CN104931563A - High-selective potential glucose sensor - Google Patents
High-selective potential glucose sensor Download PDFInfo
- Publication number
- CN104931563A CN104931563A CN201510287108.8A CN201510287108A CN104931563A CN 104931563 A CN104931563 A CN 104931563A CN 201510287108 A CN201510287108 A CN 201510287108A CN 104931563 A CN104931563 A CN 104931563A
- Authority
- CN
- China
- Prior art keywords
- glucose
- probe
- acid
- nucleoprotamine
- electric potential
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Investigating Or Analysing Biological Materials (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention belongs to the technical field of biochemical analytical testing, and particularly relates to a simple, high-selective and enzyme-free potential glucose detection method. A boric acid derivative containing double boric acid groups is used as a probe, and after condensation reaction takes place between the probe and glucose, an oligomer in the form of the polyanion can be produced; by utilizing the electrostatic interaction between the oligomer in the form of the polyanion and protamine in the form of the polycation and a protamine-sensitive polymer film electrode, potential sensing of the glucose can be realized. Because other monosaccharides and the probe cannot form oligomers, the potential response of protamine cannot be affected, i.e., detection is interference-free. The high-selective potential glucose sensor can be used for carrying out the high-selective, enzyme-free detection of the glucose.
Description
Technical field
The invention belongs to glucose analysis technical field of measurement and test, be specifically related to a kind of simple, without the electric potential type glucose sensor of enzyme, high selectivity and application thereof.
Background technology
Carbohydrate has important physiological significance in the vital movement of human body, and in blood, abnormal contents of saccharide and metabolic disorder have relation closely, and thus blood sugar level Chang Zuowei disease is as the mark of diabetes, cardiovascular and cerebrovascular disease and obesity.Meanwhile, blood sugar is also the project often detected in postoperative clinical care, is starved of a kind of simple and easy to do detection method.Traditional carbohydrate detection method needs by means of glucose oxidase as blood glucose meter, although this kind of sensor has good selectivity and sensitivity usually, but due to the instability of glucose oxidase, very easily be subject to environmental baseline as the impact of temperature, pH etc., so this kind of sensor stability is poor.Develop a kind of glucose sensor without enzyme will contribute to improving this present situation.
Boric acid can form the borate of ring-type with c/s-diol, utilizes this character, boric acid can as recognition component for build sugar without enzyme sensor.Had nearly decades and be much in the news out based on the glucose sensor of boric acid, this kind of sensor, except using boric acid base group as the recognition component of glucose, also needs another group to report identifying; Synchronous signal reads needs complicated optical device more, operates more loaded down with trivial details.Utilize boronate because of as recognition component, developing a kind of easy glucose sensor is still a challenge.
Summary of the invention
The object of the present invention is to provide a kind of electric potential type glucose sensor and application thereof of high selectivity.
For achieving the above object, the technical solution used in the present invention is:
A kind of electric potential type glucose sensor of high selectivity, use the boronic acid derivatives containing two boric acid base group as the probe to glucose identification, using the polymer film of cationite doping as electrode, and produce electric potential signal using polycation nucleoprotamine as indication ion;
Described boric acid is inorganic or organic boronic, the various boronic acid derivatives containing boric acid base group.
The described various boronic acid derivatives containing boric acid base group be containing two boronate because of lipophilicity boronic acid derivatives.
Described contain two boronate because of lipophilicity boronic acid derivatives be 4,4'-biphenyl hypoboric acid, 4,4'-benzene hypoboric acid, 9,9-dioctyl fluorene-2,7-hypoboric acid, 9,9-dihexyl fluorenes-2,7-hypoboric acid, 9,9-two dodecyl fluorenes-2,7-hypoboric acid or [9, two (2-ethylhexyl)-9H-fluorenes-2,7-bis-base of 9-] hypoboric acid.
Described electrode is made up of three parts: film matrix, plastifier and cationite; Film matrix is Polyvinylchloride, polyurethane, silicon rubber, acetate fiber, polyacrylamide or polymethylacrylic acid-dimethylaminoethyl methacrylate; Plastifier is ortho-nitrophenyl octyl ether, dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl adipate or di-n-octyl sebacate; Cationite is sodium tetraphenylborate, tetraphenyl borate derivative salt or dinonylnaphthalene sulfonic acid salt.
Utilize on probe after boric acid base group and glucose generation condensation reaction, produce the oligomer of polyanion form; Electrostatic interaction between recycling polyanion oligomer and polycation nucleoprotamine, makes to produce potential response to the electrode of nucleoprotamine sensitivity, and then realizes the potentiometric sensors to glucose.
An application for the electric potential type glucose sensor of high selectivity, utilizes in probe and testing sample after glucose generation condensation reaction, reactant again with generation electrostatic interaction, make the electrode to sensitivity causes potential response, and then the detection glucose of qualitative/quantitative.
Described testing process is:
(1) using the polymer sensitive membrane of cationite doping as working electrode, the boronic acid derivatives containing two boric acid base group as the probe to glucose identification, and carries out potentiometric detection using polycation nucleoprotamine as indication ion;
(2) writing task electrode is the potential change of the carbonate buffer solution of 10.5 at the pH containing the probe of 100 μMs and the nucleoprotamine of 1 μ g/mL;
(3) to containing the glucose solution adding variable concentrations in carbonic acid (pH the is 10.5) buffer solution of 100 μMs of hypoboric acid probes, after variable concentrations reaction 10min, then the nucleoprotamine of 1 μ g/mL is added respectively, the situation of change of record current potential;
(4) with the potential changing value obtained in step (2) for initialize signal, (3) potential change obtained in is the signal under each concentration of glucose, two signal values subtract each other as final quantifiable signal, with final quantifiable signal for ordinate concentration of glucose is for horizontal ordinate drawing curve;
(5) according to the step of (1)-(3), actual sample is tested, according to the concentration value of glucose in standard working curve calculation sample.
The advantage that the present invention has: the present invention utilizes the condensation reaction of two boric acid and glucose, reduces the design difficulty of glucose identity, improves the selectivity of detection simultaneously; Utilize the electrostatic interaction between polyanion oligomer and polycation nucleoprotamine and polymer membrane electrode to nucleoprotamine sensitivity that are formed, present invention achieves simple, the high selectivity to glucose, detect without enzyme.
Accompanying drawing explanation
The course of reaction of the hypoboric acid probe that Fig. 1 provides for the embodiment of the present invention and glucose.
The Cleaning Principle that Fig. 2 provides for the embodiment of the present invention.
Fig. 3 A for the embodiment of the present invention provide with 4,4'-biphenyl hypoboric acid for probe, be that indication ion detects the real-time potential response curve of glucose with nucleoprotamine.
Fig. 3 B for the embodiment of the present invention provide with 4,4'-biphenyl hypoboric acid for probe, with nucleoprotamine be indication ion detect glucose and standard working curve.
The selectivity of the glucose Copper diethlydithiocarbamate that Fig. 4 provides for the embodiment of the present invention.
Embodiment
The present invention utilizes the covalent bond effect of boric acid base group and c/s-diol, boronic acid derivatives probe containing two boric acid base groups can form the oligomerization borate of ring-type and linear polyanion form with the glucose containing two c/s-diol groups, other monose, if fructose and galactose etc. are only containing a c/s-diol group, thus can not form oligomer.Utilize the electrostatic interaction between the oligomerization borate of the polyanion form formed and polycation nucleoprotamine, the polyanion formed significantly can reduce the potential response of polycation nucleoprotamine on the polymer membrane electrode of dinonylnaphthalene sulfonic acid salt dopping, accordingly, the high selectivity that can realize glucose detects.Compared with traditional detection method, this invention does not need to carry out complicated probe design, simultaneously easy and simple to handle, can realize the high selectivity of glucose without enzyme potentiometric detection.
Embodiment 1
The present invention is that probe in detecting glucose is for example with 4,4'-biphenyl hypoboric acid.Its operation steps is as follows:
(1) preparation of polymer membrane electrode
Take 196mg Polyvinylchloride, 196mg ortho-nitrophenyl octyl ether, 12mg dinonylnaphthalene sulfonic acid be dissolved in 3.5mL tetrahydrofuran, pouring fixing internal diameter on a glass after stirring into is in the glass ring of 3.5cm.After treating tetrahydrofuran volatilization, using card punch film to be cut into sequin that internal diameter is 3mm and pasting bottom cover has on the liquid-transfering gun rifle head of pvc pipe.Use the NaCl solution of 12mM as internal-filling liquid and activating solution activated electrode, stand-by.
(2) potentiometric detection of glucose
1. using the polymer sensitive membrane of cationite doping as working electrode, the boronic acid derivatives containing two boric acid base group as the probe to glucose identification, and carries out potentiometric detection using polycation nucleoprotamine as indication ion;
2. use 4, the 4'-benzene hypoboric acid of dimethyl sulfoxide preparation 100mM, be add above-mentioned solution in the carbonate buffer solution of 10.5 to pH, make the diborated ultimate density of 4,4'-biphenyl be 100 μMs.Then add the nucleoprotamine of 1 μ g/mL, writing task electrode potential changes;
3. re-use 4, the 4'-benzene hypoboric acid of dimethyl sulfoxide preparation 100mM, be add above-mentioned solution in the carbonate buffer solution of 10.5 to pH, make the diborated ultimate density of 4,4'-biphenyl be 100 μMs.Add in solution glucose solution (make its ultimate density be 0.2,2,5,8,10,13mM), the nucleoprotamine then adding 1 μ g/mL, record potential change situation (see figure A).
4. with step 2. in obtain potential changing value for initialize signal, 3. the potential change obtained in is the signal under each concentration of glucose, two signal values subtract each other as final quantifiable signal, with final quantifiable signal for ordinate concentration of glucose is for horizontal ordinate drawing curve (see Fig. 3 B);
(3) selectivity test
Use the glucose of method to variable concentrations of description in (2), fructose, galactose, mannose and their potpourri to test, the selectivity of gained the results are shown in Figure 4.It is less to the interference of glucose detection when the fructose of 0.5mM, galactose and mannose exist as shown in Figure 4.
Claims (7)
1. the electric potential type glucose sensor of a high selectivity, it is characterized in that: use the boronic acid derivatives containing two boric acid base group as the probe to glucose identification, using the polymer film of cationite doping as electrode, and produce electric potential signal using polycation nucleoprotamine as indication ion;
Described boric acid is inorganic or organic boronic, the various boronic acid derivatives containing boric acid base group.
2., by the electric potential type glucose sensor of high selectivity according to claim 1, it is characterized in that: the described various boronic acid derivatives containing boric acid base group be containing two boronate because of lipophilicity boronic acid derivatives.
3. by the electric potential type glucose sensor of high selectivity according to claim 2, it is characterized in that: described contain two boronate because of lipophilicity boronic acid derivatives be 4,4'-biphenyl hypoboric acid, 4,4'-benzene hypoboric acid, 9,9-dioctyl fluorene-2,7-hypoboric acid, 9,9-dihexyl fluorenes-2,7-hypoboric acid, 9, the two dodecyl fluorenes-2 of 9-, 7-hypoboric acid or [two (2-ethylhexyl)-9H-fluorenes-2,7-bis-base of 9,9-] hypoboric acid.
4., by the electric potential type glucose sensor of high selectivity according to claim 1, it is characterized in that: described electrode is made up of three parts: film matrix, plastifier and cationite; Film matrix is Polyvinylchloride, polyurethane, silicon rubber, acetate fiber, polyacrylamide or polymethylacrylic acid-dimethylaminoethyl methacrylate; Plastifier is ortho-nitrophenyl octyl ether, dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl adipate or di-n-octyl sebacate; Cationite is sodium tetraphenylborate, tetraphenyl borate derivative salt or dinonylnaphthalene sulfonic acid salt.
5. by the electric potential type glucose sensor of high selectivity according to claim 1, it is characterized in that: utilize on probe after boric acid base group and glucose generation condensation reaction, the oligomer of generation polyanion form; Electrostatic interaction between recycling polyanion oligomer and polycation nucleoprotamine, makes to produce potential response to the electrode of nucleoprotamine sensitivity, and then realizes the potentiometric sensors to glucose.
6. the application of the electric potential type glucose sensor of a high selectivity according to claim 1, it is characterized in that: to utilize in probe and testing sample after glucose generation condensation reaction, reactant again with generation electrostatic interaction, make the electrode to sensitivity causes potential response, and then the detection glucose of qualitative/quantitative.
7., by the application of novel electric potential type glucose sensor according to claim 6, it is characterized in that: described testing process is:
(1) using the polymer sensitive membrane of cationite doping as working electrode, the boronic acid derivatives containing two boric acid base group as the probe to glucose identification, and carries out potentiometric detection using polycation nucleoprotamine as indication ion;
(2) writing task electrode is the potential change of the carbonate buffer solution of 10.5 at the pH containing the probe of 100 μMs and the nucleoprotamine of 1 μ g/mL;
(3) to containing the glucose solution adding variable concentrations in carbonic acid (pH the is 10.5) buffer solution of 100 μMs of hypoboric acid probes, after variable concentrations reaction 10min, then the nucleoprotamine of 1 μ g/mL is added respectively, the situation of change of record current potential;
(4) with the potential changing value obtained in step (2) for initialize signal, (3) potential change obtained in is the signal under each concentration of glucose, two signal values subtract each other as final quantifiable signal, with final quantifiable signal for ordinate concentration of glucose is for horizontal ordinate drawing curve;
(5) according to the step of (1)-(3), actual sample is tested, according to the concentration value of glucose in standard working curve calculation sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510287108.8A CN104931563B (en) | 2015-05-29 | 2015-05-29 | A kind of electric potential type glucose sensor of high selectivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510287108.8A CN104931563B (en) | 2015-05-29 | 2015-05-29 | A kind of electric potential type glucose sensor of high selectivity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104931563A true CN104931563A (en) | 2015-09-23 |
| CN104931563B CN104931563B (en) | 2017-09-29 |
Family
ID=54118832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510287108.8A Active CN104931563B (en) | 2015-05-29 | 2015-05-29 | A kind of electric potential type glucose sensor of high selectivity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104931563B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105548302A (en) * | 2016-02-01 | 2016-05-04 | 中国科学院烟台海岸带研究所 | Detecting method of free radical reaction |
| CN106645324A (en) * | 2016-11-30 | 2017-05-10 | 辽宁大学 | Imprinted molecular polymer and molecularly imprinted electrochemical sensor based on boric acid groups |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102262116A (en) * | 2010-05-28 | 2011-11-30 | 中国科学院烟台海岸带研究所 | Method and device for detecting polymer film ion selective electrode |
| CN102313767A (en) * | 2010-06-29 | 2012-01-11 | 中国科学院烟台海岸带研究所 | High-sensitivity polyion-selective electrode and testing method thereof |
| CN102445483A (en) * | 2011-09-30 | 2012-05-09 | 中国科学院烟台海岸带研究所 | Method for detecting heparins |
| CN104597090A (en) * | 2014-12-10 | 2015-05-06 | 中国科学院烟台海岸带研究所 | Enzyme-free potentiometric glucose sensor and detection method thereof |
-
2015
- 2015-05-29 CN CN201510287108.8A patent/CN104931563B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102262116A (en) * | 2010-05-28 | 2011-11-30 | 中国科学院烟台海岸带研究所 | Method and device for detecting polymer film ion selective electrode |
| CN102313767A (en) * | 2010-06-29 | 2012-01-11 | 中国科学院烟台海岸带研究所 | High-sensitivity polyion-selective electrode and testing method thereof |
| CN102445483A (en) * | 2011-09-30 | 2012-05-09 | 中国科学院烟台海岸带研究所 | Method for detecting heparins |
| CN104597090A (en) * | 2014-12-10 | 2015-05-06 | 中国科学院烟台海岸带研究所 | Enzyme-free potentiometric glucose sensor and detection method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105548302A (en) * | 2016-02-01 | 2016-05-04 | 中国科学院烟台海岸带研究所 | Detecting method of free radical reaction |
| CN106645324A (en) * | 2016-11-30 | 2017-05-10 | 辽宁大学 | Imprinted molecular polymer and molecularly imprinted electrochemical sensor based on boric acid groups |
| CN106645324B (en) * | 2016-11-30 | 2019-04-09 | 辽宁大学 | A kind of microsphere polymer and molecular imprinting electrochemical sensor based on boric acid base group |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104931563B (en) | 2017-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2004044120A3 (en) | Multiwell insert device that enables label free detection of cells and other objects | |
| Arrigan | Bioanalytical detection based on electrochemistry at interfaces between immiscible liquids | |
| CN108020589B (en) | Method for detecting calcium ions in seawater | |
| Volpi | Capillary electrophoresis of carbohydrates: from monosaccharides to complex polysaccharides | |
| CN104597090A (en) | Enzyme-free potentiometric glucose sensor and detection method thereof | |
| CN107525837B (en) | The method for detecting dopamine concentration in solution | |
| Li et al. | Simple chip electrophoresis titration of neutralization boundary with EDTA photocatalysis for distance-based sensing of melamine in dairy products | |
| Wang et al. | All-solid-state blood calcium sensors based on screen-printed poly (3, 4-ethylenedioxythiophene) as the solid contact | |
| CN106442515A (en) | Simple and low-cost silver ion visual quantitative detection method | |
| CN105954210A (en) | Convenient ATP (adenosine triphosphate) content detecting method adopting pressure-sensitive paint as signal reading tool | |
| Diba et al. | Amperometric sensing of sodium, calcium and potassium in biological fluids using a microhole supported liquid/gel interface | |
| CN104931563A (en) | High-selective potential glucose sensor | |
| CN102445483B (en) | Method for detecting heparins | |
| CN109459478B (en) | miRNA-21 electrochemical sensor based on copper-hexahydroxy triphenylene and detection method | |
| CN105259349B (en) | A kind of preparation for exempting to fix bio-sensing electrode and its application in label-free homogeneous photic electrification learns to farm residual detection and cancer diagnosis | |
| CN102221574A (en) | Linear sweep voltammetry for detecting vitamin content of blood sample | |
| CN107064265A (en) | A kind of electrochemica biological sensor for being used for HbA1c detections of MPBA modifications and its preparation and application | |
| Zhai et al. | Amperometric detection of carbohydrates with a portable silicone/quartz capillary microchip by designed fracture sampling | |
| CN103604854A (en) | Biosensor array based on ion sensitive field effective transistor | |
| CN105044338A (en) | Method for detecting thrombin based on barometer | |
| Wang et al. | Indirect electrochemical determination of ribavirin using boronic acid-diol recognition on a 3-aminophenylboronic acid-electrochemically reduced graphene oxide modified glassy carbon electrode (APBA/ERGO/GCE) | |
| Gao et al. | Sensitive Dual Electrochemical-Colorimetric Point-of-Care (POC) Sensor for the Rapid Detection of Mycoplasma pneumoniae | |
| Xiao et al. | Cathodic stripping determination of water in organic solvents | |
| CN104977334B (en) | A kind of experimental provision and method for measuring BOD | |
| CN105319247A (en) | Electric potential type glucose recognition element and glucose detection method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |