CN104597090A - Enzyme-free potentiometric glucose sensor and detection method thereof - Google Patents
Enzyme-free potentiometric glucose sensor and detection method thereof Download PDFInfo
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- CN104597090A CN104597090A CN201410753275.2A CN201410753275A CN104597090A CN 104597090 A CN104597090 A CN 104597090A CN 201410753275 A CN201410753275 A CN 201410753275A CN 104597090 A CN104597090 A CN 104597090A
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Abstract
Belonging to the technical field of biochemical analytical test, the invention specifically relates to an enzyme-free potentiometric glucose sensor with high selectivity and a detection method thereof. A boric acid derivative containing two boric acid groups is used as a glucose recognition molecule, and a quaternary ammonium salt doped polymer is taken as the electrode. The sensor provided by the invention is employed to detect the concentration of glucose in a whole blood sample, and the obtained result is consistent with that of commercially available glucometers.
Description
Technical field
The invention belongs to biochemical analysis technical field of measurement and test, be specifically related to a kind of high selectivity, without the electric potential type glucose sensor of enzyme and detection method thereof.
Background technology
Carbohydrate has important physiological significance in the vital movement of human body, and abnormal blood concentration of saccharide is often by the mark as metabolic disorder, and thus the detection of blood sugar has great importance.In clinical analysis and practical operation, blood sugar test generally completes by blood glucose meter.Blood glucose meter utilizes glucose oxidase identification and catalytic oxidation of glucose produces electroactive hydrogen peroxide, uses the redox current of the electrode detection hydrogen peroxide of miniaturization namely indirectly to achieve the detection of glucose.Although this kind of sensor has good selectivity and sensitivity usually, due to enzyme changeableness (being very easily subject to environmental baseline as the impact of temperature, pH etc.), the less stable of this kind of sensor.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 glucose without enzyme type sensor.Development in recent years is much based on the glucose sensor of boric acid, and this kind of sensor, except using the derivant of boric acid as except the identification molecule of glucose, also needs a reporter molecules to conduct identifying usually; Although some sensor does not need this kind of reporter molecules, spectroscopy signal that it uses reads the optical device of the many needs of means by means of complexity, and thus complex operation, cost are higher, be unsuitable for glucose simple, detect fast.Development a kind of simple and easy, be still a challenge without enzyme type glucose sensor fast.
Summary of the invention
The object of the present invention is to provide one simply, fast without enzyme electric potential type glucose sensor and detection method thereof.
For achieving the above object, the technical solution used in the present invention is:
Without an electric potential type glucose sensor for enzyme,
Use the boronic acid derivatives containing two boric acid base groups as the identification molecule of glucose, using the polymkeric substance of quaternary ammonium salt doping as electrode;
Described boronic acid derivatives is [methylene-two (3,1-phenylaminomethyl-2,1-phenyl)] hypoboric acid, [methylene-two (the third amino methyl-2,1-phenyl)] hypoboric acid or methylene-two (9,10-anthracene Methyaminomethyl-2,1-phenyl)] hypoboric acid.
Said derivative can prepare by the record in following list of references 1-5.
Utilize identify that the boric acid base group of molecule adulterates at anionite polymer film on the negative ion potential response that causes, identify that in molecule, two boric acid base groups mate with two pairs of syn diol structure of glucose on locus, itself and glucose form the covalent bond product of 1:1; The molecular recognition process of instruction boronic acid derivatives and glucose, and then realize the potentiometric detection of glucose.
Described electric potential type glucose sensor need conduct electric potential signal by polymer membrane electrode, and polymer membrane electrode is made up of three parts: film matrix, plastifier and anionite; Film matrix can be Polyvinylchloride, polyurethane, silicon rubber, acetate fiber, polyacrylamide, polymethylacrylic acid-dimethylaminoethyl methacrylate; Plastifier can be ortho-nitrophenyl octyl ether, dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl adipate, di-n-octyl sebacate; Anionite can be dotriacontyl monomethyl ammonium chloride, dotetracontane ammonium chloride, dotriacontyl monomethyl ammonium bromide, dotetracontane base ammonium bromide.
Without an application for the electric potential type glucose sensor of enzyme, utilize recognition component on polymer membrane electrode, cause the potential response of negative ion, and then the detection glucose of qualitative/quantitative.
Described testing process is:
(1) take polymer membrane electrode as working electrode, saturated calomel electrode carries out potentiometric detection for contrast electrode;
(2) writing task electrode is the initial potential value in the 50mM phosphate buffer solution of 8.0 at pH, in this solution, add 10
-5the boronic acid derivatives of M, record potential value is stablized to current potential;
(3) in above-mentioned solution, add glucose solution storing solution respectively, make the concentration of glucose in solution be respectively 10
-3, 10
-2.5, 10
-2, 10
-1.5and 10
-1m, the situation of change of record current potential;
(4) with different glucose produce electric potential signal changing value for ordinate, concentration of glucose is horizontal ordinate drawing standard working 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: used herein contain two boric acid base groups boronic acid derivatives and glucose form the compound of 1+1, realize the Selective recognition to glucose and detection, its binding ability, higher than the binding ability to its analogue, ensure that the high selectivity to glucose detection; Boric acid base group can produce negative ion potential response on the polymer film of anionite doping, thus can be directly used in the concentration of instruction glucose, enormously simplify the process of analytical test and step, decreases the kind of agents useful for same; Polymer film electric potential type sensing technology does not need to rely on complicated instrument and equipment, simultaneously electrode fabrication simple, with low cost, be easy to miniaturization, be very suitable for clinical and daily use.
Accompanying drawing explanation
Fig. 1 is Cleaning Principle figure of the present invention.
Fig. 2 is [methylene-two (3,1-phenylaminomethyl-2,1-phenyl)] diborated nuclear magnetic spectrogram.
The condition of different pH bottom electrode that Fig. 3 provides for the embodiment of the present invention to 1mM glucose (
■) and fructose (
zero) response condition figure.
The real-time potential response curve of the different glucose electrode that Fig. 4 provides for the embodiment of the present invention and standard working curve figure.
The reversible experiment figure of the electrode that Fig. 5 provides for the embodiment of the present invention.
The glucose of the variable concentrations that Fig. 6 provides for the embodiment of the present invention (
■) and potential response figure under fructose (0.1mM) and galactose (0.1mM) existence condition.
Embodiment
Use the boronic acid derivatives containing two boric acid base groups as the identification molecule of glucose, the negative ion potential response indication molecule identifying that the polymer film simultaneously utilizing boric acid base group to adulterate at anionite causes, can realize the high selectivity identification to glucose; The negative ion potential response that the polymer film utilizing boric acid base group to adulterate at anionite causes, can indicate the molecular recognition process of boronic acid derivatives and glucose, and then realize the potentiometric detection of glucose; The analogue of glucose such as the negative ion existed in fructose and galactose etc. and blood does not disturb the detection of glucose.By adding suitable screening agent, in blood, negative ion can be effectively eliminated the interference of electric potential signal.Cleaning Principle is shown in Fig. 1.
Embodiment 1
The present invention is with [methylene-two (3,1-phenylaminomethyl-2,1-phenyl)] hypoboric acid (its nuclear magnetic spectrogram is shown in Fig. 2) for identifying that Molecular Detection glucose is for example, and it can prepare according to the record in document 5.Its operation steps is as follows:
(1) preparation of polymer membrane electrode
Take 196mg Polyvinylchloride, 196mg ortho-nitrophenyl octyl ether, 4.54mg tridodecylmethylammonium ammonium chloride is 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 10mM as internal-filling liquid and activating solution activated electrode, stand-by.
(2) optimization of pH condition
Secure ph is in the phosphate buffer solution of 6.0,7.4,8.0,9.0 respectively, take polymer membrane electrode as indicator electrode, saturated calomel electrode is contrast electrode, record initial potential value.Use dimethyl sulfoxide preparation [methylene-two (3,1-phenylaminomethyl-2,1-phenyl)] hypoboric acid storing solution, hypoboric acid storing solution is added in above-mentioned phosphate buffer solution, make [methylene-two (3,1-phenylaminomethyl-2,1-phenyl)] diborated ultimate density is 10
-5m, record potential value.Add above-mentioned solution, make [methylene-two (3,1-phenylaminomethyl-2,1-phenyl)] diborated ultimate density be 50 μMs, record potential value.In above-mentioned solution, then add glucose and the fructose of variable concentrations more respectively, take potential changing value as ordinate, and sugared concentration is horizontal ordinate mapping.Experimental result is shown in Fig. 3.
(3) potentiometric detection of glucose
Use dimethyl sulfoxide preparation [methylene-two (3,1-phenylaminomethyl-2,1-phenyl)] hypoboric acid storing solution, be add above-mentioned solution in the phosphate buffer solution of 8.0 to pH, make [methylene-two (3,1-phenylaminomethyl-2,1-phenyl)] diborated ultimate density is 10
-5m, record potential value.After current potential is stable, in solution, add the glucose solution of variable concentrations, continue record potential value.Experimental result is shown in Fig. 4.
(4) reversibility of electrode test
Use the hydrochloric acid solution (ethanol containing 10% (volume fraction)) of 10Mm to rinse electrode 2 × 3 minutes, test electrode is to 10
-5m [methylene-two (3,1-phenylaminomethyl-2,1-phenyl)] diborated potential response.Experimental result is shown in Fig. 5.
(5) selectivity is investigated
Record variable concentrations glucose (
■) and potential response under fructose (0.1mM) and galactose (0.1mM) existence condition.Experimental result is shown in Fig. 6.
(6) actual sample test
Use this sensor and commercially available blood glucose meter to detect the blood sugar concentration in whole blood sample, testing result is in table 1.
Table 1
List of references
1K.Tsukagoshi and S.Shinkai,J.Org.Chem.,1991,56,4089-4091.
2Z.Q.Guo,I.Shin and J.Yoon,Chem.Commun.,2012,48,5956-4967.
3W.Yang,H.He and D.G.Drueckhammer,Angew.Chem.Int.Edit.,2001,40,1714-1718.
4T.D.James,P.Linnane and S.Shinkai,Chem.Commun.,1996,281-288.
5S.Arimori,L.I.Bosch,C.J.Ward and T.D.James,Tetrahedron Lett.,2002,43,911-913。
Claims (5)
1., without an electric potential type glucose sensor for enzyme, it is characterized in that:
Use the boronic acid derivatives containing two boric acid base groups as the identification molecule of glucose, using the polymkeric substance of quaternary ammonium salt doping as electrode;
Described boronic acid derivatives is [methylene-two (3,1-phenylaminomethyl-2,1-phenyl)] hypoboric acid, [methylene-two (the third amino methyl-2,1-phenyl)] hypoboric acid or methylene-two (9,10-anthracene Methyaminomethyl-2,1-phenyl)] hypoboric acid.
2. by the electric potential type glucose sensor without enzyme according to claim 1, it is characterized in that: utilize identify that the boric acid base group of molecule adulterates at anionite polymer film on the negative ion potential response that causes, identify that in molecule, two boric acid base groups mate with two pairs of syn diol structure of glucose on locus, itself and glucose form the covalent bond product of 1:1; The molecular recognition process of instruction boronic acid derivatives and glucose, and then realize the potentiometric detection of glucose.
3. by the electric potential type glucose sensor without enzyme described in claim 1 or 2, it is characterized in that: described electric potential type glucose sensor need conduct electric potential signal by polymer membrane electrode, and polymer membrane electrode is made up of three parts: film matrix, plastifier and anionite; Film matrix can be Polyvinylchloride, polyurethane, silicon rubber, acetate fiber, polyacrylamide, polymethylacrylic acid-dimethylaminoethyl methacrylate; Plastifier can be ortho-nitrophenyl octyl ether, dioctyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl adipate, di-n-octyl sebacate; Anionite can be dotriacontyl monomethyl ammonium chloride, dotetracontane ammonium chloride, dotriacontyl monomethyl ammonium bromide, dotetracontane base ammonium bromide.
4. an application for the electric potential type glucose sensor without enzyme according to claim 1, is characterized in that: utilize recognition component on polymer membrane electrode, cause the potential response of negative ion, and then the detection glucose of qualitative/quantitative.
5., by the application of the electric potential type glucose sensor without enzyme according to claim 4, it is characterized in that: described testing process is:
(1) take polymer membrane electrode as working electrode, saturated calomel electrode carries out potentiometric detection for contrast electrode;
(2) writing task electrode is the initial potential value in the 50mM phosphate buffer solution of 8.0 at pH, in this solution, add 10
-5the boronic acid derivatives of M, record potential value is stablized to current potential;
(3) in above-mentioned solution, add glucose solution storing solution respectively, make the concentration of glucose in solution be respectively 10
-3, 10
-2.5, 10
-2, 10
-1.5and 10
-1m, the situation of change of record current potential;
(4) with different glucose produce electric potential signal changing value for ordinate, concentration of glucose is horizontal ordinate drawing standard working 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.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104931563A (en) * | 2015-05-29 | 2015-09-23 | 中国科学院烟台海岸带研究所 | High-selective potential glucose sensor |
| CN105738415A (en) * | 2016-02-01 | 2016-07-06 | 中国科学院烟台海岸带研究所 | Potential sensor for phosphate anions and application of potential sensor |
| CN106290539A (en) * | 2016-07-29 | 2017-01-04 | 广西师范学院 | The method of tyrosine concentration in detection solution |
| CN106442653A (en) * | 2015-08-07 | 2017-02-22 | 中国科学院烟台海岸带研究所 | Application of potential sensor in detection of aromatic thiol |
| CN106442652A (en) * | 2015-08-07 | 2017-02-22 | 中国科学院烟台海岸带研究所 | Potential type sensor of oxidase and related reaction thereof |
| CN113155927A (en) * | 2021-04-01 | 2021-07-23 | 华东师范大学 | Glucose potential sensor based on SDBA-Au composite nanoenzyme |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5384028A (en) * | 1992-08-28 | 1995-01-24 | Nec Corporation | Biosensor with a data memory |
| CN102112873A (en) * | 2008-07-29 | 2011-06-29 | 庆北大学校产学协力团 | Composition for glucose sensing comprising of nanofibrous membrane and method for manufacturing non-enzymatic glucose biosensor using same |
| CN103881128A (en) * | 2014-03-10 | 2014-06-25 | 黄鹏 | Preparation method of in-situ glucose detecting membrane based on fluorescence detection method |
-
2014
- 2014-12-10 CN CN201410753275.2A patent/CN104597090A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5384028A (en) * | 1992-08-28 | 1995-01-24 | Nec Corporation | Biosensor with a data memory |
| CN102112873A (en) * | 2008-07-29 | 2011-06-29 | 庆北大学校产学协力团 | Composition for glucose sensing comprising of nanofibrous membrane and method for manufacturing non-enzymatic glucose biosensor using same |
| CN103881128A (en) * | 2014-03-10 | 2014-06-25 | 黄鹏 | Preparation method of in-situ glucose detecting membrane based on fluorescence detection method |
Non-Patent Citations (4)
| Title |
|---|
| EIICHI SHOJI等: "Potentiometric Saccharide Detection Based on the pKa Changes of Poly(aniline boronic acid)", 《J.AM.CHEM.SOC.》 * |
| HUIMIN GUO等: "Phenylacetylide ligand mediated tuning of visible-light absorption,room temperature phosphorescence lifetime and tripletetriplet annihilation based up-conversion of a diimine Pt(II) bisacetylide complex", 《DYES AND PIGMENTS》 * |
| XUEWEI WANG等: "Reporter-Free Potentiometric Sensing of Boronic Acids and Their", 《ANALYTICAL CHEMISTRY》 * |
| 李龙等: "基于联苯二硼酸寡聚反应的高选择性电位型葡萄糖传感器", 《中国化学会第29届学术年会摘要集》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104931563A (en) * | 2015-05-29 | 2015-09-23 | 中国科学院烟台海岸带研究所 | High-selective potential glucose sensor |
| CN104931563B (en) * | 2015-05-29 | 2017-09-29 | 中国科学院烟台海岸带研究所 | A kind of electric potential type glucose sensor of high selectivity |
| CN106442653A (en) * | 2015-08-07 | 2017-02-22 | 中国科学院烟台海岸带研究所 | Application of potential sensor in detection of aromatic thiol |
| CN106442652A (en) * | 2015-08-07 | 2017-02-22 | 中国科学院烟台海岸带研究所 | Potential type sensor of oxidase and related reaction thereof |
| CN105738415A (en) * | 2016-02-01 | 2016-07-06 | 中国科学院烟台海岸带研究所 | Potential sensor for phosphate anions and application of potential sensor |
| CN106290539A (en) * | 2016-07-29 | 2017-01-04 | 广西师范学院 | The method of tyrosine concentration in detection solution |
| CN113155927A (en) * | 2021-04-01 | 2021-07-23 | 华东师范大学 | Glucose potential sensor based on SDBA-Au composite nanoenzyme |
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Application publication date: 20150506 |