the following steps.

[0198] (1) Take the insulating substrate 1, and then use the magnetron sputtering method to attach a silver thin film on the insulating substrate 1 as an electrode layer, to independently obtain the first electrode 3 and the second electrode 4, both of which are silver electrodes;

[0199] (2) Use the dispensing method to attach poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT-PSS) on the detection part 6 of the first electrode and the detection part 7 of the second electrode, respectively, to independently obtain the detection part 6 of the first electrode covered with a conductive medium and the detection part 7 of the second electrode covered with a conductive medium;

[0200] (3) Cover the sensing film 5 of the first area 8 on the detection part 6 of the first electrode by dripping, and cover the sensing film 5 of the second area 9 on the detection part 7 of the second electrode by dripping; continue to add the sensing film 5 to the detection part 6 of the first electrode and the detection part 7 of the second electrode until the two areas are connected, so as to connect the detection part 6 of the first electrode and the detection part 7 of the second electrode with the sensing film 5; after the sensing film 5 of the first area 8 and the sensing film 5 of the second area 9 are formed, an insulating layer 2 is arranged on the first electrode 3 and the second electrode 4 to obtain a dry film self-calibration sensing device.

[0201] The sensing film 5 of the first area 8 is mixed from its corresponding preparation raw materials, including 0.4% valinomycin, 0.3% NaTFPB, 12.8% NPOE, 6.5% PVC, and 80.0% tetrahydrofuran;

[0202] The sensing film 5 of the second area 9 is mixed from its corresponding preparation raw materials, including 5.0% propyl tributyl phosphonium bis(trifluoromethanesulfonyl) imide salt, 30.0% NPOE, 15.0% PVC, and 50.0% tetrahydrofuran.

[0203] Example 4:

[0204] The embodiment provides a dry film self-calibration sensing device, as shown in FIG. 1, the sensing film 5 of the first area 8 and the sensing film 5 of the second area 9 are polymer macromolecular films, and the first ion carrier and the second ion carrier are the same;

[0205] The dry film self-calibration sensing device provided in the embodiment is obtained by using the following preparation method, which comprises the following steps:

[0206] (1) Take the insulating substrate 1, and then use the magnetron sputtering method to attach a silver thin film on the insulating substrate 1 as an electrode layer, to independently obtain the first electrode 3 and the second electrode 4, both of which are silver electrodes;

[0207] (2) using the dispensing method, the detection part 6 of the first electrode and the detection part 7 of the second electrode are respectively attached with poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT-PSS), and the detection part 6 of the first electrode covered with the conductive medium and the detection part 7 of the second electrode are respectively obtained independently;

[0208] (3) the sensing film 5 of the first region 8 is coated on the detection part 6 of the first electrode by dispensing, and the sensing film 5 of the second region 9 is coated on the detection part 7 of the second electrode by dispensing; continue to add the sensing film 5 to the detection part 6 of the first electrode and the detection part 7 of the second electrode until the two regions are connected in contact, so that the sensing film 5 connects the detection part 6 of the first electrode and the detection part 7 of the second electrode; after the sensing film 5 of the first region 8 and the sensing film 5 of the second region 9 are formed, an insulating layer 2 is arranged on the first electrode 3 and the second electrode 4 to obtain a dry film self-calibration sensing device.

[0209] The sensing film 5 of the first region 8 is mixed with its corresponding preparation raw materials, including 0.4% carbonate ion carrier VII, 0.3% TDMACL, 12.8% DOA, 6.5% PVC and 80.0% tetrahydrofuran;

[0210] The sensing film 5 of the second region 9 is mixed with its corresponding preparation raw materials, including 0.4% carbonate ion carrier VII, 0.3% TDMACL, 12.8% DOA, 6.5% PVC and 80.0% tetrahydrofuran.

[0211] The reaction reagent urease is introduced into the detection part 6 of the first electrode, wherein the activity of the urease is 10U.

[0212] Example 5:

[0213] The embodiment provides a dry film self-calibration sensing device, as shown in Figure 1, the sensing film 5 of the first region 8 and the sensing film 5 of the second region 9 are polymer macromolecular films, and the first ion carrier and the second ion carrier are different;

[0214] The dry film self-calibration sensing device provided by the embodiment is obtained by using the following preparation method, and the preparation method comprises the following steps:

[0215] (1) take the insulating substrate 1, then use the magnetron sputtering method to attach the gold thin film on the insulating substrate 1 as the electrode layer, and respectively independently obtain the first electrode 3 and the second electrode 4 which are both gold electrodes;

[0216] (2) using the dispensing method, poly (3, 4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT-PSS) is attached on the detection part 6 of the first electrode and the detection part 7 of the second electrode respectively, and the detection part 6 of the first electrode and the detection part 7 of the second electrode are respectively independently covered with conductive medium;

[0217] (3) the sensing film 5 of the first region 8 is coated on the detection part 6 of the first electrode by the dispensing method, and the sensing film 5 of the second region 9 is coated on the detection part 7 of the second electrode by the dispensing method; continue to add the sensing film 5 to the detection part 6 of the first electrode and the detection part 7 of the second electrode until the two regions are connected in contact, so that the sensing film 5 connects the detection part 6 of the first electrode and the detection part 7 of the second electrode; after the sensing film 5 of the first region 8 and the sensing film 5 of the second region 9 are formed, an insulating layer 2 is arranged on the first electrode 3 and the second electrode 4 to obtain a dry film self-calibration sensing device.

[0218] The sensing film 5 of the first region 8 is mixed from its corresponding preparation raw materials, including 0.4% carbonate ion carrier VII, 0.3% TDMACL, 12.8% DOA, 6.5% PVC and 80.0% tetrahydrofuran;

[0219] The sensing film 5 of the second region 9 is mixed from its corresponding preparation raw materials, including 0.4% ammonium ion carrier I, 0.3% NaTFPB, 12.8% NPOE, 6.5% PVC and 80.0% tetrahydrofuran.

[0220] The reaction reagent urease is introduced into the detection part 6 of the first electrode and the detection part 7 of the second electrode, wherein the activity of the urease is 10U.

[0221] Example 6:

[0222] The embodiment provides a dry film self-calibration sensing device as shown in FIG. 2, in which a conductive medium 10 is arranged between the first region 8, the second region 9 and the electrode detection part;

[0223] The dry film self-calibration sensing device provided by the embodiment is obtained by using the following preparation method, which comprises the following steps:

[0224] (1) take the insulating substrate 1, and then use the screen printing method to attach the ink as the electrode layer on the insulating substrate 1, and respectively independently obtain the first electrode 3 and the second electrode 4 which are both carbon electrodes;

[0225] (2) using the screen printing method, attach reduced graphene on the detection part 6 of the first electrode and the detection part 7 of the second electrode respectively, and respectively independently obtain the conductive medium 10 covering the detection part 6 of the first electrode and the detection part 7 of the second electrode;

[0226] (3) In the detection part 6 of the first electrode and the conductive medium 10 covering the detection part of the first electrode, the sensing film 5 of the first region 8 is coated, and in the detection part 7 of the second electrode and the conductive medium 10 covering the detection part of the second electrode, the sensing film 5 of the second region 9 is coated; continue to add sensing film 5 to the detection part 6 of the first electrode and the detection part 7 of the second electrode until the two regions are connected in contact, realize the connection of the detection part 6 of the first electrode and the detection part 7 of the second electrode with the sensing film 5; after the sensing film 5 of the first region 8 and the sensing film 5 of the second region 9 are formed, an insulating layer 2 is arranged on the first electrode 3 and the second electrode 4, and a dry film self-calibration sensing device is obtained.

[0227] The sensing film 5 of the first region 8 is mixed from its corresponding preparation raw materials, including 0.2% sodium ion carrier X, 0.2% NaTFPB, 13.0% NPOE, 6.6% PVC and 80.0% tetrahydrofuran;

[0228] The sensing film 5 of the second region 9 is mixed from its corresponding preparation raw materials, including 0.4% valinomycin, 0.3% NaTFPB, 12.8% NPOE, 6.5% PVC and 80.0% tetrahydrofuran.

[0229] Example 7:

[0230] The embodiment provides a dry film self-calibration sensing device as shown in Figure 2, wherein a conductive medium 10 is arranged between the detection part 6 of the first electrode and the detection part 7 of the second electrode;

[0231] The embodiment provides a dry film self-calibration sensing device, which is the same as the dry film self-calibration sensing device provided in Example 1 except that the sensing film 5 covers the conductive medium 10.

[0232] The dry film self-calibration sensing device provided in the embodiment is obtained by the following preparation method, and the preparation method comprises the following steps:

[0233] (1) Take the insulating substrate 1, and then use the silk screen printing method to attach the ink as the electrode layer on the insulating substrate 1, to independently obtain the first electrode 3 and the second electrode 4 which are both carbon electrodes;

[0234] (2) Continue to attach the reduced graphene on the insulating substrate 1 by using the silk screen printing method to obtain the conductive medium 10, and the conductive medium 10 is not connected with the first electrode 3 and the second electrode 4;

[0235] (3) the sensing film 5 of the first region 8 is coated on the detection part 6 of the first electrode by coating, and the sensing film 5 of the second region 9 is coated on the detection part 7 of the second electrode by coating; the sensing film 5 is continuously added to the detection part 6 of the first electrode and the detection part 7 of the second electrode until the two regions are connected in contact, so that the sensing film 5 connects the detection part 6 of the first electrode and the detection part 7 of the second electrode and coats the conductive medium 10; after the sensing film 5 of the first region 8 and the sensing film 5 of the second region 9 are formed, an insulating layer 2 is arranged on the first electrode 3 and the second electrode 4 to obtain a dry film self-calibration sensing device.

[0236] The sensing film 5 of the first region 8 is mixed from its corresponding preparation raw materials, including 0.2% sodium ion carrier X, 0.2% NaTFPB, 13.0% NPOE, 6.6% PVC and 80.0% tetrahydrofuran;

[0237] The sensing film 5 of the second region 9 is mixed from its corresponding preparation raw materials, including 0.4% valinomycin, 0.3% NaTFPB, 12.8% NPOE, 6.5% PVC and 80.0% tetrahydrofuran.

[0238] Example 8:

[0239] The embodiment provides a dry film self-calibration sensing device provided with a conductive medium 10 between the first region 8 and the detection part 6 of the first electrode and between the second region 9 and the detection part 7 of the second electrode

[0240] The dry film self-calibration sensing device provided by the embodiment is obtained by using the following preparation method, and the preparation method comprises the following steps:

[0241] (1) take the insulating substrate 1, then use the magnetic control sputtering method to attach a silver thin film on the insulating substrate 1 as an electrode layer, and independently obtain the first electrode 3 and the second electrode 4 which are both silver electrodes;

[0242] (2) using the magnetic control sputtering method, attach reduced graphene on the detection part 6 of the first electrode and the detection part 7 of the second electrode, and independently obtain the conductive medium 10 covering the detection part 6 of the first electrode and the detection part 7 of the second electrode;

[0243] (3) On the detection part 6 of the first electrode and the conductive medium 10 partially covering the detection part 6 of the first electrode, the sensing film 5 of the first region 8 is coated by coating, and on the detection part 7 of the second electrode and the conductive medium 10 partially covering the detection part 7 of the second electrode, the sensing film 5 of the second region 9 is coated by coating; continue to add the sensing film 5 to the detection part 6 of the first electrode and the detection part 7 of the second electrode until the two regions are connected in contact, so that the sensing film 5 connects the detection part 6 of the first electrode and the detection part 7 of the second electrode; after the sensing film 5 of the first region 8 and the sensing film 5 of the second region 9 are formed, an insulating layer 2 is arranged on the first electrode 3 and the second electrode 4 to obtain a dry film self-calibration sensing device.

[0244] The sensing film 5 of the first region 8 is mixed from its corresponding preparation raw materials, including 0.4% valinomycin, 0.3% NaTFPB, 12.8% NPOE, 6.5% PVC, and 80.0% tetrahydrofuran;

[0245] The sensing film 5 of the second ion is mixed from its corresponding preparation raw materials, including 5.0% propyl tributyl phosphonium bis(trifluoromethanesulfonyl) imide salt, 30.0% NPOE, 15.0% PVC, and 50.0% tetrahydrofuran.

[0246] Example 9:

[0247] The embodiment provides a dry film self-calibration sensing device as shown in FIG. 2, in which a conductive medium 10 is arranged between the detection part 6 of the first electrode and the detection part 7 of the second electrode;

[0248] The dry film self-calibration sensing device provided by the embodiment is obtained by using the following preparation method, and the preparation method comprises the following steps:

[0249] (1) Take the insulating substrate 1, and then use the magnetron sputtering method to attach a silver thin film on the insulating substrate 1 as an electrode layer, to independently obtain the first electrode 3 and the second electrode 4 which are both silver electrodes;

[0250] (2) Continue to attach reduced graphene on the insulating substrate 1 by using the magnetron sputtering method to obtain the conductive medium 10, and the conductive medium 10 is not connected to the first electrode 3 and the second electrode 4;

[0251] (3) the sensing film 5 of the first region 8 is coated on the detection part 6 of the first electrode by dropwise adding, and the sensing film 5 of the second region 9 is coated on the detection part 7 of the second electrode by dropwise adding; the sensing film 5 is continuously added to the detection part 6 of the first electrode and the detection part 7 of the second electrode until the two regions are connected in contact, so that the sensing film 5 connects and coats the conductive medium 10 between the detection part 6 of the first electrode and the detection part 7 of the second electrode; after the sensing film 5 of the first region 8 and the sensing film 5 of the second region 9 are formed, the insulating layer 2 is arranged on the first electrode 3 and the second electrode 4 to obtain the dry film self-calibration sensing device.

[0252] The sensing film 5 of the first region 8 is mixed by corresponding raw materials, including 0.4% valinomycin, 0.3% NaTFPB, 12.8% NPOE, 6.5% PVC and 80.0% tetrahydrofuran;

[0253] The sensing film 5 of the second region 9 is mixed by corresponding raw materials, including 5.0% propyl tributyl phosphonium bis(trifluoromethanesulfonyl) imide salt, 30.0% NPOE, 15.0% PVC and 50.0% tetrahydrofuran.

[0254] Example 10:

[0255] The embodiment provides a dry film self-calibration sensing device as shown in FIG. 3, which has three first electrodes 3 and one second electrode 4;

[0256] The sensing film 5 of the second region 9 is an electrolyte film;

[0257] The dry film self-calibration sensing device provided by the embodiment is obtained by using the following preparation method, and the preparation method comprises the following steps:

[0258] (1) take the insulating substrate 1, and then use the screen printing method to attach the ink as the electrode layer on the insulating substrate 1, so as to independently obtain three first electrodes 3 and one second electrode 4 which are all carbon electrodes;

[0259] (2) the sensing film 5 of the first region 8 is coated on the detection part 6 of the first electrode by coating, and the sensing film 5 of the second region 9 is coated on the detection part 7 of the second electrode by coating; the sensing film 5 is continuously added to the detection part 6 of the first electrode and the detection part 7 of the second electrode until the two regions are connected in contact, so that the sensing film 5 connects the detection part 6 of the first electrode and the detection part 7 of the second electrode; after the sensing film 5 of the first region 8 and the sensing film 5 of the second region 9 are formed, the insulating layer 2 is arranged on the first electrode 3 and the second electrode 4 to obtain the dry film self-calibration sensing device.

[0260] The sensing membrane 5 of the first first region 8 is mixed from its corresponding preparation raw materials, including 0.2% sodium ion carrier X, 0.2% NaTFPB, 13.0% NPOE, 6.6% PVC, and 80.0% tetrahydrofuran;

[0261] The preparation raw materials of the sensing membrane 5 of the second first region 8 include 0.4% valinomycin, 0.3% NaTFPB, 12.8% NPOE, 6.5% PVC, and 80.0% tetrahydrofuran;

[0262] The preparation raw materials of the sensing membrane 5 of the third first region 8 include 0.4% calcium ion carrier 1, 0.2% NaTFPB, 12.8% NPOE, 6.6% PVC, and 80.0% tetrahydrofuran;

[0263] The sensing membrane 5 of the second region 9 is mixed from its corresponding preparation raw materials, including 5.0% propyl tributyl phosphonium bis(trifluoromethanesulfonyl) imide salt, 30.0% NPOE, 15.0% PVC, and 50.0% tetrahydrofuran.

[0264] Example 11:

[0265] The dry film self-calibration sensing device provided in the embodiment has three first electrodes 3 and three second electrodes 4 as shown in FIG. 4;

[0266] The sensing membrane 5 of the second region 9 is a polymer macromolecular film;

[0267] The dry film self-calibration sensing device provided in the embodiment is obtained by using the following preparation method, and the preparation method includes the following steps:

[0268] (1) Take the insulating substrate 1, and then use the screen printing method to attach the ink as the electrode layer on the insulating substrate 1 to independently obtain three first electrodes 3 and three second electrodes 4 which are all carbon electrodes, and each first electrode 3 corresponds to a second electrode 4;

[0269] (2) The sensing membrane 5 of the first region 8 is coated on the detection part 6 of the first electrode by coating, and the sensing membrane 5 of the second region 9 is coated on the detection part 7 of the second electrode by coating; continue to add the sensing membrane 5 to the detection part 6 of the first electrode and the detection part 7 of the second electrode until the two regions are connected, so that the sensing membrane 5 connects the detection part 6 of the first electrode and the detection part 7 of the second electrode; after the sensing membrane 5 of the first region 8 and the sensing membrane 5 of the second region 9 are formed, the insulating layer 2 is arranged on the first electrode 3 and the second electrode 4 to obtain the dry film self-calibration sensing device.

[0270] The sensing membrane 5 of the first region 8 is mixed by its corresponding preparation raw materials, the preparation raw materials of the sensing membrane 5 of the first first region 8 include 0.2% sodium ion carrier X, 0.2% NaTFPB, 13.0% NPOE, 6.6% PVC and 80.0% tetrahydrofuran; the preparation raw materials of the sensing membrane 5 of the second first region 8 include 0.4% valinomycin, 0.3% NaTFPB, 12.8% NPOE, 6.5% PVC and 80.0% tetrahydrofuran; the preparation raw materials of the sensing membrane 5 of the third first region 8 include 0.4% calcium ion carrier 1, 0.2% NaTFPB, 12.8% NPOE, 6.6% PVC and 80.0% tetrahydrofuran.

[0271] The sensing membrane 5 of the second region 9 is mixed by its corresponding preparation raw materials, the preparation raw materials of the sensing membrane 5 of the first second region 9 include 0.2% sodium ion carrier X, 0.2% NaTFPB, 13.0% NPOE, 6.6% PVC and 80.0% tetrahydrofuran; the preparation raw materials of the sensing membrane 5 of the second second region 9 include 0.4% valinomycin, 0.3% NaTFPB, 12.8% NPOE, 6.5% PVC and 80.0% tetrahydrofuran; the preparation raw materials of the sensing membrane 5 of the third second region 9 include 0.4% calcium ion carrier 1, 0.2% NaTFPB, 12.8% NPOE, 6.6% PVC and 80.0% tetrahydrofuran.

[0272] Wherein, the first first electrode 3 corresponds to the first second electrode 4, the second first electrode 3 corresponds to the second second electrode 4, and the third first electrode 3 corresponds to the third second electrode 4.

[0273] Application Example 1-1

[0274] The application example provides a method for detecting concentration by using the dry film self-calibration sensing device provided in application example 1, and the method comprises the following steps:

[0275] Different concentrations of KCl are added in 10 mM PBS pH7.4 buffer solution, and the concentration ratio of Na and K is adjusted, so that C Na / C K The solutions with the ratios of 35, 60, 26.7, 12, 3.4 and 1.6 are obtained; the dry film signal E 干膜 The prepared solution is used to soak the detection part of the first electrode and the second electrode, and the solution signal E 样本 is measured, and the specific numerical value is shown in Table 1, and E 样本 -E 干膜 = S x lg (C Na / C K)+A, the standard curve y=53.659x-50.076 is obtained with S of 53.659 and A of -50.076, as shown in Figure 5. Where x is lg(C Na / C K ), y is E 样本 -E 干膜 .

[0276] Table 1

[0277] By measuring the electrical signal of the sample and based on the known dry film signal, the Na / K ratio of the sample can be calculated using the standard curve.

[0278] Application Example 1-2

[0279] This application example provides a method for detecting concentration using the dry film self-calibration sensor device provided in Example 6, the method comprising the following steps:

[0280] C was obtained by adding different concentrations of KCl to 10 mM PBS pH 7.4 buffer solution and adjusting the concentration ratio of Na and K. Na / C K Solutions with ratios of 35, 60, 26.7, 12, 3.4, and 1.6; determination of dry film signal E 干膜 , soak the configured solution into the detection part of the first electrode and the second electrode, and measure the solution signal E 样本 , the specific values ​​are shown in Table 2, through E 样本 -E 干膜 =S×lg(C Na / C K )+A, the standard curve y=60.286x-64.962 is obtained, where S is 60.286 and A is -64.962, as shown in FIG6 . Where x is lg(C Na / C K ), y is E 样本 -E 干膜 .

[0281] Table 2

[0282] By measuring the electrical signal of the sample and based on the known dry film signal, the Na / K ratio of the sample can be calculated using the standard curve.

[0283] Application Examples 1-3

[0284] This application example provides a method for detecting concentration using the dry film self-calibration sensor device provided in Example 7, the method comprising the following steps:

[0285] C Na / C K The solutions with the ratios of 35, 60, 26.7, 12, 3.4 and 1.6 were obtained by adding different concentrations of KCl in 10 mM PBS pH7.4 buffer solution to adjust the ratio of Na and K concentrations 干膜 The prepared solution was used to soak the detection part of the first electrode and the second electrode, and the solution signal E 样本 was measured 样本 The specific values are shown in Table 3, and the standard curve y = 61.496x + 3.9297 was obtained by the relationship of E 干膜 = S x lg(C Na / C K ) + A, in which S is 61.496 and A is 3.9297, as shown in FIG. 7. In the formula, x is lg(C Na / C K ), and y is E 样本 -E 干膜 .

[0286] Table 3

[0287] By measuring the electrical signal of the sample, the Na / K ratio of the sample can be calculated by the standard curve based on the known dry film signal.

[0288] Application Example 2-1

[0289] The application example provides a method for detecting the concentration of the dry film self-calibration sensing device provided in Embodiment 2, and the method comprises the following steps:

[0290] Potassium ion solutions with concentrations of 1 mmol / L, 2 mmol / L, 4 mmol / L, 8 mmol / L, 15 mmol / L and 30 mmol / L were prepared for use;

[0291] The dry film signal E 干膜 was measured 样本 When detecting, a known amount of KCl solid 200 mmol / L was introduced into the detection part of the second electrode, and then the prepared potassium ion solutions with different concentrations were used to soak the detection part of the first electrode and the second electrode, so as to obtain E 样本 The specific values are shown in Table 4, and the standard curve y = 60.479x - 45.601 was obtained by the relationship of E 干膜 = S x lg(C1 / (C1+C x )), in which S is 60.479 and A is -45.601, as shown in FIG. 8. In the formula, x is lg(C K / (C K +C KCl )), and y is E样本 -E 干膜 .

[0292] Table 4

[0293] By measuring the electrical signal of the sample and based on the known dry film signal, the concentration of potassium ions in the sample can be calculated using a standard curve.

[0294] Application Example 2-2

[0295] This application example provides a method for detecting concentration using the dry film self-calibration sensor device provided in Example 2, the method comprising the following steps:

[0296] Prepare potassium ion solutions with concentrations of 1mmol / L, 2mmol / L, 4mmol / L, 8mmol / L, 15mmol / L, and 30mmol / L for use;

[0297] Determination of dry film signal E 干膜 When testing, 0.1mmol / L of trifluoromethanesulfonate ions was introduced into the detection part of the second electrode, and then the detection parts of the first electrode and the second electrode were infiltrated with prepared potassium ion solutions of different concentrations to obtain E 样本 , the specific values ​​are shown in Table 5, through E 样本 -E 干膜 =S×lg(C1 / C2)+A, we can get the standard curve y=55.619x-66.306 where S is 55.619 and A is -66.306, as shown in Figure 9, where x is lg(C K / C 三氟甲基磺酸根离子 ), y is E 样本 -E 干膜 .

[0298] Table 5

[0299] By measuring the electrical signal of the sample and based on the known dry film signal, the concentration of potassium ions in the sample can be calculated using a standard curve.

[0300] Application Example 3-1

[0301] This application example provides a method for detecting concentration using the dry film self-calibration sensor device provided in Example 3, the method comprising the following steps:

[0302] Prepare potassium ion solutions with concentrations of 1mmol / L, 2mmol / L, 4mmol / L, 8mmol / L, 15mmol / L, and 30mmol / L for use;

[0303] Determination of dry film signal E 干膜 , soak the configured solution into the detection part of the first electrode and the second electrode, and measure the solution signal E 样本 , the specific values ​​are shown in Table 6, through E 样本 -E 干膜 =S×lg(C1 / C2)+A, the standard curve y=58.493x-37.849 is obtained with S of 58.493 and A of -37.849, as shown in Figure 10. Where x is lg(C K / C2), y is E 样本 -E 干膜 , C2 is the concentration of the lipophilic electrolyte - propyltributylphosphonium bis(trifluoromethanesulfonyl)imide salt on the second electrode.

[0304] Table 6

[0305] By measuring the electrical signal of the sample, the concentration of potassium ions in the sample can be calculated using a standard curve based on the known dry film signal and the concentration of the lipophilic electrolyte - propyltributylphosphonium bis(trifluoromethanesulfonyl)imide salt in the second electrode.

[0306] Application Example 3-2

[0307] This application example provides a method for detecting concentration using the dry film self-calibration sensor device provided in Example 8, the method comprising the following steps:

[0308] Prepare potassium ion solutions with concentrations of 1mmol / L, 2mmol / L, 4mmol / L, 8mmol / L, 15mmol / L, and 30mmol / L for use;

[0309] Determination of dry film signal E 干膜 , soak the configured solution into the detection part of the first electrode and the second electrode, and measure the solution signal E 样本 , the specific values ​​are shown in Table 7, through E 样本 -E 干膜 =S×lg(C1 / C2)+A, the standard curve y=58.185x+4.6233 is obtained with S of 58.185 and A of 4.6233, as shown in Figure 11. K / C2), y is E 样本 -E 干膜 , C2 is the concentration of the lipophilic electrolyte - propyltributylphosphonium bis(trifluoromethanesulfonyl)imide salt on the second electrode.

[0310] Table 7

[0311] The concentration of potassium ions in the sample can be calculated by a standard curve based on the electrical signal of the sample, the known dry film signal and the concentration of lipophilic electrolyte-propyl tributyl phosphonium bis(trifluoromethanesulfonyl) imide salt in the second electrode.

[0312] Application Example 3-3

[0313] The application example provides a method for detecting the concentration of the dry film self-calibration sensing device provided in application example 9, and the method comprises the following steps:

[0314] Potassium ion solutions with concentrations of 1 mmol / L, 2 mmol / L, 4 mmol / L, 8 mmol / L, 15 mmol / L and 30 mmol / L are configured for standby;

[0315] The dry film signal E is measured 干膜 The prepared solution is used to soak the detection part of the first electrode and the second electrode, and the solution signal E is measured 样本 The specific values are shown in Table 8, and a standard curve y=60.529x+1.7753 is obtained by the relationship E 样本 -E 干膜 = S x lg (C1 / C2) + A, wherein S is 60.529, A is 1.7753, as shown in FIG. 12. Wherein x is lg (C K / C2), and y is E 样本 -E 干膜 , and C2 is the concentration of lipophilic electrolyte-propyl tributyl phosphonium bis(trifluoromethanesulfonyl) imide salt on the second electrode.

[0316] Table 8

[0317] The concentration of potassium ions in the sample can be calculated by a standard curve based on the electrical signal of the sample, the known dry film signal and the concentration of lipophilic electrolyte-propyl tributyl phosphonium bis(trifluoromethanesulfonyl) imide salt in the second electrode.

[0318] Application Example 4-1

[0319] The application example provides a method for detecting urea nitrogen by using the dry film self-calibration sensing device provided in application example 4, and the method comprises the following steps:

[0320] Urea solutions with concentrations of 3.6 mmol / L, 7.3 mmol / L, 18.2 mmol / L, 36.4 mmol / L and 61.8 mmol / L are configured for standby;

[0321] The dry film signal E is measured 干膜, detection, 6U urease was introduced into the detection part of the second electrode, and then the detection part of the first electrode and the second electrode was immersed with different concentrations of urea solution prepared, so that E 样本 ;

[0322] Since the concentration range of carbonate ions in the sample is generally <1 mmol / L, C0 and C2 can be ignored. Therefore, E 样本 -E 干 膜 = S x lg((C0+C M ) / C2)+A relationship can be simplified as: E 样本 -E 干膜 = S x lg(C M )+A. Through the relationship of E 样本 -E 干膜 = S x lg(C M )+A, the standard curve y=66.992x-58.036 can be obtained, as shown in Figure 13, wherein x is lg(C M ), C M is the concentration of urea nitrogen, and y is E 样本 -E 干膜 . The specific values are shown in Table 9.

[0323] Table 9

[0324] By measuring the electrical signal of the sample, the concentration of urea nitrogen in the sample can be calculated by the standard curve based on the known dry film signal.

[0325] Application Example 5

[0326] The application example provides a method for detecting the concentration of the dry film self-calibration sensing device provided in application example 10, and the method comprises the following steps:

[0327] Sodium ion solutions with concentrations of 60 mmol / L, 80 mmol / L, 100 mmol / L, 140 mmol / L, 160 mmol / L and 180 mmol / L are prepared for standby;

[0328] Potassium ion solutions with concentrations of 1 mmol / L, 2 mmol / L, 4 mmol / L, 8 mmol / L, 15 mmol / L and 30 mmol / L are prepared for standby;

[0329] Calcium ion solutions with concentrations of 0.2 mmol / L, 0.4 mmol / L, 0.8 mmol / L, 1 mmol / L, 1.5 mmol / L and 2.5 mmol / L are prepared for standby;

[0330] Determination of dry film signal E 干膜 The prepared sodium ion solution was used to soak the detection part of the first first electrode, the prepared potassium ion solution was used to soak the detection part of the second first electrode, and the prepared calcium ion solution was used to soak the detection part of the third first electrode, and the solution signals were determined respectively, and the specific values are shown in Tables 10 to 12. The three different standard curves were obtained by the relationship of E = S x lg (C1 / C2) + A. 样本 -E 干膜 The three different standard curves were obtained by the relationship of E = S x lg (C1 / C2) + A.

[0331] The standard curve of the first first electrode and the second electrode is y = 63.171x - 138.56, as shown in FIG. 14, wherein x is lg (C1 / C2), y is E, C1 is the concentration of the lipophilic electrolyte - propyl tributyl phosphonium bis (trifluoromethane sulfonate) imide salt on the first electrode, and C2 is the concentration of the lipophilic electrolyte - propyl tributyl phosphonium bis (trifluoromethane sulfonate) imide salt on the second electrode. Na / C2), y is E 样本 -E 干膜 C2 is the concentration of the lipophilic electrolyte - propyl tributyl phosphonium bis (trifluoromethane sulfonate) imide salt on the second electrode.

[0332] Table 10

[0333] The standard curve of the second first electrode and the second electrode is y = 58.234x - 36.961, as shown in FIG. 15, wherein x is lg (C1 / C2), y is E, C1 is the concentration of the lipophilic electrolyte - propyl tributyl phosphonium bis (trifluoromethane sulfonate) imide salt on the first electrode, and C2 is the concentration of the lipophilic electrolyte - propyl tributyl phosphonium bis (trifluoromethane sulfonate) imide salt on the second electrode. K / C2), y is E 样本 -E 干膜 C2 is the concentration of the lipophilic electrolyte - propyl tributyl phosphonium bis (trifluoromethane sulfonate) imide salt on the second electrode.

[0334] Table 11

[0335] The standard curve of the third first electrode and the second electrode is y = 32.905x - 0.3398, as shown in FIG. 16, wherein x is lg (C1 / C2), y is E, C1 is the concentration of the lipophilic electrolyte - propyl tributyl phosphonium bis (trifluoromethane sulfonate) imide salt on the first electrode, and C2 is the concentration of the lipophilic electrolyte - propyl tributyl phosphonium bis (trifluoromethane sulfonate) imide salt on the second electrode. Ca / C2), y is E 样本 -E 干膜 C2 is the concentration of the lipophilic electrolyte - propyl tributyl phosphonium bis (trifluoromethane sulfonate) imide salt on the second electrode.

[0336] Table 12

[0337] By measuring the electrical signal of the sample, on the basis of the known dry film signal and the concentration of the lipophilic electrolyte - propyl tributyl phosphonium bis (trifluoromethane sulfonate) imide salt in the second electrode, the concentrations of sodium ions, potassium ions and calcium ions in the sample can be calculated by the standard curve.

[0338] Application Example 6

[0339] The application example provides a method for detecting concentration by using the dry film self-calibration sensing device provided in the application example 11, and the method comprises the following steps:

[0340] Sodium ion solutions with concentrations of 60 mmol / L, 80 mmol / L, 100 mmol / L, 140 mmol / L, 160 mmol / L and 180 mmol / L are configured for standby;

[0341] Potassium ion solutions with concentrations of 1 mmol / L, 2 mmol / L, 4 mmol / L, 8 mmol / L, 15 mmol / L and 30 mmol / L are configured for standby;

[0342] Calcium ion solutions with concentrations of 0.2 mmol / L, 0.4 mmol / L, 0.8 mmol / L, 1 mmol / L, 1.5 mmol / L and 2.5 mmol / L are configured for standby;

[0343] Measuring the dry film signal E 干膜 When detecting, NaCl solid 200 mmol / L is introduced into the detection part of the first second electrode, the prepared sodium ion solution is used to soak the detection part of the first first electrode and the first second electrode; KCl solid 200 mmol / L is introduced into the detection part of the first second electrode, the prepared potassium ion solution is used to soak the detection part of the second first electrode and the second second electrode; CaCl solid 200 mmol / L is introduced into the detection part of the first second electrode, the prepared calcium ion solution is used to soak the detection part of the third first electrode and the third third electrode, and the solution signal is measured respectively, and three different standard curves are obtained through the relationship formula E 样本 -E 干膜 =Sxlg(C1 / C1+C X ), and specific values are shown in Tables 13-15.

[0344] The standard curve of the first first electrode and the first second electrode is y=54.998x-34.357, as shown in FIG. 17, wherein x is lg(C Na / C Na +C NaCl ), y is E 样本 -E 干膜 .

[0345] Table 13

[0346] The standard curve of the second first electrode and the second second electrode is y=58.982x-55.446, as shown in FIG. 18, wherein x is lg(C K / (C K +CKCl )), y is E 样本 -E 干膜 .

[0347] Table 14

[0348] The standard curve of the third first electrode and the third second electrode is y = 30.713x - 7.2314, as shown in Figure 19, wherein x is lg(C Ca / (C Ca +C CaCl )), y is E 样本 -E 干膜 .

[0349] Table 15

[0350] By measuring the electrical signal of the sample, on the basis of the known dry film signal and the auxiliary salt concentration in the second electrode, the concentrations of sodium ions, potassium ions and calcium ions in the sample can be calculated by the standard curve.

[0351] The patent application connects the two electrodes of the detection potential through the sensing film, and the sensor is calibrated without loss and without calibration solution by measuring the potential signal in the dry state, so that the concentration of various ions in the sample or the direct concentration ratio can be effectively and accurately determined. When the sample is measured, the method is efficient, and the sensor and the test system are established economically and safely.

[0352] The above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto. It should be understood by those skilled in the art that any changes or replacements within the technical scope disclosed in the present application can be easily thought out by any person skilled in the art, and all fall within the protection scope and disclosure scope of the present application.

Claims

1. A dry film self-calibration sensing device comprising at least one first electrode and at least one second electrode; The detection portion of the at least one first electrode and the detection portion of the at least one second electrode are connected by being covered with a sensing film.

2. The dry film self-calibration sensing device according to claim 1, wherein: The sensing film includes at least one first region and at least one second region, the first region covers the detection portion of the first electrode, and the second region covers the detection portion of the second electrode.

3. The dry film self-calibration sensing device according to claim 2, wherein: The sensing film in the first region is a polymer film; The sensing membrane in the second region is a polymer membrane or an electrolyte membrane; The raw materials for preparing the first region sensing membrane include a first ion carrier; The raw materials for preparing the second region sensing membrane include a second ion carrier and / or a lipophilic electrolyte.

4. The dry film self-calibration sensing device according to claim 3, wherein: The first ionophore and the second ionophore are the same or different.

5. The dry film self-calibration sensing device according to claim 3, wherein: The first ionophore and the second ionophore are the same.

6. The dry film self-calibration sensing device according to claim 3, wherein: The first ionophore and the second ionophore are different.

7. The dry film self-calibration sensing device according to claim 2, wherein: The raw materials for preparing the sensing membrane of the first region and / or the second region include auxiliary agents; The adjuvant includes a neutral polymer.

8. The dry film self-calibration sensing device according to claim 7, wherein: The neutral polymer includes any one or a combination of at least two of carboxypolyvinyl chloride, polyvinyl chloride, polyurethane or silicone rubber.

9. The dry film self-calibration sensing device according to claim 7, wherein: When the sensing membrane in the first region and / or the second region is a polymer membrane, the auxiliary agent further comprises an ion additive.

10. The dry film self-calibration sensing device according to claim 9, wherein: The ionic additive includes any one of tetrakis(4-fluorophenyl)borate, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tetrakis(4-chlorophenyl)borate or tridodecylmethylammonium chloride, or a combination of at least two thereof.

11. The dry film self-calibration sensing device according to claim 10, wherein: The ionic additive includes any one or a combination of at least two of sodium tetrakis(4-fluorophenyl)borate, sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, potassium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, potassium tetrakis(4-chlorophenyl)borate or tridodecylmethylammonium chloride.

12. The dry film self-calibration sensing device according to any one of claims 2 to 11, wherein: A conductive medium is provided between the first region and the first electrode detection portion and / or between the second region and the second electrode detection portion.

13. The dry film self-calibration sensing device according to any one of claims 2 to 11, wherein: A conductive medium is provided between the detection portion of the first electrode and the detection portion of the second electrode, and the sensing film covers the conductive medium.

14. A method for detecting analyte concentration using the dry film self-calibration sensor device according to any one of claims 1 to 13, comprising the following steps: The potential values ​​of the sample measurement state and the dry film state are measured respectively and recorded as E 样本 With E 干膜 , according to the corresponding relationship, obtaining the concentration ratio of the object measured by the first electrode and the second electrode; E 样本 -E 干膜 =S×lg(C1 / C2)+A; in, C1 corresponds to the concentration of the object measured by the first electrode, C2 corresponds to the concentration of the object measured by the second electrode, S is the Nernst slope of the dry film self-calibration sensor device, and A is the inherent constant of the dry film self-calibration sensor device.

15. The method according to claim 14, wherein The analyte concentration includes ion concentration.

16. The method according to claim 15, wherein When the sensing membranes of the first and second regions are polymer membranes and the first and second electrodes have the same target, a known amount of auxiliary salt is introduced into the detection portion of the second electrode. At this time, the concentration of the target at the second electrode is expressed as C1+C x , the concentration ratio of the first electrode to the second electrode is C1 / (C1+C x ), the corresponding relationship is: E 样本 -E 干膜 =S×lg(C1 / (C1+C x ))+A; Among them, C x is the concentration of the ion to be measured corresponding to the auxiliary salt; The ion to be measured corresponding to the auxiliary salt is the same as the ion of the measurement object, and the auxiliary salt includes an inorganic salt containing the ion to be measured.

17. The method according to claim 15, wherein: When the sensing membranes of the first and second regions are polymer membranes and the first and second electrodes are measuring the same object, a substance containing co-extracted anions is introduced into the detection portion of the second electrode to obtain a concentration ratio C1 / C2 of the object measured by the first and second electrodes, and the corresponding relationship is: E 样本 -E 干膜 =S×lg(C1 / C2)+A; Wherein, C1 corresponds to the concentration of the object to be measured at the first electrode, and C2 corresponds to the concentration value of the potential signal generated by the co-extracted anions at the second electrode.

18. The method according to claim 14, wherein When the sensing membrane in the first region is a polymer membrane and the sensing membrane in the second region is an electrolyte membrane, the concentration ratio C1 / C2 of the measured object at the first electrode and the second electrode is obtained, and the corresponding relationship is: E 样本 -E 干膜 =S×lg(C1 / C2)+A; Wherein, C1 corresponds to the concentration of the object measured at the first electrode, C2 corresponds to the concentration of ions at the second electrode, S is the Nernst slope of the dry film self-calibration sensor device, and A is the inherent constant of the dry film self-calibration sensor device.

19. The method according to claim 14, wherein When the sensing membranes of the first and second regions are polymer membranes and the first and second electrodes are used to measure different objects, the concentration ratio C1 / C2 of the objects measured by the first and second electrodes is obtained, and the corresponding relationship is: 样本 -E 干膜 =S×lg(C1 / C2)+A; Wherein, C1 corresponds to the concentration of the object measured by the first electrode, C2 corresponds to the concentration of the object measured by the second electrode, S is the Nernst slope of the dry film self-calibration sensor device, and A is the inherent constant of the dry film self-calibration sensor device.

20. The method according to claim 14, wherein The analyte concentration is a metabolite concentration, including urea nitrogen concentration or creatinine concentration.

21. The method according to claim 20, wherein When the sensing membranes of the first and second regions are polymer membranes and the measurement targets of the first and second electrodes are the same, a reaction reagent is introduced into the detection portion of the first electrode. At this time, the concentration of the measurement target of the first electrode is expressed as C0+C M , the concentration ratio of the first electrode and the second electrode to measure the object (C0+C M ) / C2, the corresponding relationship is: E 样本 -E 干膜 =S×lg((C0+C M ) / C2)+A; Among them, C0+C M The concentration C1 corresponds to the concentration of the object measured by the first electrode, C2 corresponds to the concentration of the object measured by the second electrode, C0 is the concentration of the ion detected by the first electrode in the sample, C M is the concentration of metabolites in the sample, where C0=C2.

22. The method according to claim 21, wherein The polymer membrane is an ammonium ion sensing membrane or a carbonate ion sensing membrane; The first ion carrier of the first region sensing membrane includes an ammonium ion carrier or a carbonate ion carrier; the second ion carrier of the second region sensing membrane includes an ammonium ion carrier or a carbonate ion carrier; The reaction reagent is at least one of urease, carbonic anhydrase, creatinine hydrolase or creatine hydrolase; The metabolite is urea nitrogen or creatinine.

23. A method for detecting analyte concentration using the dry film self-calibration sensor device according to any one of claims 1 to 13, comprising the following steps: The potential values ​​of the sample measurement state and the dry film state are measured respectively and recorded as E 样本 With E 干膜 , according to the corresponding relationship, the concentration product of the object measured by the first electrode and the second electrode is obtained; AND 样本 -AND 干膜 =S×lg(C1×C2)+A; in, C1 corresponds to the concentration of the object measured by the first electrode, C2 corresponds to the concentration of the object measured by the second electrode, S is the Nernst slope of the dry film self-calibration sensor device, and A is the inherent constant of the dry film self-calibration sensor device.

24. The method according to claim 23, wherein When the sensing membranes of the first and second regions are polymer membranes and the objects to be measured by the first and second electrodes are different, a reaction reagent is introduced into the detection parts of the first and second electrodes. At this time, the concentration of the object to be measured by the first electrode is expressed as C0+C M The concentration of the object measured by the second electrode is expressed as C3+C M , the concentration product of the first electrode and the second electrode is obtained (C0+C M )×(C3+C M ), the corresponding relationship is: E 样本 -E 干膜 =S×lg((C0+C M )×(C3+C M ))+A; Among them, C0+C M The concentration of the object measured by the first electrode is C1, C3+C M The concentration C2 corresponds to the concentration of the object measured by the second electrode, C0 is the concentration of the ion detected by the first electrode in the sample, and C M is the concentration of the metabolite in the sample, and C3 is the concentration of the ion detected by the second electrode in the sample.

25. The method according to claim 24, wherein The polymer membrane is an ammonium ion sensing membrane or a carbonate ion sensing membrane; The first ion carrier of the first region sensing membrane includes an ammonium ion carrier or a carbonate ion carrier; the second ion carrier of the second region sensing membrane includes an ammonium ion carrier or a carbonate ion carrier; The reaction reagent is at least one of urease, carbonic anhydrase, creatinine hydrolase or creatine hydrolase; The metabolite is urea nitrogen or creatinine.

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