CN101158691A - Electrochemistry detecting method and testing apparatus of saccharification hemoglobin content - Google Patents
Electrochemistry detecting method and testing apparatus of saccharification hemoglobin content Download PDFInfo
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- CN101158691A CN101158691A CNA200710135510XA CN200710135510A CN101158691A CN 101158691 A CN101158691 A CN 101158691A CN A200710135510X A CNA200710135510X A CN A200710135510XA CN 200710135510 A CN200710135510 A CN 200710135510A CN 101158691 A CN101158691 A CN 101158691A
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Abstract
The present invention provides an electrochemical detection method for content of glycosylated hemoglobin in the blood, and is characterized in that: whole blood specimen is diluted by combined liquid ranging from 30 times to 70 times and passes through a glycosylated protein recognizer, electric activated small molecules are filled into the effluent liquid from the glycosylated protein recognizer, and electrochemical response of the liquid is detected by chemically modified electrodes after the filling, thereby obtaining the concentration of the blood glucose. The glycosylated protein recognizer is eluted by elute solvent, and the electrochemical response of the elute solvent is detected and the concentration of the glycosylated hemoglobin is obtained, thereby obtaining the content of the glycosylated hemoglobin of the sample after calculation. As the electrochemical detection is simple in operation, lower in cost and rapid in the analysis, the present invention is expected to realize the rapid determination of the clinical glycosylated hemoglobin and the rapid determination of the glycosylated hemoglobin after separation and elution.
Description
Technical field
The invention belongs to the determination techniques of glycosylated hemoglobin in a kind of blood, relate in particular to a kind of electrochemical detection method and pick-up unit of saccharification hemoglobin content.
Background technology
(Diabetes Mellitus DM) is a kind of disease of pathobolism to diabetes, and its M ﹠ M is just in rising trend, becomes one of healthy principal disease of the harm humans that is only second to angiocardiopathy and tumour.Healthy population can and be decomposed into glucose with carbohydrate digestion, and enters into blood is absorbed conduct growth and energy by cell raw material.Enter in the process of cell by blood at glucose, need the help of insulin.Insulin is a kind of hormone by pancreas secretion, and it can make glucose pass through cell membrane, makes it be converted into energy or other materials usefulness as storage.When healthy people takes food, pancreas can automatically be secreted the insulin that is fit to component glucose is taken in the cell by blood, but because diabetic can not be secreted the insulin of normal component or cell can not normally be reacted to insulin and can not normally make glucose enter cell, glucose is gathered in blood, and from urine, flow away, therefore the diabetic can lose a large amount of energy sources, and causes a series of complication.
Haemoglobin (Hemoglobin) is the endoerythrocytic respiratory protein of vertebrate, its molecule is by two α and two tetramers that the beta polypeptides chain constitutes, respectively be combined with a haemachrome molecule on each peptide chain, and it is approaching mutually, form the haemoglobin molecule of almost spherical, be the main matter of transportation oxygen in the blood, play transmission oxygen, decomposing H in vivo
2O
2, transmit the key activities relevant such as electronics with oxygen and energetic supersession, in all vital movements, play key effect.Glycosylated hemoglobin (HbA1c) is the product of the beta chain terminal amino group generation non-enzyme reaction of glucose molecule and blood red white molecule in the blood, and reacting dose increases along with the increase of concentration of glucose in the blood.Be that concentration of glucose is big more in the blood, then the content of HbA1c is just big more in the red blood cell, so HbA1c content has just reflected the level of glucose in the blood in the red blood cell.Because the erythrocytic life-span is approximately 100-120 days in the human body, therefore measures HbA1c content clinically and can determine diabetic's Blood glucose control level in 2-3 month in the past.Keep normal or approaching normal blood sugar level; help the diabetic to prevent because that the rising of blood sugar causes is blind, kidney, nerve and cardiovascular and cerebrovascular complication, therefore fast, content sensitive, that detect glycosylated hemoglobin in the blood accurately and reliably has important practice significance to the midium or long term control of diabetic's blood sugar level and the early warning of diabetes.
Glycosylated hemoglobin is measured and is originated from the late nineteen seventies the eighties initial stage in last century as medical diagnosis, main measure the adhesive ability of glucose molecule on red blood cell in the blood, as diabetic's evaluation of blood sugar level control quality in 2-3 month in the past.Usually the content of HbA1c represents recently that with the percentage that HbA1c accounts for haemoglobin total amount in the blood reference value of HbA1c content is 5-20% clinically, and thinks that 4-6% is normal.The best every three months of ADA suggestion diabetic is done the mensuration of a glycosylated hemoglobin, and makes it remain on level below 7% to avoid the generation of multiple complications.The method that is used at present the HbA1c assay clinically mainly contains immunity, ion-exchange chromatography, boron affinity chromatography and Capillary Electrophoresis etc.These methods all included a separating step before luminosity quantitative measurement HbA1c content, for example based on the ion-exchange chromatography of HbA1c and Hb surface charge difference and electrophoretic separation and based on the immunity and the boron affinity chromatography method of HbA1c and Hb structural difference, testing process needs repeatedly wash-out and instrumentation to detect, sense cycle is long, complex operation step, instrument and reagent are quite expensive, thereby are restricted in the application aspect the midium or long term control of the early warning of diabetes, diabetic's blood sugar level.Developing new detection technique, reduce and detect cost, simplify and detect step, accelerate detection speed, improve sensitivity, the accuracy of detection means, is problem demanding prompt solution.
Summary of the invention
Technical matters: the present invention is directed to above-mentioned technical matters, provide a kind of reduction to detect cost, simplify and detect step, accelerate detection speed, the electrochemical detection method of saccharification hemoglobin content in the sensitivity of raising detection means, the blood of accuracy.
Technical scheme: the electrochemical detection method of saccharification hemoglobin content in a kind of blood, whole blood sample is used in conjunction with after 30-70 times of the liquid dilution, cross the glycated proteins recognizer, in the whole blood sample effluent of glycated proteins recognizer, add electroactive micromolecule, and with the electrochemical response of solution behind the chemically modified electrode measuring column, obtain the concentration of haemoglobin; With eluent the glycated proteins recognizer is carried out wash-out, measure the electrochemical response of eluent, obtain the concentration of glycosylated hemoglobin, calculate the content of glycosylated hemoglobin in the sample.The glycosylated hemoglobin recognizer is with the recognizer of glass pellet, silane heterozygosis colloidal sol or the Ago-Gel medium of phytolectin ConA or the modification of aminobenzene boric acid.In conjunction with liquid is the Heps buffer solution of pH value 7.0～8.5.Chemically modified electrode is aminothiopropionic acid modified gold electrode or platinum and glass carbon modified electrode.Electroactive micromolecule is the potassium ferricyanide or hydrogen peroxide.Eluent is a pH value 4.5, contains the 0.1mol/L citric acid-sodium citrate buffer of 0.2%triton.This device is for to be made up of application of sample control device, tripping device and proving installation, and wherein the application of sample control device is connected by delivery pipe with tripping device, and tripping device is connected with proving installation.The application of sample control device is by micro-processor controlled peristaltic pump.Tripping device is the glycated proteins recognizer.Proving installation is a chemically modified electrode.
Beneficial effect: the present invention utilizes the specific interaction of phytolectin or boric acid base group and glycosylated hemoglobin, prepare little separating column, and combined with electrochemical analyzes easy, easy row, inexpensive characteristics, set up the separation and the detection method of glycosylated hemoglobin concentration in a kind of blood.The more existing glycosylated hemoglobin analytical approach of this method has the following advantages:
(1) utilize immobilization phytolectin or the boric acid base group recognition reaction to glycosylated hemoglobin, the realization glycosylated hemoglobin separates with haemoglobin, and detects its content respectively with electrochemical method.The discrete testing process need not used large-scale instrument such as spectral detection or chromatography of ions detection etc., avoids using high toxic materials such as Drabkin reagent, TMB, has good application prospects.
(2) this method shows good accuracy, repeatability and stable, and the preparation method is simple, detects the more existing assay method of cost, and is much lower.
(3) the electrochemical apparatus convenient and flexible operation, cost is lower, analysis speed is fast, be applicable to clinical fast detecting and the exploitation portable instrumentation.
The present invention is by grafting phytolectin or boric acid base group on little glass bead, heterozygosis silicon gel, chitosan gel rubber and Ago-Gel, and be filled in the glass tube as the little separating column of glycosylated hemoglobin, utilize immobilization phytolectin or boric acid base group recognition reaction to glycosylated hemoglobin, the realization glycosylated hemoglobin separates with haemoglobin, this separating column is made simple, and has good chemical stability and bio-compatibility.It is combined with above-mentioned modified electrode, utilize electroactive micromolecule and reduced hemoglobin molecule generation oxidation-reduction reaction, and carry out Amperometric Detection Coupled according to the electroactive material that generates, foundation is used for the assay method of blood haemoglobin, saccharification hemoglobin content, have high sensitivity and selectivity, have good application prospects.Because Electrochemical Detection is simple to operate, cost is lower, analysis speed is fast, carry out fast measuring after being expected to realize the fast measuring of clinical glycosylated hemoglobin and glycosylated hemoglobin being separated wash-out.
Description of drawings
Fig. 1 is the process flow diagram of the electrochemical detection method of saccharification hemoglobin content.
Embodiment
Embodiment 1:
The preparation of glycosylated hemoglobin recognizer
(1) glass pellet of the little 5-10 micron of particle diameter is earlier with 0.1mol/L sodium hydroxide solution activation 1 hour, join in 10mmol/L trimethoxy-solution after clear water is cleaned and soaked 2 hours, promptly get trimethoxy silane and modify glass bead, and at glass bead surface this reactive group of introducing-CHO.Wash centrifugal after, the glass pellet of modified was soaked 5 hours in 10mmol/L phytolectin ConA (pH value 7.4) or aminobenzene BAS respectively, phosphate buffered solution with pH7.4 is washed 3 times, promptly get phytolectin ConA or aminobenzene boric acid and modify glycosylated hemoglobin identification medium, insert glass tube, promptly get the glycosylated hemoglobin separating column after the curing.
(2) press Si: H
21: 4 ratio of O mol ratio is got a certain amount of tetraethoxysilane or tetraethoxysilane and is accounted for silicon mole total amount 5,10,20,30,40% triethoxy-3-silane mixture places gauge water, the 1mol/L acetic acid that adds Si and water integral molar quantity 10%, after ultrasonic hydrolysis also at room temperature left standstill 2 hours in 3 hours, ratio added 10mmol/L phytolectin ConA (pH value 7.4) or aminobenzene BAS in 1: 1 by volume, after fully mixing, insert glass tube, promptly get the glycosylated hemoglobin separating column after the curing.
(3) in Ago-Gel, add 1: 8 CDI of mol ratio, reaction is 48 hours in 4 ℃ of refrigerators, thereby active amino on the Ago-Gel surface graft, shake reacted 24 hours in the glutaraldehyde cross-linking agent of adding and CDI equivalent and 4 ℃ of refrigerators of aminobenzene boric acid again, promptly get the boron Ago-Gel, insert glass tube, promptly get the glycosylated hemoglobin separating column after the curing.
The separation detection of glycosylated hemoglobin in the blood
(1) optimization of separation condition comprises following five aspects:
A) separating medium is selected: phytolectin or the aminobenzene boric acid grafting density difference on different carriers, so its separation efficiency is also inequality.Above-mentioned three kinds of identification media are inserted respectively in 2.5 * 80mm glass tube, solidified after 24 hours, it is constant to wash to the post the medium packing volume with 0.1M pH6.8 phosphate buffered solution.With saccharification hemoglobin content is that 10% haemoglobin standard liquid was circulated throughout post 30 minutes, the content of glycosylated hemoglobin in the liquid behind the spectral detection post, find that the pillar separation efficiency of filling with the boron Ago-Gel is the highest, after crossing post in 30 minutes, almost detect existence less than glycosylated hemoglobin.
B) retention time is selected in the post: the hemoglobin solutions residence time difference in post that contains glycosylated hemoglobin, the separation efficiency of glycosylated hemoglobin is also different, with saccharification hemoglobin content is that 10% haemoglobin standard liquid keeps 2 respectively in post, 3,5,10,20,30 minutes, the content of glycosylated hemoglobin in the liquid behind the spectral detection post, discovery has 2% glycosylated hemoglobin to exist after keeping in 2 minutes, after keeping in 3 minutes, there is 1.2% glycosylated hemoglobin to exist, after keeping in 5 minutes, there is 0.8% glycosylated hemoglobin to exist, and after keeping in 10 minutes, almost detects existence less than glycosylated hemoglobin.Therefore retention time was advisable with 2-10 minute.
C) selection of column internal diameter and column length: the size of column internal diameter has influence on the flow velocity of sample in post, this is particularly important to current system, therefore pump speed is mainly seen in the selection of column internal diameter, can in post, at the uniform velocity flow with sample for good, the peristaltic pump flow velocity that we select for use is 12 rev/mins, be 0.6mL/ minute, select the 2.5mm internal diameter tube to mate the most.And the separation efficiency of post is relevant with column length, we select 2.5 * 25,40,60,80, the glass tube filled media of 100mm, inject the haemoglobin standard liquid that 20 microlitres contain glycosylated hemoglobin 10%, kept 5 minutes, and found that the 40mm column length can separate glycosylated hemoglobin fully, we select the 80mm column length can separate the higher concentration glycosylated hemoglobin that may occur fully.
D) select in conjunction with liquid: the specific interaction between boron Ago-Gel and the glycosylated hemoglobin with combine the liquid kind and the pH value is relevant, its pH value of binding soln commonly used should be greater than 7.0, this be because boric acid base group in the pH value greater than the binding ability that had in 7.0 o'clock with the glycated proteins maximum, the haemoglobin sample that will contain glycosylated hemoglobin 10% is respectively 7.0 in the pH value that contains protein acid 2%, 7.5,8.0,8.5,9.0 phosphate buffered solution or Tris or Heps buffer solution in the dilution 50 times, and in above-mentioned boron Ago-Gel post, kept 10 minutes, the spectral detection separating effect, find to use Heps buffer solution separating effect best, and the pH value is high more, separate complete more, when the pH value detects less than glycosylated hemoglobin in the liquid behind post greater than 8.0 the time, thus we to select best combination liquid be the Heps buffer solution of pH value 8.5.
E) eluent is selected: eluent commonly used has acetic acid-sodium acetate buffer solution (pH value 4.0) solution, sorbitol aqueous solution (pH value 6.8) and the citric acid-sodium citrate buffer (pH value 4.5) of moderate acid.We find to use citric acid-sodium citrate buffer (pH value 4.5) elute effect the best of the 0.1mol/L that contains 0.2%triton, one time eluting rate can reach more than 98%, substantially detect existence during the secondary wash-out less than glycosylated hemoglobin, therefore the citric acid-sodium citrate buffer (pH value 4.5) of selecting to contain the 0.1mol/L of 0.2%triton is an elute soln, and illustrates that thus our pillar is reusable.
(2) detect behind the post of haemoglobin,
A) aminothiopropionic acid modified gold electrode preparation: golden disc electrode (the gold surface diameter is 1mm) uses the aluminium oxide slurry polishing to minute surface earlier on fur, soaked 5 hours in the phosphate buffered solution that contains the 5mmol/L aminothiopropionic acid (pH value 7.0) with the clean back of redistilled water supersound washing, the redistilled water supersound washing gets final product, and its surface coverage is greater than 1.6 * 10
-10Mol/cm
-2
B) platinum and glass-carbon electrode are modified: platinum disk electrode (the gold surface diameter is 1mm) uses the aluminium oxide slurry polishing to minute surface earlier on fur with glass-carbon electrode (glass carbon surface diameter is 3mm), clean with the redistilled water supersound washing, after drying up, pastes nitrogen a cellulose acetate film and fixing stand-by thereon with o shape circle.
C) electroactive micromolecule is selected: because about haemoglobin more than 99% exists to go back the ortho states form in the blood, electroactive micromolecule such as the potassium ferricyanide and hydrogen peroxide etc. can diffuse to haemoglobin electric activity center place and go back ortho states galvanochemistry micromolecule with the oxidation-reduction reaction generation of its generation exchange electronics, and further be diffused into take place on the electrode the reduction reaction of electronics, thereby provide reduction current, the size of this reduction current is directly proportional with the concentration of haemoglobin, therefore can be used for the mensuration of haemoglobin in the blood.Because hydrogen peroxide easily decomposes, so we select the potassium ferricyanide as electroactive micromolecule, and its addition is controlled at about 10 times hemoglobin concentration.
D) measuring best current potential selects: the haemoglobin such as 120g/L and the 150g/L that add the equivalent concentration known in the phosphate buffered solution of 0.1mol/L pH 6.8, it is 30mmol/L that the potassium ferricyanide of adding capacity makes its concentration, change different potentials, measure the value of reduction current respectively with modified gold electrode, platinum or glass-carbon electrode, seek and measure best current potential, to obtain optimum sensing range and sensitivity.
Therefore e) the pH value of buffer solution: haemoglobin just has optimum activity in the normal pH condition of human body, prepares haemoglobin standard liquid and measures and should select neutrality or slightly acidic solution for use with buffer solution as far as possible.
(3) measuring system:
The glycosylated hemoglobin measurement comprises and separating and test two parts that test macro of one-tenth capable of being combined such as accompanying drawing 1 wherein include peristaltic pump, separating column and detection chip, and its flow velocity and application of sample amount are by system controlled by computer, and separating column caliber and flow velocity will mate.
(4) typical curve is drawn and is proofreaied and correct:
A) typical curve is drawn: the response magnitude difference on the different modifying electrode, therefore different electrodes are also inequality at the current signal that same hemoglobin concentration provides, oxidation current with same determination of electrode variable concentrations haemoglobin standard solution, the drawing standard curve is determined the optimum range of linearity.
B) saccharification hemoglobin content is measured: add the glycosylated hemoglobin sample in measuring system, the current-responsive of liquid behind the measuring column is obtained corresponding hemoglobin concentration from typical curve.In separating column, add eluent, measure its current-responsive with modified electrode, obtain corresponding hemoglobin concentration from typical curve, as the concentration of glycosylated hemoglobin, obtain the content of glycosylated hemoglobin in the sample divided by the integral molar quantity of glycosylated hemoglobin and haemoglobin with the molar weight of glycosylated hemoglobin.
C) typical curve is proofreaied and correct: use modified electrode that the hemoglobin concentration in the blood sample is detected, read hemoglobin concentration from corresponding standard curve, by the numeric ratio measured with clinical detection numerical value and standard method, draw related coefficient and corresponding standard curve is proofreaied and correct correctness and accuracy that raising detects.
Embodiment 2:
A kind of electrochemical detection method of saccharification hemoglobin content, whole blood sample is used in conjunction with after 30-70 times of the liquid dilution, cross the glycated proteins recognizer, in the whole blood sample effluent of glycated proteins recognizer, add electroactive micromolecule, and with the electrochemical response of solution behind the chemically modified electrode measuring column, obtain the concentration a of haemoglobin; With eluent the glycated proteins recognizer is carried out wash-out, measure the electrochemical response of eluent, obtain the concentration b of glycosylated hemoglobin, calculate the content that b/ (b+a) obtains glycosylated hemoglobin in the sample.The glycosylated hemoglobin recognizer is with the recognizer of glass pellet, silane heterozygosis colloidal sol or the Ago-Gel medium of phytolectin ConA or the modification of aminobenzene boric acid.In conjunction with liquid is the Heps buffer solution of pH value 7.0～8.5.Chemically modified electrode is aminothiopropionic acid modified gold electrode or platinum and glass carbon modified electrode.Electroactive micromolecule is the potassium ferricyanide or hydrogen peroxide.Eluent is a pH value 4.5, contains the 0.1mol/L citric acid-sodium citrate buffer of 0.2%triton.A kind of device of realizing the electrochemical detection method of saccharification hemoglobin content, this device is for to be made up of application of sample control device, tripping device and proving installation, wherein the application of sample control device is connected by delivery pipe with tripping device, and the tripping device outlet is connected with the proving installation injection port.The application of sample control device is by micro-processor controlled peristaltic pump.Tripping device is the glycated proteins recognizer.Proving installation is a chemically modified electrode.
Below measure with the aminothiopropionic acid modified gold electrode that glycosylated hemoglobin is an example in the blood:
1. aminothiopropionic acid modified gold electrode preparation
Gold disc electrode (the gold surface diameter is 1mm) uses the aluminium oxide slurry polishing to minute surface earlier on fur, soaked 5 hours in the phosphate buffered solution that contains the 5mmol/L aminothiopropionic acid (pH value 7.0) with the clean back of redistilled water supersound washing, the redistilled water supersound washing gets final product, and its surface coverage is greater than 1.6 * 10
-10Mol/cm
-2
2. the optimization of test condition
A) measuring current potential selects: the haemoglobin such as 120g/L and the 150g/L that add the equivalent concentration known in the phosphate buffered solution of 0.1mol/L pH6.8, it is 30mmol/L that the potassium ferricyanide of adding capacity makes its concentration, change different potentials, measure the value of reduction current, seek and measure best current potential, to obtain optimum sensing range and sensitivity.Experimental result shows that applying current potential has maximum current-responsive when 0.30V.
B) the pH value of buffer solution: haemoglobin just has optimum activity in the normal pH condition of human body, and experimental result shows that electrode provides peak response in dilution pH6.5-7.4 scope, so we select for use the phosphate buffer of pH7.0 as dilution.
3. typical curve is drawn
Use the aminothiopropionic acid modified gold electrode, measure the reduction current of same haemoglobin standard solution, the repeatability of checking electrode at 0.30V.Measure of the reduction current response of different hemoglobin concentration, the drawing standard curve at 0.30V.
Experimental result shows that this modification has good repeatability, and is less than 7%, and linear in hemoglobin concentration 50g/L～400g/L scope to the measuring error of same hemoglobin concentration.
4. content of hemoglobin detects in the blood sample
Under optimal experimental conditions, with whole blood sample with the Heps of pH value 8.5 in conjunction with 50 times of liquid dilutions, cross 2.5 80cm boron Ago-Gel separating columns, the electrochemical response of solution behind the measuring column, the concentration of reading haemoglobin according to current value from typical curve; Contain the 0.1mol/L citric acid-sodium citrate eluant solution of 0.2%triton with pH value 4.5, measure the electrochemical response of eluent, the concentration of reading glycosylated hemoglobin according to current value from typical curve; The content of glycosylated hemoglobin in the sample is obtained in calculating, and relatively proofreaies and correct with the standard method measured value.Utilize the haemoglobin value and the standard method contrast of 100 samples that the present invention measures, the result of mensuration has good consistance.
Claims (10)
1. the electrochemical detection method of a saccharification hemoglobin content, it is characterized in that: whole blood sample is used in conjunction with after 30-70 times of the liquid dilution, cross the glycated proteins recognizer, in the whole blood sample effluent of glycated proteins recognizer, add electroactive micromolecule, and with the electrochemical response of solution behind the chemically modified electrode measuring column, obtain the concentration a of haemoglobin; With eluent the glycated proteins recognizer is carried out wash-out, measure the electrochemical response of eluent, obtain the concentration b of glycosylated hemoglobin, calculate the content that b/ (b+a) obtains glycosylated hemoglobin in the sample.
2. the electrochemical detection method of saccharification hemoglobin content according to claim 1 is characterized in that the recognizer of described glycosylated hemoglobin recognizer with glass pellet, silane heterozygosis colloidal sol or the Ago-Gel medium of phytolectin ConA or the modification of aminobenzene boric acid.
3. the electrochemical detection method of saccharification hemoglobin content according to claim 1 is characterized in that described is the Heps buffer solution of pH value 7.0～8.5 in conjunction with liquid.
4. the electrochemical detection method of saccharification hemoglobin content according to claim 1 is characterized in that described chemically modified electrode is aminothiopropionic acid modified gold electrode or platinum and glass carbon modified electrode.
5. the electrochemical detection method of saccharification hemoglobin content according to claim 1 is characterized in that described electroactive micromolecule is the potassium ferricyanide or hydrogen peroxide.
6. the electrochemical detection method of saccharification hemoglobin content according to claim 1 is characterized in that described eluent is a pH value 4.5, contains the 0.1mol/L citric acid-sodium citrate buffer of 0.2%triton.
7. device of realizing the electrochemical detection method of the described saccharification hemoglobin content of claim 1, it is characterized in that this device is for to be made up of application of sample control device, tripping device and proving installation, wherein the application of sample control device is connected by delivery pipe with tripping device, and the tripping device outlet is connected with the proving installation injection port.
8. the device of the electrochemical detection method of saccharification hemoglobin content according to claim 7 is characterized in that described application of sample control device is by micro-processor controlled peristaltic pump.
9. the device of the electrochemical detection method of saccharification hemoglobin content according to claim 7 is characterized in that described tripping device is the glycated proteins recognizer.
10. the device of the electrochemical detection method of saccharification hemoglobin content according to claim 7 is characterized in that described proving installation is a chemically modified electrode.
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| CN102282468A (en) * | 2008-11-13 | 2011-12-14 | 模式诊断有限公司 | Electrode, electrochemical sensor and apparatus, and methods for operating the same |
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| CN103430028A (en) * | 2010-09-16 | 2013-12-04 | 通用医疗公司 | Red blood cell dynamics for diagnosis |
| CN104024841A (en) * | 2011-09-15 | 2014-09-03 | 株式会社Ndd | Glycated protein measurement sensor and portable glycated protein measurement apparatus including same |
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| CN107064265A (en) * | 2017-05-23 | 2017-08-18 | 中国科学院上海高等研究院 | A kind of electrochemica biological sensor for being used for HbA1c detections of MPBA modifications and its preparation and application |
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| CN104024841A (en) * | 2011-09-15 | 2014-09-03 | 株式会社Ndd | Glycated protein measurement sensor and portable glycated protein measurement apparatus including same |
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| CN107064265A (en) * | 2017-05-23 | 2017-08-18 | 中国科学院上海高等研究院 | A kind of electrochemica biological sensor for being used for HbA1c detections of MPBA modifications and its preparation and application |
| CN107192831A (en) * | 2017-05-24 | 2017-09-22 | 青岛科技大学 | A kind of method that chemiluminescence detects glycosylated hemoglobin |
| CN107192831B (en) * | 2017-05-24 | 2019-03-05 | 青岛科技大学 | A kind of method of chemiluminescence detection glycosylated hemoglobin |
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