CN113588759B - Siphon type ion selective electrode electrolyte detection test paper - Google Patents
Siphon type ion selective electrode electrolyte detection test paper Download PDFInfo
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- CN113588759B CN113588759B CN202110786572.7A CN202110786572A CN113588759B CN 113588759 B CN113588759 B CN 113588759B CN 202110786572 A CN202110786572 A CN 202110786572A CN 113588759 B CN113588759 B CN 113588759B
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- KRIOVPPHQSLHCZ-UHFFFAOYSA-N propiophenone Chemical compound CCC(=O)C1=CC=CC=C1 KRIOVPPHQSLHCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Polymers [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/447—Systems using electrophoresis
- G01N27/44704—Details; Accessories
- G01N27/44747—Composition of gel or of carrier mixture
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/49—Systems involving the determination of the current at a single specific value, or small range of values, of applied voltage for producing selective measurement of one or more particular ionic species
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Electrochemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Investigating Or Analysing Biological Materials (AREA)
Abstract
The invention discloses siphon type ion selective electrode electrolyte test paper which comprises a plastic substrate layer, an electrode layer, an insulating layer, a bridging layer, a hydrophilic film layer, a sealing film layer and a cover plate layer which are sequentially arranged. The test paper of the invention has the advantages of no reference solution, direct trace fingertip blood one-step rapid and accurate detection of electrolyte, easy batch automatic production and low cost.
Description
Technical Field
The invention belongs to the technical field of electrochemical test paper, and particularly relates to siphon type ion selective electrode electrolyte test paper.
Background
Na in blood, urine, cerebrospinal fluid and dialysate + 、K + 、Ca ++ 、Cl - The electrolytes are common biochemical test items, the content of the electrolytes in a human body can be known through testing the substances, the electrolytes can be timely supplemented to maintain the osmotic pressure and the acid-base balance in the body, and the electrolytes are important bases for diagnosis, treatment evaluation and prognosis judgment of various diseases. Under the background that the population is aggravated, policies such as medical insurance cost control and grading diagnosis and treatment are promoted, intelligent digital medical treatment is rapidly laid out, and the mouths of slow patients such as hypertension, diabetes mellitus and the like which are easy to be accompanied by electrolyte disorder are gradually enlarged, the electrolyte detection is very necessary for adapting to modern mobile rapid detection scenes such as emergency treatment, field rescue, basic medical treatment, pharmacy monitoring, home management and the like.
At present, the electrolyte detection which is matched with a mobile quick detection scene is an electrolyte analyzer based on an electrochemical principle, the measurement of the concentration of target ions is realized through an ion selection electrode, and the electrolyte detection can be roughly classified into three types from low to high according to the mobile convenience degree. The first category is: the rod-shaped ion selective electrode matched with the wet electrolyte analyzer is required to be filled with an internal reference liquid and is matched with a reagent pack containing an external reference liquid, a cleaning liquid and a calibration liquid for use, the structure is complex, the maintenance cost of the electrode and a liquid path is high, the mass production is difficult, and the electrode is only suitable for being used for extracting arterial or venous blood detection by professional medical staff in relatively static occasions such as an operating room, an intensive care unit, an anesthesia department and the like. The second category is: a plate-type ion-selective electrode matched with a wet electrolyte analyzer. Although the ion selective electrode solidifies the liquid internal reference liquid, the ion selective electrode still needs to be matched with a reagent pack containing the external reference liquid, the problems of high manufacturing cost, troublesome use, severe storage conditions, inconvenient carrying and the like are not improved essentially, and the ion selective electrode can only be used for extracting arterial or venous blood by professional medical staff and is used in relatively static occasions such as operating rooms, intensive care units, anesthesia departments and the like. The third category is: a flat plate type ion selective electrode matched with a dry electrolyte analyzer. Compared with the second category, although an external reference liquid bag does not need to be packaged in a matched instrument, a reference solution with known ion concentration is provided along with a test card, a tester manually drops the solution into a designated area, and then drops a sample to be tested in steps to realize complete measurement, so that the detection process is complicated, and the risk of cross contamination is high. In addition, the structure design of the electrode is limited at present, only dripping sample injection is supported, and a non-professional person is difficult to extract an adaptive sample at any time in a flexible scene, and the reference solution and the ion selection electrode which can be effectively stored only in a low-temperature environment such as refrigeration or freezing are relied on, so that the modern mobile rapid detection adaptability of the electrode is further weakened, and the electrode is especially suitable for field rescue, pharmacy monitoring, home management and other scenes.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides the siphon type ion selective electrode electrolyte detection test paper which is matched with a handheld dry electrolyte analyzer, a reference solution is not added during the test, the electrolyte is directly and rapidly and accurately detected by a trace of fingertip blood in one step, the mass automatic production is easy, and the cost is low.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the utility model provides a siphon ion selective electrode electrolyte test paper, includes plastic substrate layer, electrode layer, insulating layer, bridging layer, hydrophilic rete, sealing rete and cover plate layer, the electrode layer adheres to on plastic substrate, the electrode layer includes monitoring electrode and ion selective electrode, and every group monitoring electrode or ion selective electrode are by working electrode and reference electrode constitution, working electrode and reference electrode are concentrated respectively and are arranged in sample cell district and reference cell district and separate each other, every working electrode and reference electrode are connected with a metal guide disc through the metal wire for with detecting instrument connection switch on.
The insulating layer covers the electrode layer, and leaks out of the effective areas of the working electrode and the reference electrode and the metal guide disc.
The bridging layer is covered on the insulating layer, and is provided with a first through groove and a second through groove, one end of the first through groove is open and is positioned in the sample pool area for siphoning and collecting the detection sample, the periphery of the second through groove is closed and is positioned in the reference pool area for containing the reference liquid; the bridging layer is provided with a hollow fiber for communicating the sample pool area and the reference pool area.
The reference solution of the invention contains poly (N-isopropyl acrylamide-co-methacrylic acid) or glycerol.
The hydrophilic membrane layer covers the bridging layer, three through holes are respectively formed in the hydrophilic membrane layer, namely a sample cell exhaust hole, a reference cell exhaust hole and a reference cell sample injection hole, the sample cell exhaust hole corresponds to the inner side of the first through groove and is used for forming a sample cell with the first through groove to collect samples, the reference cell exhaust hole and the reference cell sample injection hole correspond to two sides of the second through groove respectively, and the reference cell is formed with the second through groove to be used for containing reference liquid.
The sealing film layer is larger than the second through groove, and the corresponding second through groove is covered on the hydrophilic film layer and is used for sealing the reference cell exhaust hole and the reference cell sample injection hole.
The cover plate layer covers on the sealing film layer, the cover plate layer is provided with a third through groove corresponding to the first through groove, and a visual sample injection observation area is provided.
The ion selective electrode is formed by sequentially superposing metal, corresponding metal salt, a solid-state gelled internal reference electrolyte film and an ion selective electrode film.
The metal is selected from gold, silver, platinum, iridium or titanium, and is integrated on the plastic substrate by screen printing, electroplating, chemical plating or vacuum plating.
The corresponding metal salt is insoluble salt of the metal.
The solid state gelation internal reference electrolyte film consists of a gel polymer, a gel polymer cross-linking agent, a plasticizer, inorganic salt and a surfactant.
The ion selective electrode film consists of a film-forming polymer, a plasticizer, an ionophore, ionic salt and a solvent.
The beneficial effects of the invention are as follows:
the invention changes the reference aqueous solution with easy change of ion concentration into gel solution with stable ion concentration through the formula improvement and the innovative structural design of the reference solution, changes the card electrode into a light and thin test strip electrode, changes the reference solution of an independent external package into a test paper to be directly integrated inside, changes the complicated multi-step measurement into one-step measurement, changes the harsh test conditions of low-temperature storage or rewarming waiting and the like into normal temperature and normal pressure to be measured at any time, and changes the drip sample into fingertip whole blood to be directly sampled only by venous or arterial blood sampling, thereby realizing rapid and accurate electrolyte detection. Not only improving the convenience of user operation, but also reducing the detection cost, and realizing the real electrolyte movement quick detection. In addition, the sample injection monitoring electrode is integrated on the test paper, so that guarantee is further provided for the accuracy response of the ion selection electrode, the misjudgment rate is reduced, and the test paper detection function is enriched.
Drawings
FIG. 1 is a schematic diagram of the structure of a test strip of the present invention;
FIG. 2 is a schematic diagram of the electrode layer structure of the test paper of the present invention;
FIG. 3 is a schematic diagram of the insulating layer structure of the test paper of the present invention;
FIG. 4 is a schematic diagram of a bridge layer structure of the test strip of the present invention;
FIG. 5 is a schematic diagram of the hydrophilic membrane layer structure of the test paper according to the present invention;
FIG. 6 is a schematic diagram of the sealing film layer structure of the test paper of the present invention;
FIG. 7 is a schematic view of the structure of the test strip cover sheet of the present invention;
FIG. 8 shows the test strip of the present invention at various concentrations K + Potential response curve in buffer solution; wherein K in the reference solution + The concentration is 9.3mmol/L;
FIG. 9 shows the test strip of the present invention at different Na concentrations + Potential response curve in buffer solution; wherein the reference solution contains Na + The concentration is 195mmol/L;
in the figure, 1, a plastic substrate layer, 2-4, a working electrode, 5-7, a reference electrode, 8-13, a metal wire, 14-19, a metal guide disc, 20, an insulating layer, 21-26, an opening, 27, a bridging layer, 28, a first through groove, 29, a hollow fiber, 30, a second through groove, 31, a hydrophilic film layer, 32, a sample cell exhaust hole, 33, a reference cell exhaust hole, 34, a reference cell sample injection hole, 35, a sealing film layer, 36, a cover plate layer, 37 and a third through groove.
Detailed Description
The following description of the present invention will be made more complete and clear in view of the detailed description of the invention, which is to be taken in conjunction with the accompanying drawings that illustrate only some, but not all, of the embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
As shown in fig. 1, the present invention provides a siphon type ion selective electrode electrolyte test paper comprising a plastic substrate layer 1, an electrode layer, an insulating layer 20, a bridging layer 27, a hydrophilic film layer 31, a sealing film layer 35 and a cover sheet layer 36 arranged from below.
As shown in fig. 2, an electrode layer is integrated on the plastic substrate layer 1 by screen printing, electroplating, chemical plating or vacuum plating, and the electrode layer is composed of working electrodes (2-4), reference electrodes (5-7) and metal guide plates (14-19). The working electrodes (2-4) are distributed on the left side of the plastic substrate layer 1 to form a sample pool area, the reference electrodes (5-7) are distributed on the right side of the plastic substrate to form a reference pool area, the metal guide plates (14-19) are arranged on the top of the plastic substrate layer 1, and each working electrode (2-4) and each reference electrode (5-7) are correspondingly connected with one metal guide plate through metal wires (8-13).
The electrode layers are classified into two types according to the test function: the sample injection monitoring electrode is formed by a pair of same metals and is positioned at the bottom end of the sample pool, the filling degree of the sample filled in the sample pool and the ion selection electrode is covered to influence the conductivity of the monitoring electrode, and whether the sample injection amount is proper or not can be judged according to the impedance signal; the other type is an ion selective electrode formed by sequentially superposing metal, corresponding metal salt, a solid state gelation internal reference electrolyte film and an ion selective electrode film.
Specifically, in this embodiment, the working electrode 2 and the reference electrode 5, the working electrode 3 and the reference electrode 6 are paired to form an ion selection electrode, the working electrode 2 and the reference electrode 5 form a sodium ion selection electrode, the working electrode 3 and the reference electrode 6 form a potassium ion selection electrode, and the potassium ion selection electrode, the calcium ion selection electrode, the chloride ion selection electrode, the lithium ion selection electrode, the magnesium ion selection electrode and the phosphorus ion selection electrode can also be used as needed. The working electrode 4 and the reference electrode 7 are paired to form a monitoring electrode, and the metal wires (8-13) are respectively connected with the working electrode 2 and the metal guide disc 14, the working electrode 3 and the metal guide disc 15, the working electrode 4 and the metal guide disc 16, the reference electrode 5 and the metal guide disc 17, the reference electrode 6 and the metal guide disc 18, the reference electrode 7 and the metal guide disc 19, and are communicated with a detection instrument to form a complete electrolyte detection loop.
The monitoring electrode consists of a pair of inert conductive metals and is positioned at the top end of the sample pool, the filling degree of the sample filled in the sample pool and covering the ion selection electrode can influence the impedance change of the electrode, the impedance threshold value with insufficient sample injection amount is determined in advance and written into the instrument, and then whether the sample injection amount is proper or not can be intelligently judged according to the actually measured impedance signal and reminding and indication can be made. When the sample injection amount is insufficient, a user is prompted on a display screen of the matched handheld electrolyte analyzer that the sample amount is insufficient for retesting, so that the risk that the user is misled by an error result in the using process is reduced, the detection stability is ensured, and the experience of the user is improved.
Wherein the plastic substrate layer 1 is a test paper support body and is selected from one or more of polyethylene terephthalate, polyethylene, polypropylene, polyimide and nylon, and preferably polyethylene terephthalate.
The metal in the electrode is selected from gold, silver, platinum, iridium and titanium, and is integrated on the plastic substrate by screen printing, electroplating, chemical plating and vacuum plating methods, preferably a vacuum plating mode of uniform, low-impedance and high-purity (nearly 100%) silver film with the thickness of 200-1000nm can be obtained.
The corresponding metal salt in the electrode is an insoluble salt of the above metal, preferably silver chloride. The metal salt is uniformly adhered on the surface of the metal and is formed by potassium permanganate oxidation, potassium dichromate oxidation and ferric chloride oxidation, and ferric chloride solution with the concentration of 0.01-1mol/L is preferable, and the oxidation time is 0.5-10min.
The chemical components of the solid state gelled internal reference electrolyte film in the electrode include: gel polymer, gel polymer cross-linking agent, plasticizer, inorganic salt and surfactant.
The gel polymer provides a network structure for inorganic salt molecules to be uniformly embedded and dispersed in, so that water vapor molecules rapidly permeate into the solid gel film during testing, the migration rate of salt ions is increased, and rapid and accurate measurement can be realized. One or more selected from polyvinyl alcohol, polyethylene glycol, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, chitosan, sodium alginate, polyacrylate, and polyacrylamide-acrylic acid, preferably polyvinyl alcohol. The gel polymer accounts for 30% -90% of the total mass of the internal reference electrolyte film.
The gel polymer cross-linking agent is subjected to cross-linking with active groups on the molecular chain of the gel polymer through the principles of chemical bonding, coordination complexing, van der Waals action and the like, so that the mesh size of the locking inorganic salt becomes smaller, the probability that the inorganic salt micromolecule breaks loose from the inner reference electrolyte layer to the test solution is strongly reduced, and the stability of the inner reference is improved. Boric acid is preferred, and the boric acid is selected from one or more of boric acid, citric acid, glutaraldehyde, urea, tannic acid, barium chloride, ferric chloride and magnesium chloride.
Plasticizers are used to adjust the flexibility and hygroscopicity of the films. Selected from propylene glycol, glycerol, isopropanol, pentaerythritol, ethanolamine, urea, dibutyl ester, caprolactam, low molecular polyethylene glycols, preferably glycerol. The plasticizer accounts for 3-20% of the total mass of the internal reference electrolyte film.
The inorganic salt is the electrolyte active ingredient of the internal reference electrode, and a mixture of sodium chloride and potassium chloride is selected, and the total mass of the two is preferably 30% of the total mass of the internal reference electrolyte film.
The surfactant utilizes the amphiphilic property of the surfactant, and is helpful for reducing phase separation among components in the film forming process of the internal reference electrolyte solution, and improving the uniform stability of the film. One or more selected from polyoxyethylene lauryl ether, octyl phenyl polyoxyethylene ether and polysorbate nonionic surfactant.
The chemical components of the ion-selective electrode film in the electrode comprise: film-forming polymers, plasticizers, ionophores, ionic salts, and solvents.
The film-forming polymer is a supporting net component of the ion-selective electrode film, and other small molecular substances are uniformly dispersed or complexed in the film-forming polymer. Selected from polyvinyl chloride, polyvinylidene chloride, polyurethane, polyamide, polymethyl methacrylate and blends or copolymers thereof, preferably polyvinyl chloride.
On one hand, the plasticizer is matched with the film-forming polymer to improve the flexibility of the film, and on the other hand, the plasticizer which has a large polarity and strong dissolving capacity for the ionophore plays a role in dissolving the ionophore, thereby being helpful for reducing the internal resistance of the film. The material is selected from fatty acid esters such as dioctyl adipate and dioctyl sebacate, phthalic acid esters such as dioctyl phthalate and diisooctyl phthalate, phosphoric acid esters such as tricresyl phosphate and triphenyl phosphate, and one or more of nitrobenzene octyl ethers such as o-nitrobenzene octyl ether and p-nitrobenzene octyl ether, preferably dioctyl sebacate which can provide low temperature flexibility.
Ionophores are compounds that have a chelating complexing action on target ions, forming a selective response. The sodium ion carrier is selected from one or more of N, N ', N ' -triheptyl-N, N ', N ' -trimethyl-4, 4' -propyltri (3-oxabutyramide), N, N ' -dibenzyl-N, N ' -diphenyl-1, 2-benzene dioxydiacetamide, N, N, N ', N ' -tetracyclohexyl-1, 2-benzene dioxydiacetamide, 4-octadecanoic acid methyl-N, N, N ', N ' -tetracyclohexyl-1, 2-benzene dioxydiacetamide, bis (12-crown ether-4) methyl-2-dodecyl-2-malonic acid dimethyl ester and 4-tertiary butyl calixarene-tetraacetic acid tetraethyl ester; the potassium ion carrier is selected from one or more of 2-dodecyl-2-methyl-1, 3-propylene-diyl-N-5 '-nitro (benzo-15-crown-5) -4' -carbamic acid ester, 18-crown ether-6, 15-crown ether-5, 12-crown ether-4, dibenzo-18-crown ether-6 and valinomycin.
The ionic salt is a lipophilic salt that reduces interference of non-target ions with ionophore selectivity. Selected from potassium tetrakis (4-chlorophenyl) borate, sodium tetraphenylborate, potassium tetraphenylborate.
The solvent is selected according to its dissolving capacity and self-volatility for other components in the film, and organic solvents with different polarities and boiling points are often blended and matched. One or more selected from cyclohexanone, N-N dimethylformamide, tetrahydrofuran, propiophenone, N-methylpyrrolidone and chloroform.
As shown in fig. 3, the insulating layer 20 is an insulating plastic film with a back adhesive, the insulating layer 20 covers the electrode layer, the bottom edge is flush with the plastic substrate layer 1, openings (21-26) are arranged on the insulating layer 20 and correspond to the working electrodes (2-4) and the reference electrodes (5-7) respectively, and the effective areas of the metal guide plates (14-19) and the working electrodes (2-4) and the reference electrodes (5-7) are leaked out, so that other conductive parts are completely covered.
As shown in fig. 4, the bridge layer 27 is covered on the insulating layer 20, and the bridge layer 27 is provided with a first through groove 28 and a second through groove 30, wherein the bottom of the first through groove 28 is in an opening shape and is used as a sample cell component, the second through groove 30 is in a closed rectangular shape and is used as a reference cell component, the first through groove 28 corresponds to the working electrode (2-4) areas and leaks out of the openings (21-23), and the second through groove corresponds to the reference electrode (5-7) areas and leaks out of the openings (24-26). A hollow fiber 29 is arranged on the bridging layer 27 and is communicated with the first through groove 28 and the second through groove 30, and is used for communicating the working electrodes (2-4) and the corresponding reference electrodes (5-7).
The bridging layer 27 of the present invention communicates the working electrodes (2-4) and their corresponding reference electrodes (5-7), unlike the conventional connection of a reference electrode immersed in a high concentration salt solution to the working electrode via a complex capillary salt bridge, neither a fine capillary flow channel nor the introduction of a liquid salt solution is required, and the working electrodes (2-4) and the reference electrodes (5-7) are communicated only through one hollow fiber 29.
As shown in fig. 5, the hydrophilic membrane layer 31 is covered on the bridging layer 27, and three through holes, namely, a sample cell vent hole 32, a reference cell vent hole 33 and a reference cell sample injection hole 34, are respectively formed on the hydrophilic membrane layer 31, wherein the sample cell vent hole 32 is positioned at the top of the corresponding first through groove 28, the reference cell vent hole 33 is positioned at the top of the corresponding second through groove 30, the reference cell sample injection hole 34 is positioned at the bottom of the corresponding second through groove 30, the sample cell vent hole 32 is arranged at the top of the first through groove 28, and forms a siphoning effect with the bottom working electrode (2-4) areas, so that the sample liquid is facilitated to be distributed in the first through groove 28 areas, the direct micro fingertip whole blood siphoning sample injection is realized, and in addition, the sample tests of various forms such as venous whole blood, arterial whole blood, blood plasma, serum, dialysate and the like can be simultaneously supported. The method not only simplifies the measurement process, widens the application range, ensures the moving convenience, but also improves the anti-interference capability, and provides better guarantee for accurate measurement.
As shown in fig. 6, the sealing film layer 35 is rectangular, and is correspondingly covered above the second through groove 30 to seal the reference cell exhaust hole 33 and the reference cell sample injection hole 34, thereby providing a safety for the stable storage of the reference solution in the test paper.
The sealing film layer is one or more of aluminum, nylon, polypropylene, polyethylene terephthalate, polycarbonate and polyvinyl chloride, and is preferably a polyethylene terephthalate/nylon/aluminum/polyethylene composite aluminum foil with excellent air resistance, water resistance and light insulation.
As shown in fig. 7, a cover sheet 36 overlies the sealing film layer 35 for dual purposes of the outer package and label. A third through slot 37 corresponding to the first through slot 28 is provided on the cover sheet 36 to leak out the effective areas of the sample cell exhaust hole 32 and the working electrodes (2 to 4) while providing a visual sample injection observation area.
Example 2
The embodiment of the invention also provides a preparation method of the reference liquid.
The preparation method comprises the following steps:
1) 0.1100g of NaCl and 0.0066g of KCl are weighed, and then 5g of ultrapure water is added to be magnetically stirred for 10min at the normal temperature and at 300 rpm;
2) 0.9g of ultrapure water was weighed, then 0.1g of 5-bromo-5-nitro-1, 3-dioxane was added thereto, and magnetically stirred at 300rpm at room temperature for 30 minutes;
3) The pipette removes 10uL of the above solution 2) to the above solution 1), and then magnetically stirs it at 300rpm for 30min at normal temperature.
4) 0.1g of poly (N-isopropylacrylamide-co-methacrylic acid) copolymer was weighed, added to 5g of ultra-pure water under magnetic stirring at 1000rpm, and then heated at 120℃for 1 hour by means of condensation reflux.
5) Mixing the solution 3) with the solution 4), and magnetically stirring at 300rpm at normal temperature for 30min to obtain reference solution, and sealing and preserving.
The preparation method comprises the following steps:
1) Weighing 0.1100g of NaCl and 0.0066g of KCl, stirring and dissolving in 0.5g of ultrapure water at normal temperature, then adding 12g of glycerol solution, and magnetically stirring at 300rpm at normal temperature for 30min;
2) 0.9g of propylene glycol solution is weighed, then 0.1g of 5-bromo-5-nitro-1, 3-dioxane is added, and magnetic stirring is carried out for 30min at the normal temperature and at the speed of 300 rpm;
3) And transferring 10uL of the solution 2) by a liquid transferring gun, adding the solution into the solution 1), and magnetically stirring at 300rpm for 30min at normal temperature to obtain a reference solution, and sealing and storing.
In order to keep the concentration of electrolyte ions in the reference solution stable at normal temperature and normal pressure, the viscosity and the temperature sensitivity of the reference solution are regulated by using poly (N-isopropyl acrylamide-co-methacrylic acid) or glycerol in the reference solution, the method is suitable for the conditions of encapsulation in test paper, realizes the stable storage in the test paper, and can be used for adding a sample to be tested in one step during measurement, thereby simplifying the operation steps, increasing the mobile portability, reducing the types of consumables and saving the cost.
Example 3
The manufacturing method of the ion selective electrode electrolyte test paper comprises the following steps:
1) Sputtering a pure silver target material on a designated area of a polyethylene terephthalate substrate to form a silver conducting disc, a silver connecting wire and a silver electrode point, wherein the purity of silver is more than 99.9%;
2) Preparing 0.01mol/L ferric chloride solution, dripping the solution onto the surface of a silver spot, waiting for 20min to obtain a silver chloride film layer, washing the silver chloride film layer with ultrapure water, and then drying the silver chloride film layer in an oven at the drying temperature of 50 ℃ for 30min.
3) 5g of a 2% polyvinyl alcohol solution was prepared using a glycerol/ultrapure water mixed solvent at a mass ratio of 1:10, 0.025g of NaCl and 0.005g of KCl were added thereto and dissolved with stirring, and then 200uL of a boric acid saturated solution was added thereto with magnetic stirring at 65℃and 1000rpm to carry out a reaction. And finally, coating and covering the electrode points of the silver and the silver chloride by a proper amount of solution drops, and drying in a drying oven to obtain the solid gel internal reference electrolyte film, wherein the drying temperature is 40 ℃ and the time is 30min.
4) Preparing 2g of sodium and potassium ion selective membrane solution respectively, taking a proper amount of drip coating and covering the reference electrolyte film in the solid gel, and baking for 30min at 40 ℃ to obtain the sodium and potassium ion selective membrane. Wherein, the mixed solvent of cyclohexanone and tetrahydrofuran is used, potassium tetra (4-chlorophenyl) borate is used as an ion interfering agent, N, N, N ', N' -tetracyclohexyl-1, 2-benzene dioxydiacetamide is used as a carrier of sodium ions, valinomycin is used as a carrier of potassium ions, polyvinyl chloride is used as a film forming polymer, the mass ratio is 40 percent, and dioctyl sebacate is used as a plasticizer, and the mass ratio is 55 percent.
5) After drying the ion selective electrode film, sequentially attaching an insulating film, a bridging film and a hydrophilic film, then injecting the prepared reference solution into a holding tank, sealing the sample injection hole and the air hole by using an aluminum foil film, and finally attaching a cover plate. The insulating film is a PET sheet with back glue, the bridging film is adhered with a polyester hollow fiber with the diameter smaller than 0.2mm, the polyester hollow fiber penetrates through the sample cell and the reference cell, the joint surface of the hydrophilic film and the sample cell is treated by a hydrophilic agent, the aluminum foil film is a polyethylene terephthalate/nylon/aluminum/polyethylene composite film, and the cover plate is made of synthetic paper.
6) The prepared ion selective electrode electrolyte test paper is used for respectively testing different K + And Na (Na) + The concentration of the human body simulated liquid and the potential response curve are shown in fig. 8 and 9.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (3)
1. The siphon type ion selective electrode electrolyte detection test paper comprises a plastic substrate layer, an electrode layer, an insulating layer, a bridging layer, a hydrophilic film layer, a sealing film layer and a cover plate layer which are sequentially arranged, and is characterized in that the electrode layer is attached to the plastic substrate and comprises monitoring electrodes and ion selective electrodes, each group of monitoring electrodes or ion selective electrodes consists of working electrodes and reference electrodes, the working electrodes are intensively arranged in a sample cell area, the reference electrodes are intensively arranged in a reference cell area, and each working electrode and each reference electrode are connected with a metal guide disc through metal wires and are used for being connected and conducted with a detection instrument;
the monitoring electrode consists of a pair of inert conductive metals; the ion selective electrode is formed by sequentially superposing metal, corresponding metal salt, a solid state gelation internal reference electrolyte film and an ion selective electrode film;
the insulating layer exposes the effective areas of the working electrode and the reference electrode and the metal guide disc; the bridging layer is provided with a first through groove and a second through groove, one end of the first through groove is open and positioned in the sample pool area for siphoning and collecting detection samples, the periphery of the second through groove is closed and positioned in the reference pool area for containing reference liquid; the bridging layer is provided with a hollow fiber for communicating the sample pool area and the reference pool area;
three through holes are formed in the hydrophilic film layer, namely a sample cell exhaust hole, a reference cell exhaust hole and a reference cell sample injection hole, wherein the sample cell exhaust hole corresponds to the inner side of the first through groove, and the reference cell exhaust hole and the reference cell sample injection hole correspond to the two sides of the second through groove respectively;
the sealing film layer covers the hydrophilic film layer corresponding to the second through groove, and seals the reference cell exhaust hole and the reference cell sample injection hole;
the cover plate layer is provided with a third through groove corresponding to the first through groove, and a visual sample injection observation area is provided;
the reference liquid contains poly (N-isopropyl acrylamide-co-methacrylic acid) or glycerol.
2. The siphonic ion-selective electrode electrolyte test strip according to claim 1, wherein the sealing membrane layer covers the hydrophilic membrane layer corresponding to the second through groove, and seals the reference cell vent and the reference cell sample injection hole.
3. The siphonic ion-selective electrode electrolyte test strip according to claim 1, wherein the cover sheet is provided with a third through slot corresponding to the first through slot, providing a visual sample injection observation zone.
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