CN110133084A - A kind of Integrated electrode detection card and preparation method thereof that can detect magnesium, chloride ion simultaneously - Google Patents
A kind of Integrated electrode detection card and preparation method thereof that can detect magnesium, chloride ion simultaneously Download PDFInfo
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Abstract
The invention discloses the Integrated electrode detection cards that one kind can detect magnesium, chloride ion simultaneously, which is characterized in that the Integrated electrode detection card includes ion-selective electrode and reference electrode；The electrodes selective is made of conductive substrates and selective macromolecule sensing membrane, and the electrodes selective includes magnesium ion sensor and chloride ion sensor.The present invention is successfully realized in (the K of interfering ion containing high concentration+、Na+、Ca2+) complex sample in directly detect the concentration of ionic magnesium.The concentration for directly detecting chloride ion in complex samples is realized in success.Compare with traditional optical means, the electrochemical method accuracy in detection that we use is high, reproducible, easy to operate, detection time is short, instrument is small and exquisite.
Description
Technical field
This application involves electrochemical technology fields, can detect the integrated electricity of magnesium, chloride ion simultaneously in particular to one kind
Pole detection card and preparation method thereof.
Background technique
The detection and measurement of ionic species are in multiple fields such as biomedical research, environmental monitoring and production process controls
It is significant.Electrolyte ion is changed by itself complexity over time and space so that organism is to various types of thorns
Swash and responds, thus reach maintenance homeostasis, catalysis reaction, the effect for adjusting cell function.
For a long time, the detection of ionic species, it is largely highly sensitive by development, accurately, correctly analyze
Method.So far people have been able to successfully measure some inorganic ions of monitoring, example using some chemical method near real-times
Such as Ca2+,Mg2+,H+,Na+,K+,Cl-Deng, the relevant ionic drug of some biomedicines and metabolite and amino acid, one
A little required minor metallic element ions etc., but used analysis method generally requires expensive large-scale instrument (efficiently
Liquid chromatography mass instrument (HPLC-MS), capillary electrophoresis (CZE), Atomic Absorption Spectrometer (AAS), inductively coupled plasma
Body Atomic Emission Spectrometer AES (ICP-OES), icp ms (ICP-MS) etc., while needing by complexity
Purification procedures, all there is expensive equipments, complicated for operation time-consuming, not portable for these methods, it is difficult to carry out real-time on-site
The disadvantages of measurement.More importantly these methods typically only allow for discontinuous measurement, and cannot obtain practical biology or
In relation to the multidate information of ionic activity in sample.
The Main Trends of The Development of Modern Analytical Chemistry first is that research have consumption sample it is few, analysis time is short, sensitivity
Height, price is low, portable, a variety of advantage detection devices such as can abandon.Compared with above-mentioned method, chemistry and bio-sensing skill
Art provides a possibility that measurement monitors various ions in specific true environment, so as to better, real-time on the spot
The cooperation and interaction for understanding these ions are without complicated instrument and equipment.Especially selective support chemistry sensing
Device, such as ion-selective electrode and optrode are established in reversible host-guest chemistry identification process, and extraction can be selectively combined
The ion of small molecule is taken to enter lipophilicity organic film, to be particularly suitable for the various ionic species in research biosystem.
In electrolyte balance, magnesium (Mg2+) it is most one of the cation of in-vivo content.Adult body includes magnesium 0.823-
1.234mol, wherein 50% is present in bone, 45% liquid, extracellular fluid account for 5% in the cell.Liver, kidney and muscle are more containing magnesium,
The content of liquid magnesium is only second to potassium and occupies second in the cell, and concentration is about 10 times of extracellular fluid.In extracellular fluid, magnesium
Content be only second to sodium, potassium, calcium and occupy the 4th.Magnesium, which is involved in, during many plysiochemical reacts and accounts for critical role, than
The activator of a variety of enzymes in this way.It is alkalinity and acid phosphatase, transphosphorylase, pyrophosphatase, creatine kinase, hexokinase, bright
Histidine amino group peptase and carboxylase etc., their catalytic action must all have the activation of magnesium ion；Magnesium is composition DNA, RNA and ribose
Body macromolecular structure necessary element；It is also the important element for maintaining normal neuro-function and muscle.
Magnesium in extracellular serum has 3 kinds of forms: in conjunction with albumin (25%), with anion (phosphate radical, bicarbonate
Root, citrate etc.) (8%) is combined, free ion state (65%).Wherein ionic state magnesium (iMg) is that having for extracellular magnesium is given birth to
The part of activity and Clinical significance of detecting of science.Common detection method is that Biochemical Analyzer detects all Mg concentration (optics side in serum
Method), then it is converted into iMg concentration, often result in detection error.
Summary of the invention
Aiming at the deficiencies in the prior art, the present invention uses highly selective ion chelating agent and high molecular material,
Magnesium ion and chloride ion selectivity sensing membrane and all-solid-state reference electrode are prepared, is realized on Integrated electrode detection card to blood
IMg, Cl in liquid sample-Joint-detection.
The Integrated electrode detection card of the present invention that magnesium, chloride ion can be detected simultaneously, the Integrated electrode detect card
Including electrodes selective and reference electrode；The electrodes selective is made of conductive substrates and selective macromolecule sensing membrane,
The electrodes selective includes magnesium ion sensor and chloride ion sensor.
Specifically, the magnesium ion sensor includes lower layer and upper layer, the lower layer is conductive materials, and described is upper
Layer is magnesium ion macromolecule sensing membrane, is dispersed in Polymer Systems comprising magnesium ion chelating agent, ion-exchanger co-dissolve.
The ion-exchanger are as follows: sodium tetraphenylborate, tetraphenylphosphonichloride chloride arsenic, four (4- chlorphenyl) potassium borates, four (3,
5- bis- (trifluoromethyl) phenyl) Boratex, four [3,5- bis- (trifluoromethyl) phenyl] potassium borates, three (dodecyl) methyl chlorides
One of ammonium is a variety of；
The macromolecule are as follows: one of polyvinyl chloride, polyurethane, silicon rubber are a variety of.
The magnesium ion chelating agent are as follows: N, N '-diheptyl-N, N '-dimethyl -1,4- succinamide, N, N "-octamethylene
Bis- (N '-heptyl-N '-methyl-methylmalonyl amine), N, N ', N "-three [3- (heptyl methylamino) -3- oxo propionyl] -8,8 ' -
Imino-diacetic octylame, two azo-cycle of 4,13- [bis- (N- adamantylcarbamoyl) acetyl group] four oxygen -4,13- of -1,7,10,16-
One of octadecane；
Further, magnesium ion macromolecule sensing membrane of the present invention also contains adjuvant, plasticizer, the adjuvant
Are as follows: one of resin particle, silica flour, silica dioxide granule, silica white, aluminium oxide are a variety of.The plasticizer is not wave
The liquid organic compounds of hair.
Specifically, chloride ion sensor of the present invention includes lower layer and upper layer, the lower layer is conductive materials, institute
The upper layer stated is chloride ion macromolecule sensing membrane, includes this agent and curing agent.
This described agent are as follows: one of epoxy resin, acrylic resin, Polyurethane are a variety of；
The curing agent are as follows: one of fatty amine, aliphatic cyclic amine, aromatic amine, polyamide, aromatics curing agent are more
Kind.
Specifically, the reference electrode includes lower layer and upper layer, the lower layer is conductive materials, and the upper layer is
Reference electrode macromolecule sensing membrane is dispersed in Polymer Systems comprising hydrophobicity organic ionic compounds co-dissolve.
The hydrophobicity organic ionic compounds are as follows: tetra-n-butyl ammonium tetraphenylborate, tetra-n-butyl tetrabutyl boric acid
Ammonium, four (4- chlorphenyl) boric acid four (dodecyl) ammoniums；
The macromolecule are as follows: polyvinyl chloride, polyurethane, silicon rubber.
Heretofore described conductive material are as follows: gold, platinum, palladium, carbon, silver, silver/silver chlorate, metal-conducting polymer etc..
Electrodes selective described in Integrated electrode provided by the present invention detection card mainly include magnesium ion sensor and
Chloride ion sensor, but both sensors are not limited to, it can also be used cooperatively with other sensors, including sodium ion electricity
Pole, potassium ion electrode, calcium ion electrode, li-ion electrode, pH electrode, bicarbonate radical electrode, oxygen electrode, carbon dioxide electricity
One of pole, hematocrit electrode, creatinine electrode, urea nitrogen electrode, bilirubin electrode, blood glucose electrode, lactic acid electrode or
It is a variety of.
Further, electrodes selective of the present invention further include: sodium ion electrode, potassium ion electrode, calcium ion electrode,
Li-ion electrode, hematocrit electrode.
Further, electrodes selective of the present invention further include: sodium ion electrode, potassium ion electrode, calcium ion
Electrode, li-ion electrode, pH electrode, bicarbonate radical electrode, oxygen electrode, carbon dioxide electrode, hematocrit electrode.
Further, electrodes selective of the present invention further include: sodium ion electrode, potassium ion electrode, calcium ion
Electrode, li-ion electrode, pH electrode, bicarbonate radical electrode, oxygen electrode, carbon dioxide electrode, hematocrit electrode, creatinine
Electrode, urea nitrogen electrode, bilirubin electrode, blood glucose electrode, lactic acid electrode.
In addition, including the following steps: the present invention also provides the preparation method of above-mentioned Integrated electrode detection card
A) by the raw material containing magnesium ion chelating agent, ion-exchanger, macromolecule, co-dissolve in volatile solvent,
After completely dissolution, magnesium ion high score is prepared behind conductive substrates surface, property solvent volatilization completely to be evaporated in solution drop coating
Sub- sensing membrane；
B) this agent and curing agent are dissolved in respectively in different solvents, after being mixed in a certain proportion, drop coating or are impregnated into conduction
It in substrate, is used after being fully cured, chloride ion macromolecule sensing membrane is prepared；
C) by hydrophobicity organic ionic compounds, macromolecule, co-dissolve in suitable volatile solvent, sufficiently it is molten
Xie Hou by solution drop coating or is impregnated in conductive substrates surface, and reference electrode is prepared after property solvent volatilization completely to be evaporated；
D) magnesium ion electrode, chlorine ion electrode and reference electrode are placed on same plane bottom plate and are fixed, collection is prepared
At electrode detection card；Or use silk-screen printing blank Integrated electrode array, in different conductive substrates distinguish drop coating magnesium from
Son sensing coating solution, chloride ion sensing coating solution and reference electrode coating solution, obtain Integrated electrode inspection after solvent volatilizees completely
Survey card.
Volatile solvent described in this preparation method refers to the volatile solvent for being temporarily used for mixing each component, and meeting exists
It volatilizees and removes in film forming procedure.
When needing to adjust sensing membrane solution viscosity and sensing film thickness, the present invention can be added auxiliary in step a, step c
Agent, sufficiently oscillation are mixed and made into homogeneous solution.
When needing to adjust rigidity, film forming and the electrode selectivity of macromolecule sensing membrane, the present invention can be in step a, step
In rapid c, plasticizer is added, sufficiently dissolution is mixed and made into homogeneous solution.
When the electrode is not only magnesium ion sensor and chloride ion sensor, other electrodes selectives be
It is added in step a, remaining steps are identical as step d, and details are not described herein again.
The utility model has the advantages that the present invention is successfully realized in (the K of interfering ion containing high concentration+、Na+、Ca2+) complex sample in directly
Detect the concentration of ionic magnesium.The concentration for directly detecting chloride ion in complex samples is realized in success.With traditional optical means
Compare, the electrochemical method accuracy in detection that we use is high, reproducible, easy to operate, detection time is short, instrument is small and exquisite.
Detailed description of the invention
Fig. 1 is the working curve diagram of magnesium ion
Fig. 2 is the working curve diagram of magnesium ion in the presence of interfering ion
Fig. 3 is chlorine ion electrode response time and signal intensity figure
Fig. 4 is working curve diagram of Cl ion electrode in the presence of disturbance ion
Fig. 5 is flat surface pH electrode to pH responsive operation curve graph
Fig. 6 is the response time of flat surface pH electrode and the schematic diagram of stability
Fig. 7 is responsive operation curve graph of the glucose plane electrode to glucose
Specific embodiment
In order to make those skilled in the art more fully understand application scheme, below in conjunction in the embodiment of the present application
Attached drawing, the technical scheme in the embodiment of the application is clearly and completely described, it is clear that described embodiment is only
The embodiment of the application a part, instead of all the embodiments.
Embodiment 1: magnesium ion selects electrode sensing film preparation and electrode property characterization
Magnesium ion carrier, ion-exchanger, macromolecule and plasticizer (mass ratio 1:2) are added to the organic solvent of 3mL
In dissolution fullys shake.It finally takes 1~2 μ L drop coating of organic solution being uniformly dissolved to electrode surface, stands overnight at room temperature, to
Solvent volatilize completely after affixed magnesium ion electrode.Conducting polymer, nano-sized carbon can be used between polymeric membrane and electrode
The conductive materials such as pipe, to increase system stability.
Potential value method for measuring is: electrode being immersed in 20mL deionized water at room temperature, it is female that 0.01M magnesium chloride is added dropwise
Liquid obtains the magnesium ion solution of various concentration after stirring stops, the measurement of potential value is carried out with 6 channel EMF devices.Using double
Liquid connects Ag/AgCl reference electrode (built-in 3M KCl, outer solution are 1M lithium acetate).The ionic activity coefficient used in experimental data
It is calculated referring to debye-huckel's equation, all potential values pass through the correction of Martin Henderson equation, and all data are 5 parallel electricity
The average value of pole data measured.Available from Fig. 1, electrode is to magnesium ion 10-5M-10-1There is good linear sound within the scope of M
It answers (R=0.99982), Monitoring lower-cut 10-5M。
Under same experiment condition, magnesium ion electrode and reference electrode are co-located in 20mL metal ion salt solution containing interference
In (4.3mM KCl, 141.99mM NaCl, 2.29mM CaCl2), 0.01M chlorination mother liquid of magnesium is added dropwise, is obtained after stirring stops
The magnesium ion solution of various concentration carries out potential measurement, obtains result shown in Fig. 2.According to formula 1, magnesium ion Monitoring lower-cut and
The concentration calculation selectivity factor of interfering ion in background solution: Na+: -2.32 ± 0.067；K+: -0.35 ± 0.008；Ca2+:-
0.11±0.011
[selectivity factor accounting equation]
aA: the Monitoring lower-cut of magnesium ion；aB: interfering ion activity；zA: magnesium ion charge number；zB: interfering ion charge number
Embodiment 2: Chloride selective electrode senses film preparation and electrode property characterization
A certain amount of A glue (this agent) and B glue (curing agent) (A:B=1:1wt%) are weighed, organic solvent is added, is mixed
Uniformly.On Ag/AgCl basal electrode, the choosing of Cl ion is made after dry solidification for each drop coating suitable AB glue mixture solution
Select electrode.
Potential value method for measuring is: electrode being immersed in 20mL deionized water at room temperature, the chlorine of various concentration is added dropwise
Change mother liquid of sodium, obtains the Chloride Solution of various concentration after stirring stops, the measurement of potential value is carried out with 6 channel EMF devices.
Connect Ag/AgCl reference electrode using biliquid (built-in 3M KCl, outer solution are 1M lithium acetate).The ion used in experimental data is living
It spends coefficient to calculate referring to debye-huckel's equation, all potential values pass through the correction of Martin Henderson equation, and all data are 5
The average value of parallel pole data measured.From Fig. 3, (wherein (a) is the time trace of Cl ion electrode；It (b) is Cl ion
Working curve) it is available, electrode has good linear response (R=0.99982) to chloride ion within the scope of 98-106mM.
Detection target based on ion-selective electrode is blood, and the anionic species that may contain in sample may be to Cl
The detection of ion generates interference, therefore uses Br-、ClO4 -, salicylate, thiocyanate radical as interfering substance to chloride ion select electricity
The performance of pole carries out anti-interference test, and the specific method is as follows:
Electrode is immersed in sodium bromide, sodium perchlorate, salicylic acid, the sulphur that 20mL contains [1-10mM] concentration respectively at room temperature
Zassol is gone in solution, and the chlorination mother liquid of sodium of various concentration is added dropwise, and the chloride ion that various concentration is obtained after stirring stops is molten
Liquid carries out the measurement of potential value with 6 channel EMF devices.Ag/AgCl reference electrode (built-in 3M KCl, outer solution are connect using biliquid
For 1M lithium acetate).The selectivity factor (table 1) of chlorine ion electrode passes through Fig. 4 (wherein (a) bromide ion；(b) perchlorate；
(c) salicylic acid: (d) thiocyanate radical) in each working curve Monitoring lower-cut and interfering ion concentration calculation obtain.
1 chlorine ion electrode selectivity factor table of table
| Interfering ion | Selectivity factor |
| Bromine | -2.207±0.076 |
| Perchlorate | -1.44±0.216 |
| Salicylate | -0.295±0.064 |
| Thiocyanate radical | -0.112±0.052 |
The selectivity factor analysis of these interfering ions is found according to above-mentioned Cl ion-selective electrode, in blood testing
When, the testing result of this Cl ion-selective electrode can't be impacted because of the presence of above-mentioned interfering ion.
Since target detection is blood sample or serum sample, for sample size generally between tens microlitres to several milliliters, biliquid connects glass
Glass reference electrode size is big, is not suitable for the detection of small sample volume, and detects need to clean among different samples to remove every time
Remaining sample prevents sample room cross contamination, time-consuming and laborious；Directly use Ag/AgCl electrode as reference, due to difference
The Cl ion concentration contained in blood sample is different, can cause a deviation to Cl ion detection；Therefore of the present invention all solid state integrated
Reference electrode is contained in ion-selective electrode, meets the needs of single blood examination, is stablized and not by the heterogeneous shadow of sample
It rings.
Embodiment 3: the production of all-solid-state reference electrode
1.2mL organic solvent is first added in sample bottle；PVC is added in concussion again, after PVC is completely dissolved, then plus
Enter TBA-TPB；It is eventually adding NPOE solution (PVC:NPOE=1:2).Above-mentioned vial is finally tightened into lid, is put into shaking table
In, it 50 DEG C, 300rpm, rocks to mixture uniform dissolution into viscous liquid.Then the drop coating in Ag/AgCl electrode basement
0.6~2ul solution obtains all-solid-state reference electrode after dry solidification.
The Mg2+、Cl-Select electrode production used in conductive substrates material the production method is as follows:
Conductive material (carbon slurry, silver paste, silver/chlorination silver paste) is uniformly applied on electrode plate, or uses Vacuum Deposition
Different metal is covered base material by film instrument or magnetron sputtering, is then carved in the substrate for have conductive coating using laser engraving machine
The electrod-array (multiple electrodes for being 0.5~1.5mm comprising diameter) of regular shape out.Electrode with coating is carried out at surface
Reason is to obtain stable detection current potential.Sensing material solution by pipettor or dispenser drop coating or is printed onto electrode surface,
All-solid-state ion-selective electrode is obtained after drying.The sensing membrane of detection different ions is fixed on the Different electrodes base in same an array
On bottom, the different ions in same sample can be carried out while be measured.By electrod-array and reference electrode be respectively placed in containing
In the standard solution and sample to be tested of various ions, obtained potential value is calculated using some correction or two point correction method
The concentration of each ion and weighing value are compared in sample to be tested, calculate the rate of recovery.The detection of each sample repeatedly weighs
It is multiple, from standard deviation and mean value calculation precision (CV%), it the results are shown in Table 2.
Accuracy of 2 integrated card of table in analog sample
Electrod-array and reference electrode are respectively placed in the standard solution and blood sample containing various ions, obtained
Potential value, using some correction or two point correction method, calculate blood sample in each ion concentration, and commercialization instrument
Testing result is compared, and calculates correlation.The detection of each sample is repeated several times, from standard deviation and mean value calculation essence
Density (CV%), the results are shown in Table 3.
3 integrated card of table measures the accuracy of Sheep Whole Blood
| Correlation/I-STAT mM/mM | CV/% | |
| Cl | 119.3/105 | 4.19 |
| Mg | / | 6.41 |
Experimental result shows that the electrod-array may be implemented in complicated authentic sample (whole blood) while detect Mg2+And Cl-,
Reproducible, the accuracy height of measurement.
Embodiment 4
The Integrated electrode detection card is by magnesium ion sensor, chloride ion sensor, sodium ion electrode, potassium ion electricity
Pole, calcium ion electrode and reference electrode composition.
Conductive material (carbon slurry, silver paste) is uniformly applied on electrode plate, or is splashed using vacuum coater or magnetic control
It penetrates and different metal is covered into base material, then carve regular shape in the substrate for have conductive coating using laser engraving machine
Electrod-array (1.7cm wide, 6 electrodes for being 1mm comprising diameter).Electrode with coating is surface-treated to be stablized
Detection current potential.Sensing material solution by pipettor or dispenser drop coating or is printed onto electrode surface, drying at room temperature.For
The sensing material of different metal ions detection uses the system of PVC and plasticizer, uses sodium ion chelating agent, potassium ion respectively
Chelating agent, calcium ion chelator, magnesium ion chelating agent are active sensing material, and NaTFPB is ion-exchanger.Cl ion sensor
Film uses this agent and curing agent glue, is made after electrode surface solidification.The sensing membrane of detection different ions is fixed on same an array
In interior Different electrodes substrate, the different ions in same sample can be carried out while be measured.By electrod-array and reference electricity
Pole is respectively placed in the standard solution and sample to be tested containing various ions, obtained potential value, uses some correction or two o'clock
Bearing calibration, the concentration and weighing value for calculating each ion in sample to be tested are compared, and calculate the rate of recovery.Each sample
Detection is repeated several times, and from standard deviation and mean value calculation precision (CV%), the results are shown in Table 4.
Accuracy of 4 integrated card of table in analog sample
| Ion | The rate of recovery | CV/% |
| Na | 98.09 | 1.34 |
| K | 100.47 | 0.06 |
| Ca | 101.97 | 1.51 |
| Mg | 93.62 | 0.62 |
| Cl | 100.7 | 5.09 |
Electrod-array and reference electrode are respectively placed in the standard solution and blood sample containing various ions, obtained
Potential value, using some correction or two point correction method, calculate blood sample in each ion concentration, and commercialization instrument
Testing result is compared, and calculates correlation.The detection of each sample is repeated several times, from standard deviation and mean value calculation essence
Density (CV%), the results are shown in Table 5.
5 integrated card of table measures the accuracy of whole blood
| Correlation/I-STAT mM/mM | CV/% | |
| Na | 83.64/131 | 5.03 |
| K | 4.74/ > 9 | 5.19 |
| Ca | 0.93/ < 0.25 | 6.00 |
| Cl | 119.3/105 | 4.19 |
| Mg | / | 6.41 |
Experimental result shows that the electrod-array may be implemented disposably to detect multiple ions in complicated authentic sample, surveys
That measures is reproducible, and accuracy is high, and the correlation of commercialization instrument is good.The electrod-array is realized for the first time in serum and whole blood
While detecting common electrolyte in product, to the Accurate Determining of ion magnesium, calcium ion does not generate interference to magnesium ion electrode.
The detection of electrolyte of the Integrated electrode detection card of the present embodiment suitable for serum, blood plasma, whole blood, urine.
Embodiment 5
The Integrated electrode detection card is by magnesium ion sensor, chloride ion sensor, sodium ion electrode, potassium ion electricity
Pole, calcium ion electrode, li-ion electrode, pH electrode, bicarbonate radical electrode, oxygen electrode, carbon dioxide electrode, reference electrode group
At.
Ion-selective electrode uses the system of PVC and plasticizer, is chelated respectively using sodium ion chelating agent, potassium ion
Agent, calcium ion chelator, magnesium ion chelating agent, hydrogen ion chelating agent, bicarbonate radical and carbonate chelating agent are activity sensing material
Ion-exchanger is added in material.Cl ion sensor film uses this agent and curing agent glue, is made after electrode surface solidification.Oxygen electricity
Pole uses plane Clark electrode, and carbon dioxide electrode is Severinghaus type gas sensing electrode.
Fig. 5 is flat surface pH electrode to pH responsive operation curve
Fig. 6 is response time and the stability of flat surface pH electrode
Table 6 measures the CV value and the rate of recovery (n=5) of pH in simulation blood sample
CV value and accuracy (n=5) of 7 dissolved oxygen electrode of table in different type sample
| Sample type | The rate of recovery/% | CV/% |
| Buffer PBS | 101 | 5.62 |
| Serum | 95 | 5.74 |
| Whole blood | 113 | 8.17 |
Integrated electrode detection card electrolyte and while vim and vigour suitable for blood sample of the present embodiment, quickly measures.
Embodiment 6
The Integrated electrode detection card is by magnesium ion sensor, chloride ion sensor, sodium ion electrode, potassium ion electricity
Pole, calcium ion electrode, li-ion electrode, pH electrode, bicarbonate radical electrode, oxygen electrode, carbon dioxide electrode, hematocrit
Electrode, creatinine electrode, urea nitrogen electrode, bilirubin electrode, blood glucose electrode, lactic acid electrode and reference electrode composition.
Ion-selective electrode uses the system of PVC and plasticizer, is chelated respectively using sodium ion chelating agent, potassium ion
Agent, calcium ion chelator, magnesium ion chelating agent, hydrogen ion chelating agent, bicarbonate radical and carbonate chelating agent are activity sensing material
Ion-exchanger is added in material.Cl ion sensor film uses this agent and curing agent glue, is made after electrode surface solidification.Oxygen electricity
Pole uses plane Clark electrode, and carbon dioxide electrode is Severinghaus type gas sensing electrode.Creatinine electrode, urea nitrogen electrode,
Bilirubin electrode, blood glucose electrode, lactic acid electrode fix creatinine hydroamidase, urease, bilirubin in conductive substrates respectively
Oxidizing ferment, glucose oxidation enzyme or dehydrogenase, lactate oxidase or dehydrogenase are prepared.
Fig. 7 is responsive operation curve graph of the glucose plane electrode to glucose
The electrode of glucose oxidase modification and reference electrode are placed in the standard solution containing a certain concentration glucose sugar
In (5mM) and sample to be tested, the average value of electric current in the 40s-60s time after being loaded is taken, working curve is as shown in Figure 7.Use one
Point method calculates concentration of glucose and theoretical value in sample to be tested and compares, and calculates the rate of recovery.Sample size n >=5 of detection, from standard
Deviation and mean value calculation precision (CV%), the results are shown in Table 8:
CV value and the rate of recovery of 8 glucose oxidase electrode of table in different type sample
| Sample type | The rate of recovery/% | CV/% |
| Buffer PBS | 94.74 | 3.84 |
| Serum | 110.4 | 11.24 |
| Whole blood | 86.5 | 11.16 |
The Integrated electrode detection card of the present embodiment is suitable for quickly measuring clinical critical disease index simultaneously, can be used for emergency treatment,
Operating room, bedside detect immediately.
The foregoing is merely preferred embodiment of the present application, are not intended to limit this application, based in the application
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
The range of the application protection should belong to.
Claims (11)
1. the Integrated electrode detection card that one kind can detect magnesium, chloride ion simultaneously, which is characterized in that the Integrated electrode detects card
Including electrodes selective and reference electrode；
The electrodes selective is made of conductive substrates and selective macromolecule sensing membrane,
The electrodes selective includes magnesium ion sensor and chloride ion sensor.
2. Integrated electrode detection card according to claim 1, which is characterized in that the magnesium ion sensor includes lower layer
And upper layer, the lower layer be conductive materials, the upper layer be magnesium ion macromolecule sensing membrane, comprising magnesium ion chelating agent,
Ion-exchanger co-dissolve is dispersed in Polymer Systems.
3. Integrated electrode detection card according to claim 2, which is characterized in that
The ion-exchanger are as follows: sodium tetraphenylborate, tetraphenylphosphonichloride chloride arsenic, four (4- chlorphenyl) potassium borates, four (3,5- bis-
(trifluoromethyl) phenyl) Boratex, four [3,5- bis- (trifluoromethyl) phenyl] potassium borates, in three (dodecyl) ammonio methacrylates
It is one or more；
The macromolecule are as follows: one of polyvinyl chloride, polyurethane, silicon rubber are a variety of.
The magnesium ion chelating agent are as follows: N, N '-diheptyl-N, N '-dimethyl -1,4- succinamide, N, N "-octamethylene are double
(N '-heptyl-N '-methyl-methylmalonyl amine), N, N ', N "-three [3- (heptyl methylamino) -3- oxo propionyl] -8,8 '-sub-
Amino dioctylamine, two azo-cycle ten of 4,13- [bis- (N- adamantylcarbamoyl) acetyl group] four oxygen -4,13- of -1,7,10,16-
One of eight alkane.
4. Integrated electrode detection card according to claim 2, which is characterized in that the magnesium ion macromolecule sensing membrane is also
Containing adjuvant, plasticizer, the adjuvant are as follows: resin particle, silica flour, silica dioxide granule, silica white, one in aluminium oxide
Kind is a variety of.
5. Integrated electrode detection card according to claim 1, it is characterised in that the chloride ion sensor includes lower layer
And upper layer, the lower layer are conductive materials, it includes this agent and curing agent that the upper layer, which is chloride ion macromolecule sensing membrane,.
6. Integrated electrode detection card according to claim 5, it is characterised in that
This described agent are as follows: one of epoxy resin, acrylic resin, Polyurethane are a variety of；
The curing agent are as follows: one of fatty amine, aliphatic cyclic amine, aromatic amine, polyamide, aromatics curing agent are a variety of.
7. Integrated electrode according to claim 1 detection card, it is characterised in that the reference electrode includes lower layer and upper
Layer, the lower layer are conductive materials, and it includes hydrophobicity organic ion that the upper layer, which is reference electrode macromolecule sensing membrane,
Object co-dissolve is closed to be dispersed in Polymer Systems.
8. Integrated electrode detection card according to claim 7, which is characterized in that
The hydrophobicity organic ionic compounds are as follows: tetra-n-butyl ammonium tetraphenylborate, tetra-n-butyl tetrabutyl ammonium borate, four
(4- chlorphenyl) boric acid four (dodecyl) ammonium；
The macromolecule are as follows: polyvinyl chloride, polyurethane, silicon rubber.
9. Integrated electrode detection card according to claim 7, it is characterised in that the reference electrode macromolecule sensing membrane
Also contain adjuvant, plasticizer；The adjuvant is resin particle, silica dioxide granule.
10. the detection of Integrated electrode described in any one card according to claim 1~9, it is characterised in that the selectivity electricity
Pole further include: sodium ion electrode, potassium ion electrode, calcium ion electrode, li-ion electrode, pH electrode, bicarbonate radical electrode, oxygen
Electrode, carbon dioxide electrode, hematocrit electrode, creatinine electrode, urea nitrogen electrode, bilirubin electrode, blood glucose electrode, lactic acid
One of electrode is a variety of.
11. the preparation method of Integrated electrode detection card described in claim 1, which comprises the steps of:
A) by the raw material containing magnesium ion chelating agent, ion-exchanger, macromolecule, co-dissolve in volatile solvent, sufficiently
After dissolution, magnesium ion macromolecule biography is prepared behind conductive substrates surface, property solvent volatilization completely to be evaporated in solution drop coating
Feel film；
B) this agent and curing agent are dissolved in respectively in different solvents, after being mixed in a certain proportion, drop coating or are impregnated into conductive substrates
On, it is used after being fully cured, chloride ion macromolecule sensing membrane is prepared；
C) by hydrophobicity organic ionic compounds, macromolecule, co-dissolve in suitable volatile solvent, after completely dissolution,
By solution drop coating or it is impregnated in conductive substrates surface, reference electrode is prepared after property solvent volatilization completely to be evaporated；
D) magnesium ion electrode, chlorine ion electrode and reference electrode are placed on same plane bottom plate and are fixed, integrated electricity is prepared
Pole detection card；Or silk-screen printing blank Integrated electrode array is used, drop coating magnesium ion is distinguished in different conductive substrates to be passed
Feel coating solution, chloride ion sensing coating solution and reference electrode coating solution, Integrated electrode detection card is obtained after solvent volatilizees completely.
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