CN109142490A - All-solid sodium ion selective sensor and its preparation and application - Google Patents
All-solid sodium ion selective sensor and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of all-solid sodium ion selective sensor and its preparations and application.The all-solid sodium ion selective sensor includes sodium ion selection working electrode, and the working electrode includes conductive layer (4), reaction electrode (5), solid-state electrolyte layer (6) and sodium ion sensitive membrane (7).Present invention greatly simplifies the fabrication processing of sodium ion selective sensor, response is accurate rapid, and small volume and less weight is convenient for carrying, and is suitble to produce in enormous quantities.
Description
Technical field
The present invention relates to a kind of all-solid sodium ion selective sensor and its preparations and application.
Background technique
The measurement of electrolyte sodium ion is the routine and emergency treatment detection project of clinical diagnosis and treatment and rescue, because sodium ion is thin
Most cation in extracellular fluid (such as blood), to keep extracellular fluid capacity, adjust acid-base balance, maintain normal osmotic pressure and
Cell physiological function is significant, and participates in maintaining the normal irritability of neuro-muscular.Usual sodium balance disorder is often accompanied by water
The eubolism and balance of Balance disorders, water and sodium are the key factors for maintaining human internal environment stable.Therefore, serum sodium determination
One of the important content studied with celiac seawater immersion wound in important clinical meaning and military medicine.The normal value of blood sodium: 136
~146mmol/L.Its common detection methods is flame spectrometry and ion selective electrode method, but the two is required to expensive instrument
Device, and complicated for operation, signal low-response cannot conveniently and efficiently obtain analysis result.And it can be suitably used for field environment just
It is considerably less to take formula first aid biochemical instruments, and and full-automatic biochemical it is expensive with matched electrode, therefore the detection of blood sodium at present
Means are unable to satisfy the trend of field environment and domestic medicine.
Detecting for clinic Na ion concentration mainly uses the blomelicalbloodgasandelectrolrteanalyzers based on electrochemical method at present, and sodium ion
Selective sensor is the core of blomelicalbloodgasandelectrolrteanalyzers measurement sodium ion, and that there are preparation process is numerous for traditional sodium selective electrode
Trivial, with high costs, volume is larger, not readily portable disadvantage.
Patent 02137034.6 discloses a kind of sodium selective electrode and preparation method thereof for electrochemical sensor,
Its sodium selective electrode is that filling is equipped with sodium ion-conductive ceramics in conductive port containing conductive epoxy resin is received in insulation sleeve
Piece can measure sodium ion in liquor concentration with reference electrode pairing.But this selection electrode fabrication process is complicated, fabrication cycle compared with
It is long, be not suitable for Mass production.Patent 101852761A discloses a kind of all-solid sodium ion selective electrode and preparation method thereof,
It uses silk screening techniques and vacuum coating technology, makes in the planar substrates of high-molecular organic material, by sodium ion sensitive membrane
On using conducting polymer as solid-state electrolyte layer, and it is dense quickly to detect sodium ion with the pairing of outer reference electrode
Degree.But the working electrode of 101852761A is by the suspension of conductive polymer polymer using silk screening techniques in reaction carbon
To form solid-state electrolyte layer on electrode, this technique can have the following problems in implementation process: (1) conductive polymer polymer
For aqueous suspension, the very low unsuitable silk-screen printing of viscosity, it is hydrophobic surface that (2), which react carbon electrodes, with macromolecule
The aqueous slurry compatibility of conducting polymer is poor, and the web plate of (3) silk-screen printing is hydrophily when scraper plate lifts, web plate and slurry
Between be easy to pull out bubble, cause film forming uneven, a certain amount of adhesive be usually added into slurry in order to solve the above problem
And parent of the special inorganic agent Qula logical -100 to guarantee uniformity that slurry forms a film in printing process and with carbon electrode is reacted
And property, the cost of this virtually increased production, and even by above-mentioned improvement, there are still machines for prepared solid electrolyte layer
Tool performance is poor, and cracking, aliquation, breakage are easy in drying, measurement.
Summary of the invention
Complicated for the electrode structure of sodium ion selective sensor in traditional Na ion concentration detection, detection process is numerous
The disadvantages of trivial, with high costs, volume is larger, not portable, it is an object of that present invention to provide a kind of for portable biochemical instrument
Solid-state sodium ion selective sensor.
Technical solution of the present invention is summarized as follows:
The embodiment of the present invention provides a kind of sodium ion selection working electrode, and the working electrode includes conductive layer 4, reaction electricity
Pole 5, solid-state electrolyte layer 6 and sodium ion sensitive membrane 7.Specifically, the conductive layer 4 is silver conductive layer, the reaction electrode 5
For silver chlorate reaction electrode, the solid-state electrolyte layer 6 is sodium chloride/gelatin solid-state electrolyte layer；The thickness of the conductive layer 4
Be 30 microns, the solid-state electrolyte layer 6 with a thickness of 30 microns, the sodium ion sensitive membrane 7 with a thickness of 20 microns；It is described
The equal length of conductive layer 4 and the sodium ion sensitive membrane 7.
The embodiment of the present invention also provides the method for preparing above-mentioned sodium ion selection working electrode, which is characterized in that the side
Method includes the following steps:
(1) 30 microns of thick silver conductive layers of evaporation plating on PET polyester substrate, are divided into the mask plate of 8mm to upper using
It states conductive layer and is masked processing, the electrolytic cell that the electrically-conductive backing plate after mask process is immersed the KCl that concentration is 0.1mol/L is molten
In liquid, carries out anodic oxidation 1 hour, obtain silver chlorate reaction electrode, completely dried afterwards with distilled water flushing；
(2) the hac buffer 20ml for taking PH=5.5 is added 0.29 gram NaCl and 2.25 gram of gelatin and is configured to contain
The electrolyte solution is coated on silver chlorate reaction electrode with selectively applied instrument, is protected from light nature by the electrolyte solution of NaCl
Solid-state electrolyte layer is formed after drying, coating layer thickness is about 30m；
(3) 10mg benzyloxymethyl -11- crown- 3,3.5mg tetraphenylboron are added in 9 milliliters of N, N dimethyl formamide
Potassium, 1g dioctyl sebacate (DOS) and 0.5g polyvinyl chloride (PVC), concussion is dissolved into sodium ion sensitivity film liquid, with selective painting
The film liquid is coated in solid-state electrolyte layer by cloth instrument, forms sodium ion sensitive membrane after being protected from light natural drying, coating layer thickness is about
20m；
(4) the PET polyester sheet handled well by (1)-(3) step is handled through demoulding, is masked the part conduct of plate covering
The conductive layer of sodium selective electrode plays and is connected to conductive effect with external circuit, which is pressed along the direction of mask
The interval of 16mm carries out cutting strip, which should be including the coating and 8mm conductive coating of the sodium ion sensitive membrane of 8mm.
The embodiment of the present invention provides a kind of all-solid sodium ion selective sensor again, including above-mentioned sodium ion selects work
Electrode.Specifically, the all-solid sodium ion selective sensor includes that two identical above-mentioned sodium ions select work
Make electrode, described two identical sodium ion selection working electrodes are contactless placed side by side on inertia PVC substrate.
The embodiment of the present invention also provides the method for preparing above-mentioned all-solid sodium ion selective sensor, the method packet
It includes: two identical above-mentioned sodium ion selection working electrodes are contactless placed side by side on inertia PVC substrate.
The invention further relates to application of the above-mentioned sodium ion selection working electrode in the detection of electrolyte sodium ion.
The invention further relates to application of the above-mentioned all-solid sodium ion selective sensor in the detection of electrolyte sodium ion.
The embodiment of the present invention at least realizes following technical effect:
The embodiment of the present invention, greatly simplifies the fabrication processing of sodium ion selective sensor, and response is accurate fast
Speed, small volume and less weight are convenient for carrying, and are suitble to produce in enormous quantities.
For the present invention compared with patent 101852761A, main distinctive points are that reaction electrode is that silver coating passes through anode
Oxidation forms silver chloride layer, and it is hydrophily that the reaction electrode formed in this way, which has even film layer and surface, then with it is water-soluble with gelatin
When the solid-state electrolyte layer of liquid configuration combines, it can fundamentally solve aliquation of the reaction electrode in conjunction with solid-state electrolyte layer, open
The problems such as splitting, and the related solid-state electrolyte layer of the invention patent be made into only with cheap sodium chloride and gelatin it is water-soluble
Liquid, production cost are significantly lower than 101852761A.
Other features and advantages of the present invention will be illustrated in the following description, also, partly becomes from specification
It obtains it is clear that understand through the implementation of the invention.The objectives and other advantages of the invention can be by written explanation
Specifically noted structure is achieved and obtained in book, claims and attached drawing.
Detailed description of the invention
Fig. 1 is the top view of all-solid sodium ion selective sensor of the invention；
Fig. 2 is that the substrate of all-solid sodium ion selective sensor of the invention and sodium ion select working electrode assembling
Figure；
Fig. 3 is that the sodium ion of all-solid sodium ion selective sensor of the invention selects working electrode schematic diagram；
Fig. 4 is all-solid sodium ion selective sensor cover layer schematic diagram of the invention；
Fig. 5 is all-solid sodium ion selective sensor cover layer A-A diagrammatic cross-section of the invention；
Fig. 6 is that the sodium ion selective electrode prepared using embodiment 1 measures 16-220mmol/L calibration solution Sodium in Serum
The potential response calibration curve of ion concentration；
Fig. 7 is that the sodium ion selective electrode prepared using embodiment 2 measures 16-220mmol/L calibration solution Sodium in Serum
The potential response calibration curve of ion concentration；
Fig. 8 measures 16-220mmol/L calibration solution Sodium in Serum using sodium ion selective electrode prepared by the present embodiment 3
The potential response calibration curve of ion concentration；
Fig. 9 is that the all-solid sodium ion selective sensor of embodiment 1 saves 60 days under room temperature normality, is detected weekly
Response gradient, its response gradient drawn out change with time relational graph；
Figure 10 is to take 7 parts to include high, middle low value serum sample in the 80-160mmol/L range of linearity respectively, using the present invention
The measurement of solid-state sodium ion selective sensor and VITROS method be compared, correlation analysis figure is unfolded.
Wherein, 1 is substrate, and 2 be sodium ion selective working electrode, and 3 be cover layer, and 4 be conductive layer, and 5 be reaction electrode,
6 be solid-state electrolyte layer, and 7 be sodium ion sensitive membrane, and 8 be circular opening, and 9 be gas vent, and 10 be rectangular opening, and 11 be micro- grid
Salt bridge.
Specific embodiment
It is described in more detail below the exemplary embodiment of the disclosure.Although this part shows the exemplary reality of the disclosure
Apply example, it being understood, however, that may be realized in various forms the disclosure and should not be limited by the embodiments set forth herein.Phase
Instead, these embodiments are provided to facilitate a more thoroughly understanding of the present invention, and can completely pass the scope of the present disclosure
Up to those skilled in the art.
Present invention summary
The present invention provides a kind of solid-state sodium ion selective sensor for portable biochemical instrument, the sodium ion selective
Sensor includes the completely the same sodium ion selective working electrode 2 of substrate 1, two structures placed side by side, cover layer 3 and micro-
Grid salt bridge 11；The sodium ion selective working electrode 2 includes conductive layer 4, reaction electrode 5, solid-state electrolyte layer 6 and sodium
Ion sensitive membrane 7.
Cover layer 3 sets that there are two diameters as the circular opening 8 of 1-2mm, the rectangular opening 10 of two 2-3mm and 0.2mm's
Gas vent 9.The position of the corresponding sodium ion sensitive membrane 7 of circular opening 8, the conductive layer position of the corresponding working electrode of rectangular opening 10,
Gas vent 9 is located at the middle position of micro- grid salt bridge 11.Cover layer is covered on sodium ion selective working electrode, and two
The sodium ion sensitivity film surface of a working electrode respectively forms groove 8, and that solution and reference to be measured is added is molten when being respectively used to detection
Liquid is equipped with the micro- grid salt bridge 11 for being connected to solution and reference solution to be measured between two grooves.
The preparation method of the above-mentioned solid-state sodium ion selective sensor for portable biochemical instrument is prepared, including as follows
Step:
(1) on one whole high-molecular organic material substrate, it is evaporated silver-plated production conductive electrode, then uses exposure mask
Technology carries out equidistant mask process to the silver coating, and the substrate after mask process carries out anode in the solution of chloride ion-containing
Oxidation, the chloro ion-containing solution include KCL, HCL solution, and the concentration of the solution is 0.01%-10%, exposed to cover
Silver coating outside film version generates silver chloride layer by anodic oxidation, the reaction electrode as sodium ion selective electrode；
(2) based on mass percentage, the sodium chloride of sodium ion is dissolved in the gelatin solution of 3%-15%, is configured to be electrolysed
The solution spraying is protected from light drying on silver chlorate reaction electrode and forms solid-state electrolyte layer by matter solution.
(3) based on mass percentage, by sodium ion neutral carrier 0.5-5.0%, lipophilicity macromolecular 0.01-1.5%,
Plasticizer 60~80%, polyvinyl chloride 25.0-40% are dissolved in N, are configured to viscous fluid in N dimethyl formamide or cyclohexanone
Sodium ion sensitivity film liquid of the body as sodium ion selective electrode；The sodium ion sensitivity film liquid is coated in solid-state electrolyte layer
It is protected from light drying, forms sodium ion sensitive membrane；
(4) the micro- grid salt bridge 11 for being connected to solution and reference solution to be measured is equipped between two grooves 8；
(5) the solid state sensor preparation method that portable biochemical instrument is used for described in (1)-(3) in claim 2 is pressed,
It is characterized in that preparation process is silver-plated to entire volume high molecular material substrate progress ion evaporation, 3-10mm is carried out in silver-plated layer surface
Mask process at equal intervals, exposure mask width is all 3-10mm, is not made by Mask portion by (1)-(3) step in claim 2
Sodium ion selective working electrode, and the silver coating after mask plate is removed, as the conductive layer of sodium selective electrode, and by rule
Scale cun is cut into sodium ion selective sensor.
The sodium ion neutral carrier is selected from the load based on crown ether-like, cyclodextrin, schiff bases, calixarenes and its derivative
Body, preferably N, N '-dibenzyl-N, N '-two oxygroup diacetayl amide of diphenyl -1,2- benzene, N, N, N ',-four cyclohexyl -1,2- benzene of N '
One or more of two oxygroup diacetayl amides, benzyloxymethyl -11- crown- 3, methyl coban, coban.
The plasticizer is different selected from hexanedioic acid two (2- ethyl hexyl) ester, diisobutyl phthalate, azelaic acid two
The one or more of last of the ten Heavenly stems ester, dibutyl sebacate.
The lipophilic macromolecular is selected from tetraphenylboron sodium, four (4- chlorphenyl) potassium borates, four [3,5- bis- (trifluoromethy)
One or more of phenyl] potassium borate.
The salt bridge is using microchannel grid to be connected to solution and reference solution to be measured.
It uses full page vacuum plating silver technology to plate a layer thickness on PET thin slice as the silver layer of 10-80m, as conductive layer, leads to
It crosses mask technique and the conductive layer is subjected to mask process by the interval of 3-10mm, the product of full page, which is then immersed concentration, is
0.01-2mol/L's carries out anodic oxidation containing solutions of chlorine, is not reacted by the silver layer that mask plate covers with the chloride ion in solution
Silver chlorate, the layer is as reaction electrode, and spraying covering solid-state electrolyte layer and sodium ion sensitive membrane on this reaction electrode, keeps away
After light is dry, demoulding processing is carried out, and full page PET thin slice is cut into having a size of 5*6mm-5*20mm small pieces, the length of the small pieces
Degree depends on the interval of mask plate, is usually cut by 2 times of mask space, to guarantee that the small on piece contains sodium ion simultaneously
Sensitive membrane and plating silver conductive layer select working electrode to constitute a complete sodium ion sensitivity.Take the above-mentioned small pieces of two panels side by side
It is placed on substrate, above plus cover layer encapsulation constitutes a piece of sodium ion sensor.The sodium ion selective working electrode packet
Include conductive layer, reaction electrode, the sensitive membrane that respective sodium ion is all covered on each reaction electrode；
Two circular holes in the cover layer are respectively overlay in two sodium selective electrodes on substrate, and are sealed in
In sodium selective electrode, the self-assembling formation groove at circular hole, the groove is the sample to be tested and ginseng of sodium ion sensor
Than the adding mouth of liquid, the microchannel grid on the cover board forms capillary channel, is used as being connected to solution and reference liquid to be measured
Salt bridge.
The substrate is high molecular material, such as polyvinyl chloride, polyethylene and polyester；The conductive is preferably
Silver-plated thin layer is evaporated, the reaction electrode is the silver chloride electrode of anodic oxidation.
The sodium ion sensitivity film liquid of configuration is coated in the reaction electricity of sodium ion selective working electrode in the method sprayed
In the solid-state electrolyte layer of pole, it is protected from light drying, forms sodium ion selective working electrode film.
Setting is connected to the salt bridge of solution and reference liquid to be measured between two grooves of cover board, to guarantee the conducting of circuit,
Measurement circuit is formed, solution and reference solution to be measured in two grooves is connected only in salt bridge, but is not easy to spread.The salt bridge
It forms by the microchannel grid in cover layer and between cover board a thin layer capillary channel and constitutes.
When measurement, by reference drop in the groove of the sodium ion selective working electrode of side, by whole blood, serum or urine
The samples to be tested such as liquid drip in the groove of other side sodium ion selective working electrode, when the liquid in two grooves is led by salt bridge
After logical, it is connect with the detection circuit of periphery, potential value can be obtained.
Test solution amount needed for detection is seldom, it is only necessary to which 2-20l, detection time is shorter, can respond stabilization within 30-40 seconds.
The neutral carrier of sodium ion is generally caged, ring-type or chain organic compound, molecule in sodium ion sensitive membrane
In have multiple polarity dentates containing oxygen atom, due to oxygen atom there are two lone pair electrons provide dipole moment-ions binding power, make
The complex compound at 1:1 can be complexed in it with the sodium ion in solution to be measured, to change the electrode potential of sodium ion sensitive membrane.It is practical
In measurement, the sodium ion sensitive membrane of side sodium ion selective working electrode is certain to the electrode potential of reference solution in film
, as the sodium ion sensitive membrane of other side sodium ion selective working electrode surveys the variation of the electrode potential of test serum
The potential difference obtained between the two can extrapolate the Na ion concentration in solution to be measured according to Nernst equation.
Wherein, R is mol gas constant, and T is senor operating temperature, and Z is the valence state to measured ion, and F is that faraday is normal
Number, a1 are test serum intermediate ion concentration, and a2 is reference solution intermediate ion concentration, and the electrode electromotive force of reference electrode is generally fixed
Value, reference solution intermediate ion concentration is also known, then by measuring cell emf, so that it may calculate solution to be measured
Ion concentration.
In order to illustrate technical solutions according to the invention, the following is a description of specific embodiments.
Case study on implementation 1
(1) 30 microns of thick silver conductive layers of evaporation plating on the PET polyester substrate of 150*200mm, are divided into 8mm's using
Mask plate is masked processing to above-mentioned conductive layer, and the electrically-conductive backing plate after mask process is immersed the KCl that concentration is 0.1mol/L
Electrolytic cell solution in, carry out anodic oxidation 1 hour, obtain silver chlorate reaction electrode, completely dried afterwards with distilled water flushing.
(2) 0.29 gram NaCl and 2.25 gram of gelatin is added (using me in the hac buffer 20ml for taking PH=5.5
The lot number that fourth chemical reagent provides is G108397) it is configured to the electrolyte solution containing NaCl, with selectively applied instrument, by the electricity
Electrolyte solution is coated on silver chlorate reaction electrode, forms solid-state electrolyte layer after being protected from light natural drying, coating layer thickness is about
30m。
(3) 10mg benzyloxymethyl -11- crown- 3,3.5mg tetraphenylboron are added in 9 milliliters of N, N dimethyl formamide
Potassium, 1g dioctyl sebacate (DOS) and 0.5g polyvinyl chloride (PVC), concussion is dissolved into sodium ion sensitivity film liquid, with selective painting
The film liquid is coated in solid-state electrolyte layer by cloth instrument, forms sodium ion sensitive membrane after being protected from light natural drying, coating layer thickness is about
20m。
(4) the PET polyester sheet handled well by (1)-(3) step is handled through demoulding, is masked the part conduct of plate covering
The conductive layer of sodium selective electrode plays and is connected to conductive effect with external circuit, which is pressed along the direction of mask
The interval of 16mm carries out cutting strip, which should include the coating and 8mm conductive coating of the sodium ion sensitive membrane of 8mm,
5*16mm small pieces are cut by above-mentioned strip is horizontal again, take the above-mentioned small pieces of two panels placed side by side on the inertia PVC substrate of 25*25mm,
The encapsulation of upper plus cover layer constitutes a piece of all-solid sodium ion selective sensor.
(5) the all-solid sodium ion selective sensor prepared is accessed into (the ion voltage detection of ion voltage detector
Instrument is the instrument for detecting the potential difference between two electrodes), the standard solution or serum for being added dropwise 10 microlitres with pipettor are in complete solid
In the circular groove 8 of state sodium ion selective sensor (shown in Fig. 4), as working electrode；Drop in the circular groove of the other side
The reference solution for adding 10 microlitres, as reference electrode.The solution that reference liquid is made of electrolyte and polypyrrole alkanone, effect
It is that a stable fixation reference potential can be provided.The sensor is incubated for about 2 minutes in 37 DEG C, starting ion voltage inspection
Instrument record is surveyed, the potential difference between measured sodium ion selective working electrode and reference electrode is recorded, is denoted as E (mv), according to
Nernst equation, the potential value and the Na ion concentration in fluid to be measured are linearly related, thus obtained electromotive force response,
The Na ion concentration in solution to be measured can be extrapolated.
(6) Fig. 6 is to measure 16-220mmol/L calibration solution serum using sodium ion selective electrode manufactured in the present embodiment
The potential response calibration curve of middle Na ion concentration, equation E=59.2lgC-151.8, as shown in straight line in figure, phase relation
Number R2It is 99.5, according to Nernst equationWhen corresponding ion is monovalent ion, according to Nernst equation
Calculating electrode slope theoretical value of the electrode at 37 DEG C is 59.5mv/dec, if electrode is close to the response slope of monovalent ion
When this numerical value, then claiming the electrode to have can this spy's response.Sodium ion selective electrode manufactured in the present embodiment is rung as seen from the figure
Gradient is answered to meet Nernst equation.The sodium selective electrode to Sodium in Serum ion concentration within the scope of 16-220mmol/L at
Good linear response, and the serum-concentration can cover reference value and medical science decision level clinically.
(7) it will save 60 days, examine under room temperature normality by all-solid sodium ion selective sensor manufactured in the present embodiment
Response gradient weekly is surveyed, its response gradient is drawn out and changes with time relationship, if Fig. 9 is shown, sodium prepared by the present invention
Ion selective electrode its response gradient in 60 days substantially remains in 59mv/-PNa, illustrates that the present invention has good work
Stability.
Case study on implementation 2
(1) 30 microns of thick silver conductive layers of evaporation plating on the PET polyester substrate of 150*200mm, are divided into 8mm's using
Mask plate is masked processing to above-mentioned conductive layer, and the electrically-conductive backing plate after mask process is immersed the HCl that concentration is 0.2mol/L
Electrolytic cell solution in, carry out anodic oxidation 0.5 hour, obtain silver chlorate reaction electrode, completely dried afterwards with distilled water flushing.
(2) the hac buffer 20ml for taking PH=5.5 is added 0.29 gram NaCl and 2.25 gram of gelatin and is configured to contain
The electrolyte solution is coated on silver chlorate reaction electrode with selectively applied instrument, is protected from light nature by the electrolyte solution of NaCl
Solid-state electrolyte layer is formed after drying, coating layer thickness is about 30 μm.
(3) 15mg benzyloxymethyl -11- crown- 3,7.5mg tetraphenylboron sodium, 1g decanedioic acid two are added in 9 milliliters of cyclohexanone
Butyl ester (DBS) and 0.5g polyvinyl chloride (PVC), concussion are dissolved into sodium ion sensitivity film liquid, with selectively applied instrument by the film liquid
Coated in sodium ion sensitive membrane is formed after in solid-state electrolyte layer, being protected from light natural drying, coating layer thickness is about 20 μm.
(4) the PET polyester sheet handled well by (1)-(3) step is handled through demoulding, is masked the part conduct of plate covering
The conductive layer of sodium selective electrode plays and is connected to conductive effect with external circuit, which is pressed along the direction of mask
The interval of 16mm carries out cutting strip, which should include the coating and 8mm conductive coating of the sodium ion sensitive membrane of 8mm,
5*16mm small pieces are cut by above-mentioned strip is horizontal again, take the above-mentioned small pieces of two panels placed side by side on the inertia PVC substrate of 25*25mm,
The encapsulation of upper plus cover layer constitutes a piece of all-solid sodium ion selective sensor.
(5) the all-solid sodium ion selective sensor prepared is accessed into EC550 electrochemical workstation, is dripped with pipettor
The standard solution or serum for adding 10 microlitres in the circular groove 8 of all-solid sodium ion selective sensor (shown in Fig. 4), as
Working electrode；10 microlitres of reference solution is added dropwise in the circular groove of the other side, as reference electrode, is incubated for about 2 in 37 DEG C
Minute, start electrochemical workstation open-circuit voltage measurement method, records measured sodium ion selective working electrode and reference electricity
Potential difference between pole is denoted as E (mv), linear according to the Nernst equation potential value and the Na ion concentration in fluid to be measured
Correlation, thus obtained electromotive force response, can extrapolate the Na ion concentration in solution to be measured.
(6) Fig. 7 is to measure 16-220mmol/L calibration solution serum using sodium ion selective electrode manufactured in the present embodiment
The potential response calibration curve of middle Na ion concentration, equation E=58.3lgC+14.1, as shown in straight line in figure, phase relation
Number R2 is 99.8, illustrates that the electrode has this spy's response of energy.Sodium ion selective electrode manufactured in the present embodiment is rung as seen from the figure
Gradient is answered to meet Nernst equation.The sodium selective electrode to Sodium in Serum ion concentration within the scope of 16-220mmol/L at
Good linear response.
Case study on implementation 3
(1) 30 microns of thick silver conductive layers of evaporation plating on the PET polyester substrate of 150*200mm, are divided into 8mm's using
Mask plate is masked processing to above-mentioned conductive layer, and the electrically-conductive backing plate after mask process is immersed the KCl that concentration is 0.2mol/L
Electrolytic cell solution in, carry out anodic oxidation 20min, obtain silver chlorate reaction electrode, completely dried afterwards with distilled water flushing.
(2) the hac buffer 20ml for taking PH=5.5 is added 0.29 gram NaCl and 2.25 gram of gelatin and is configured to contain
The electrolyte solution is coated on silver chlorate reaction electrode with selectively applied instrument, is protected from light nature by the electrolyte solution of NaCl
Solid-state electrolyte layer is formed after drying, coating layer thickness is about 30 μm.
(3) it is added 15mgN, N, N ' in 9 milliliters of cyclohexanone, two oxygroup diacetayl amide of-four cyclohexyl -1,2- benzene of N ',
7.5mg tetraphenylboron sodium, 1g dioctyl sebacate (DOS) and 0.5g polyvinyl chloride (PVC), concussion are dissolved into sodium ion sensitive membrane
The film liquid is coated in solid-state electrolyte layer with selectively applied instrument, forms sodium ion sensitive membrane after being protected from light natural drying by liquid,
Coating layer thickness is about 20 μm.
(4) the PET polyester sheet handled well by (1)-(3) step is handled through demoulding, is masked the part conduct of plate covering
The conductive layer of sodium selective electrode plays and is connected to conductive effect with external circuit, which is pressed along the direction of mask
The interval of 16mm carries out cutting strip, which should include the coating and 8mm conductive coating of the sodium ion sensitive membrane of 8mm,
5*16mm small pieces are cut by above-mentioned strip is horizontal again, take the above-mentioned small pieces of two panels placed side by side on the inertia PVC substrate of 25*25mm,
The encapsulation of upper plus cover layer constitutes a piece of all-solid sodium ion selective sensor.
(5) the all-solid sodium ion selective sensor prepared is accessed into EC550 electrochemical workstation, is dripped with pipettor
The standard solution or serum for adding 10 microlitres in the circular groove 8 of all-solid sodium ion selective sensor (shown in Fig. 4), as
Working electrode；10 microlitres of reference solution is added dropwise in the circular groove of the other side, as reference electrode, is incubated for about 2 in 37 DEG C
Minute, start electrochemical workstation open-circuit voltage measurement method, records measured sodium ion selective working electrode and reference electricity
Potential difference between pole is denoted as E (mv), linear according to the Nernst equation potential value and the Na ion concentration in fluid to be measured
Correlation, thus obtained electromotive force response, can extrapolate the Na ion concentration in solution to be measured.
(6) Fig. 8 is to measure 16-220mmol/L calibration solution serum using sodium ion selective electrode manufactured in the present embodiment
The potential response calibration curve of middle Na ion concentration, equation E=49.5lgC+34.7, as shown in straight line in figure, phase relation
Number R2 is 99.6, illustrates that the electrode has this spy's response of energy.Sodium ion selective electrode manufactured in the present embodiment is rung as seen from the figure
Gradient is answered to meet sub- Nernst equation, the sodium selective electrode is to Sodium in Serum ion concentration in 16~220mmol/L range
It is interior at good linear response.
The correlation analysis of the VITROS method of all-solid sodium ion selective sensor and OCD company of the invention
7 parts are taken to include high, middle low value serum sample in the 80-160mmol/L range of linearity respectively, using solid-state of the invention
Sodium ion selective sensor is compared with the measurement of VITROS method, and correlation analysis is unfolded, and relationship is shown in Figure 10.Illustrate electricity
There are preferable repeatability and accuracy in pole.It can be seen that two methods correlation analysis measured result has high correlation.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of sodium ion selects working electrode, which is characterized in that the working electrode includes conductive layer (4), reaction electrode
(5), solid-state electrolyte layer (6) and sodium ion sensitive membrane (7).
2. sodium ion described in claim 1 selects working electrode, which is characterized in that the conductive layer (4) is silver conductive layer, described
Reaction electrode (5) is silver chlorate reaction electrode, and the solid-state electrolyte layer (6) is sodium chloride/gelatin solid-state electrolyte layer.
3. sodium ion described in claim 1 select working electrode, which is characterized in that the conductive layer (4) with a thickness of 30 microns,
The solid-state electrolyte layer (6) with a thickness of 30 microns, the sodium ion sensitive membrane (7) with a thickness of 20 microns.
4. sodium ion described in claim 1 selects working electrode, which is characterized in that the conductive layer (4) and the sodium ion are quick
Feel the equal length of film (7).
5. the method for preparing any one of claim 1-4 sodium ion selection working electrode, which is characterized in that the method packet
Include following steps:
(1) 30 microns of thick silver conductive layers of evaporation plating on PET polyester substrate, are led using the mask plate for being divided into 8mm to above-mentioned
Electric layer is masked processing, the electrically-conductive backing plate after mask process is immersed in the electrolytic cell solution for the KCl that concentration is 0.1mol/L,
It carries out anodic oxidation 1 hour, obtains silver chlorate reaction electrode, completely dried afterwards with distilled water flushing；
(2) the hac buffer 20ml for taking PH=5.5 is added 0.29 gram NaCl and 2.25 gram of gelatin and is configured to containing NaCl's
The electrolyte solution is coated on silver chlorate reaction electrode, after being protected from light natural drying by electrolyte solution with selectively applied instrument
Solid-state electrolyte layer is formed, coating layer thickness is about 30m；
(3) 10mg benzyloxymethyl -11- crown- 3,3.5mg potassium tetraphenylborate, 1g are added in 9 milliliters of N, N dimethyl formamide
Dioctyl sebacate (DOS) and 0.5g polyvinyl chloride (PVC), concussion is dissolved into sodium ion sensitivity film liquid, with selectively applied instrument
The film liquid is coated in solid-state electrolyte layer, forms sodium ion sensitive membrane after being protected from light natural drying, coating layer thickness is about 20m；
(4) the PET polyester sheet handled well by (1)-(3) step is handled through demoulding, be masked the part of plate covering as sodium from
The conductive layer of son selection electrode, plays and is connected to conductive effect with external circuit, by the polyester sheet along the direction of mask by 16mm's
Interval carries out cutting strip, which should be including the coating and 8mm conductive coating of the sodium ion sensitive membrane of 8mm.
6. a kind of all-solid sodium ion selective sensor, which is characterized in that including any one of the claim 1-4 sodium ion
Select working electrode.
7. all-solid sodium ion selective sensor described in claim 6, which is characterized in that the all-solid sodium ion selective
Sensor includes that any one of two identical claim 1-4 sodium ion selects working electrode, described two complete
Identical sodium ion selection working electrode is contactless placed side by side on inertia PVC substrate.
8. the method for preparing any all-solid sodium ion selective sensor of claim 6 or 7, which is characterized in that described
Method includes: that any one of two identical claim 1-4 sodium ion selection working electrode is contactless side by side
It is placed on inertia PVC substrate.
9. application of any one of the claim 1-4 sodium ion selection working electrode in the detection of electrolyte sodium ion.
10. any one of claim 6 or 7 the all-solid sodium ion selective sensor answering in the detection of electrolyte sodium ion
With.
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| CN113588759A (en) * | 2021-07-12 | 2021-11-02 | 成都云芯医联科技有限公司 | Siphon type ion selective electrode electrolyte detection test paper |
| CN113671007A (en) * | 2021-09-13 | 2021-11-19 | 上海神开石油科技有限公司 | Suspension chloride ion online measurement device and measurement method |
| CN113702469A (en) * | 2020-05-20 | 2021-11-26 | 无锡锦帛诚医疗器械科技有限公司 | Quantitative detection method for carbon dioxide |
| CN113702466A (en) * | 2020-05-20 | 2021-11-26 | 无锡锦帛诚医疗器械科技有限公司 | Sodium ion quantitative detection dry tablet and preparation method thereof |
| CN113702467A (en) * | 2020-05-20 | 2021-11-26 | 无锡锦帛诚医疗器械科技有限公司 | Calcium ion quantitative detection dry tablet and preparation method thereof |
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