CN105203609A - Sodium ion biochemical analysis dry plate and preparation method thereof - Google Patents
Sodium ion biochemical analysis dry plate and preparation method thereof Download PDFInfo
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- CN105203609A CN105203609A CN201510694616.8A CN201510694616A CN105203609A CN 105203609 A CN105203609 A CN 105203609A CN 201510694616 A CN201510694616 A CN 201510694616A CN 105203609 A CN105203609 A CN 105203609A
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Abstract
The invention relates to a sodium ion biochemical analysis dry plate and a preparation method thereof, belongs to the technical field of blood-gas biochemical sensors, and is used for detecting sodium ion concentration in body fluid. The dry plate disclosed by the invention comprises a supporting layer, an insulating layer, a salt bridge, electrodes, reference layers and sodium ion-selective membranes. Metal/metal salt thin slice electrodes are prepared; each reference layer is attached to the corresponding electrode; the pH value and the water content of each reference layer are constant; each sodium ion-selective membrane is attached to the corresponding solid-state reference layer to prepare a sodium ion-selective electrode; acrylic ester is used as a bonding agent for the sodium ion-selective membranes; the salt bridge is sealed in the insulating layer; the two sodium ion-selective electrodes, the supporting layer and the insulating layer are bonded to assemble the dry plate; during testing, to-be-tested solution and reference solution are conducted through the salt bridge. According to the dry plate prepared by the preparation method disclosed by the invention, the defect that the traditional ion-selective electrode is complicated in operation, high in use and maintenance cost, slow in response and is not easy to carry and the like is overcome; the operation is simple, the response speed is fast, and the size is small; moreover, the preparation process is simple, low in production cost and suitable for industrial production.
Description
Technical field
The present invention relates to vim and vigour biochemical sensor technologies field, particularly relate to a kind of sodion biochemical analysis dry plate and preparation method thereof.
Background technology
Human body fluid electrolyte concentration is clinical examination, treatment is assessed and the important evidence of Index for diagnosis.And as the dominant cation of the outer liquid of human body cell, sodion is one of important indicator judging that human electrolyte balances.In measurement human body fluid conventional at present, sodium ions content equipment is the wet type biochemical analysis detector relying on ion-selective electrode principle.
Traditional wet type biochemical analysis detect have that complicated operation, operation and maintenance cost are high, low-response, the shortcoming such as not portable.Novel electrolyte detection method---dry type detects, and has and measures the features such as accurate, with low cost, simple to operate, can be widely used in multiple environment.
Chinese patent CN101852761A discloses a kind of all-solid sodium ion selective electrode and preparation method thereof, but needs to match with external contrast electrode when the ion-selective electrode in patent is tested to use, and using method is complicated; Chinese patent CN104330449A discloses a kind of sodium ion sensor and manufacture method thereof, the sodium ion sensor method complexity that this patent system is standby, and measurement range and stability also need to improve.Above-mentioned patent all adopts screen printing technique to prepare electrode, but the metal level purity that serigraphy obtains is inadequate, and surface is uneven, can affect stability and the response time of electromotive force.
In existing solid ionic choice electrode, all select Polyvinylchloride as the high polymer binder (patent CN101852761A, CN104330449A, CN102636532A, CN101871912A, CN102558724A) of ion-selective membrane.Polyvinylchloride has higher intensity and chemical stability, low price, but it must add plastifier just can guarantee that ion-selective membrane responds, and As time goes on, plastifier be dissolved in carrier wherein can together with leak out from ion-selective membrane, cause ion-selective membrane to respond lower limit to be deteriorated, lifetime.
Summary of the invention
For existing sodium selective electrode Problems existing, the invention provides a kind of sodion biochemical analysis dry plate and preparation method thereof, prepared dry plate measuring accuracy is high, long-time stability are good, response time is short, and structure is simple, volume is little, preparation technology is simple, production cost is low, is applicable to producing in enormous quantities.
Sodion biochemical analysis dry plate of the present invention comprises supporting layer, insulation course, salt bridge, electrode, reference layer and sodion selective membrane.Preparation technology is as follows: (1) prepares metal/metal salt thin electrode; (2) on electrode, be coated with the reference layer solution prepared and sodion selective membrane solution also dry preparation sodium selective electrode; (3) convince pore by patient analysis on the insulating layer, salt bridge is sealed in insulation course; (4) by two panels sodium selective electrode and supporting layer, the bonding assembling dry plate of insulation course.
In the present invention, supporting layer plays protection, supports sodium selective electrode effect, and insulation course plays bonding electrode, the effect of sealing salt bridge, and salt bridge plays the effect of connection electrode; Insulation course has gas port, the flow rate of reference liquid and test fluid during test, can be improved, shorten the test duration; Supporting layer, insulation course are selected from polypropylene, Polyvinylchloride, tygon, polyester non-conductive polymer material, and salt bridge is filter paper material.
Electrode.Electrode of the present invention comprises metal level and metal salt.Metal salt and metal level form phase boundary potential, have stable electromotive force response.Metal is selected from gold, silver, copper, mercury, platinum, nickel, and slaine is selected from the insoluble metallic salt of metal level metal.Metal salt can use the oxide of metal level metal, such as metal halide.Preferred electrode is silver/silver chloride electrode.
Electrode metal layer is attached to non-conductive polymer surface, be improve electrode stability, shorten the response time, the present invention can adopt vacuum coating, the mode of electroless plating or plating prepares metal level, preferred electroless plating method.Use electroless plating method, layer on surface of metal is even, can set up the balance between phase boundary instantaneously, form stable response electromotive force, shortens the response time.Metal salt can adopt the method for chemical oxidation to obtain, and uses iron chloride or liquor potassic permanganate to be oxidized metal level.
Reference layer.Reference composition of layer comprises: cementing agent, buffering agent, slaine, surfactant.Reference layer is attached on electrode metal salt deposit by the mode of lamination or coating.
For guaranteeing that sodion biochemical analysis dry plate has good measuring accuracy and long-time stability, reference layer pH scope is 5 ~ 8.5, simultaneously for ensureing the bond strength of reference layer and sodion selective membrane, prevent sodion biochemical analysis dry plate response signal accuracy and long-time stability from reducing, reference layer water cut can not be too high or too low, and reference layer optimum moisture content is 30% ~ 40%.
The present invention by controlling drying time of reference layer, temperature, humidity fixes reference layer pH and water cut, optimum drying condition: temperature 25 DEG C, relative humidity 50%, time 40min.
Reference layer binder is selected from one or more in gelatin, agar, polyacrylamide, polyvinyl alcohol (PVA) or other polyvinyl, accounts for 30% ~ 80% of reference layer gross mass.
Need containing the identical negative ion of electrode metal salt deposit and kation sodion to be measured in reference layer used herein, preferred sodium chloride, accounts for 20% ~ 50% of reference layer gross mass.
The present invention uses buffering agent to adjust reference layer pH, and buffering agent is selected from Dicarboxylic Acids and alkaline metal thereof or ammonium compounds, and organic carboxyl acid need have 3 ~ 8 carbon atoms and appropriate acidity coefficient usually, could provide good buffering effect like this for reference layer.Buffering agent is selected from one or more in maleic acid, malic acid, malonic acid, glutaric acid, succinic acid, preferred succinic acid, accounts for 0.01% ~ 5% of reference layer gross mass.
Sodion selective membrane.Sodion selective membrane composition comprises: high polymer binder, ionophore, carrier solvent, negative ion agent interfering and surfactant.
For reducing the consumption of plastifier, reduce carrier and run off, promote the long-time stability of sodion selective membrane, the high polymer binder that the present invention uses is acrylate materials.Its physical and mechanical property is controlled, can reduce the use of plastifier, and the physical property of its excellence can promote the adhesion property of ion-selective membrane and solid electrolyte reference layer simultaneously, improves the stability of the response signal of ion-selective electrode.Acrylate has lower coefficient of diffusion, is conducive to obtaining wider sensing range, and lower coefficient of diffusion be conducive to carrier dispersed and suppress carrier run off, eliminate carrier run off on response electromotive force impact, improve the accuracy of test.Esters of acrylic acid cementing agent is selected from one or more in ethyl acrylate, methyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, glycidyl methacrylate, methacrylic acid ester in the positive last of the ten Heavenly stems, preferable methyl methyl acrylate, accounts for 15% ~ 40% of sodion selective membrane gross mass.
Carrier solvent requires energy dissolved ions carrier, and has good compatibility with high polymer binder, guarantees that carrier moves in high polymer binder.Usual carrier solvent can be used as macromolecular material plastifier and uses, and is selected from one or more in phthalic ester, sebacate, ortho-nitrophenyl octyl ether, adipate mixing aromatic aliphatic phosphate, accounts for 30% ~ 70% of sodion selective membrane gross mass.
Negative ion agent interfering can get rid of lipophilic anion in liquid to be measured (as long-chain fatty acid, long chain alkyl sulphonates or long-chain Acidic phosphates salt) to ionophoric interference, improve the sensitivity of electrode pair cation selective, expand the linear response range of ion-selective electrode.Be selected from one or more in tetraphenylboron sodium, potassium tetraphenylborate, four (4-chlorphenyl) potassium borate, four [two (trifluoromethyl) phenyl of 3,5-] potassium borate, account for 0.5% ~ 2% of sodion selective membrane gross mass.
Ionophore selects compound sodion to selective response, carrier is selected from N, N, N ', N '-four cyclohexyl-1, 2 phenyl dioxy diacetayl amides, N, N ', N ' '-three heptyl-N, N ', N ' '-trimethyl-4, 4 ', 4 ' '-propylidyne (3-oxo butyramide), N, N '-dibenzyl-N, N '-diphenyl-1, 2-phenylene dioxy oxalamide, 2, two [(12-crown ether-4) methyl] ester of the two dodecyl malonic acid of 2-, polyetheramides, coban methyl esters, calixarenes two caves ether, one in crown ether and derivant thereof, account for 1% ~ 5% of sodion selective membrane gross mass.
Surfactant is selected from one or more in organosilicon or siloxane type surfactants, accounts for 0.1% ~ 3% of sodion selective membrane gross mass.
Be different from the sodium selective electrode of existing patent, the present invention does not need to match with outer contrast electrode to use, and two panels sodium selective electrode is identical.Major advantage of the present invention has: (1) eliminates liquid electrolyte layer, adopts structure of whole solid state, convenient and swift, does not need long-time activation during use; (2) control reference layer pH and water cut by drying process, select acrylate to be the high polymer binder of sodion selective membrane, promote measuring accuracy and the long-time stability of sodion biochemical analysis dry plate; (3) the metal/metal salt thin electrode surface uniform prepared, shortens the sodion biochemical analysis dry plate response time greatly, can equilibrium establishment within 7s, forms stable response electromotive force; (4) structure is simple, volume is little, and size is 10mm × 10mm, is easy to integrated, can be developed into superminiature biochemical analysis dry plate, and preparation technology is simple, with low cost, is suitable for large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is sodion biochemical analysis dry plate schematic diagram.
Fig. 2 is sodium selective electrode (electrode, reference layer, sodion selective membrane) schematic diagram.
Fig. 3 is sodion biochemical analysis dry plate testing standard liquid response potential curve.
Fig. 4 is sodion selective membrane test variable concentrations NaNO
3solution response electromotive force.
Fig. 5 is sodion biochemical analysis dry plate family curve.
Fig. 6 is sodion biochemical analysis dry plate long term stability tests result.
Embodiment
The present invention is described in detail with embodiment by reference to the accompanying drawings.
As shown in Figure 1, sodion biochemical analysis dry plate comprises: supporting layer 1, sodium selective electrode 2, insulation course 3, salt bridge 4.
As shown in Figure 2, sodium selective electrode comprises: silver layer 21, silver chloride layer 22, reference layer 23, sodion selective membrane 24.
Concrete implementation step is as follows.
By the method for electroless plating at polyethylene terephthalate plated surface silver layer, prepare silver layer 21.
Chemical method is adopted to be oxidized by front for silver layer 21 2/3 section.The contact electrode being oxidized position will be needed to be immersed in 0.1mol/L ferric chloride solution after 60s, and taking-up pure water cleans up and drying, obtains silver chloride layer 22.
Reference layer is coated with.By 6g polyvinyl alcohol (PVA), 1g glycerine, 3g sodium chloride, 0.02g citric acid, 0.02g germifuge, 0.004g surfactant H212 is dissolved in 100g water, is coated on silver chloride layer 22, drying condition: 25 DEG C, relative humidity 50%, dry 40min.
Sodion selective membrane is coated with.By 0.1g methyl methacrylate, 0.1g ortho-nitrophenyl octyl ether, 0.004gN, N, N, N
'-four cyclohexyl-1,2 phenyl dioxy diacetayl amides, 0.003g tetraphenylboron sodium, 0.005g surfactant H212 is dissolved in acetone, is coated on reference layer 23, and drying at room temperature.
After sodion selective membrane 24 drying, it is bonding with insulation course 3 to get two panels sodium selective electrode 2, by bonding with supporting layer 1 for insulation course 3 assembling dry plate after solidification.
Sodion biochemical analysis dry plate long-term storage conditions is :-18 ~-10 DEG C.
Sodion biochemical analysis dry plate using method, uses after needing to place 1h at normal temperatures when taking out from low temperature environment, keeps probe temperature 37 ± 0.1 DEG C during test.During test, dry plate is inserted in test trough, two lateral opening dropping reference liquid and test fluid respectively, required sample 5 ~ 10 μ L.
In order to advantage of the present invention is better described, the invention provides 4 groups of experimental datas, specific as follows.
Experiment 1, with sodion biochemical analysis dry plate testing standard liquid, response electromotive force and the curve of test duration are as shown in Figure 3.
Experiment 2, prepares sodion selective membrane test variable concentrations NaNO
3solution (0.01mol/L, 0.14mol/L, 0.6mol/L) responds electromotive force, and test result as shown in Figure 4.
Experiment 3, calibrates sodion biochemical analysis dry plate.By known Na ion concentration titer (Na ion concentration 95mmol/L and 220mmol/L), test sodion biochemical analysis dry plate response electromotive force, obtains electromotive force response corrections curve.Correction equation is: Y=61.4X+54.89, and wherein Y represents response electromotive force, and X represents logC, and C is sodium ion in liquor concentration.Family curve as shown in Figure 5.
Experiment 4, sodion biochemical analysis dry plate long term stability tests, with the response electromotive force of measurement standard liquid (Na ion concentration 220mmol/L) respectively in the sodion biochemical analysis dry plate 90 days of a collection of preparation, test result as shown in Figure 6.
The above its object is to person skilled in the art can be understood content of the present invention and implement according to this only for technical conceive of the present invention and feature are described, can not limit the scope of the invention with this.All modifications done according to the Spirit Essence of main technical schemes of the present invention, all should be encompassed within protection scope of the present invention.
Claims (9)
1. sodion biochemical analysis dry plate and preparation method thereof, is characterized in that: described sodion biochemical analysis dry plate comprises supporting layer, insulation course, salt bridge, electrode, reference layer and sodion selective membrane; The main preparation process of described sodion biochemical analysis dry plate comprises, and (1) prepares metal/metal salt thin electrode; (2) on electrode, be coated with the reference layer solution prepared and sodion selective membrane solution also dry preparation sodium selective electrode; (3) convince pore by patient analysis on the insulating layer, salt bridge is sealed in insulation course; (4) by two panels sodium selective electrode and supporting layer, the bonding assembling dry plate of insulation course.
2. salt bridge, supporting layer, insulation course according to claim 1, is characterized in that: described salt bridge is filter paper material; Described supporting layer and insulation course are selected from polypropylene, Polyvinylchloride, tygon and polyester non-conductive polymer material.
3. supporting layer, insulation course according to claim 1, is characterized in that: described supporting layer and insulation course are schistose texture, thickness 0.5 ~ 2mm.
4. electrode according to claim 1, is characterized in that: described electrode is metal/metal salt thin electrode, and electrode comprises metal level and metal salt; Metal level metal is selected from gold, silver, copper, mercury, platinum, nickel; Slaine is selected from the insoluble metallic salt of metal level metal.
5. electrode according to claim 1, is characterized in that: described electrode adopts electroless plating, the mode of Vacuum Deposition or plating is attached on substrate, metal level and metal salt thickness 0.1 ~ 10 μm on substrate.
6. reference layer according to claim 1, is characterized in that: described reference composition of layer comprises cementing agent, buffering agent, slaine, surfactant; Buffering agent is selected from one or more in maleic acid, malic acid, malonic acid, glutaric acid, succinic acid, accounts for 0.01% ~ 5% of reference layer gross mass; Slaine contains negative ion identical with electrode metal salt deposit, accounts for 20% ~ 50% of reference layer gross mass.
7. reference layer according to claim 1, is characterized in that: described reference layer is attached on electrode, baking temperature 20 ~ 40 DEG C, dry environment relative humidity 20% ~ 50%, drying time 30 ~ 100min, reference layer pH5 ~ 8.5, water cut 30% ~ 40%.
8. sodion selective membrane according to claim 1, is characterized in that: described sodion selective membrane composition comprises high polymer binder, ionophore, carrier solvent, negative ion agent interfering, surfactant; High polymer binder is selected from one or more in ethyl acrylate, methyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, glycidyl methacrylate, methacrylic acid ester in the positive last of the ten Heavenly stems, accounts for 15% ~ 40% of sodion selective membrane gross mass.
9. sodion selective membrane according to claim 1, is characterized in that: described sodion selective membrane be attached to dry after on reference layer.
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Cited By (2)
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| CN109142490A (en) * | 2017-06-15 | 2019-01-04 | 无锡德医爱德医疗器材有限公司 | All-solid sodium ion selective sensor and its preparation and application |
| 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 |
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| CN109142490A (en) * | 2017-06-15 | 2019-01-04 | 无锡德医爱德医疗器材有限公司 | All-solid sodium ion selective sensor and its preparation and application |
| 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 |
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