CN105319247A - Electric potential type glucose recognition element and glucose detection method thereof - Google Patents
Electric potential type glucose recognition element and glucose detection method thereof Download PDFInfo
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- CN105319247A CN105319247A CN201410380589.2A CN201410380589A CN105319247A CN 105319247 A CN105319247 A CN 105319247A CN 201410380589 A CN201410380589 A CN 201410380589A CN 105319247 A CN105319247 A CN 105319247A
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Abstract
The invention belongs to the technical field of glucose analysis tests and particularly relates to a high-selectivity and non-enzyme electric potential type glucose detection method. The method specifically includes the steps that boric acid can cause anionic potential response on a polymer membrane electrode doped with quaternary ammonium salt, a boronic acid derivative containing double boric acid groups is utilized as a probe, after the probe and glucose generate an oligomerization function, further reduction of electric potential is caused, and other monosaccharides cannot generate an oligomer with the probe, so that obvious reduction of electric potential does not exist. By means of the high-selectivity and non-enzyme electric potential type glucose detection method, high-selectivity and non-enzyme electric potential detection can be achieved.
Description
Technical field
The invention belongs to glucose analysis technical field of measurement and test, be specifically related to a kind of high selectivity, without enzyme electric potential type glucose recognition component and detect the method for glucose.
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 high selectivity, without enzyme electric potential type glucose recognition component and detect the method for glucose.
For achieving the above object, the technical solution used in the present invention is:
A kind of electric potential type glucose sensor, sensor is using the described boronic acid derivatives containing two boric acid base group as recognition component, using the polymkeric substance of quaternary ammonium salt doping as membrane electrode.
The polymer membrane electrode that described recognition component adulterates at quaternary ammonium salt causes negative ion potential response, and in recognition component, two boric acid base group and the effect of glucose generation oligomerization, cause the change of current potential, and then the detection glucose of qualitative/quantitative.
Described recognition component is inorganic boric acid, organic boronic or boronic acid derivatives.
Described boronic acid derivatives 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 polymer membrane electrode is made up of film matrix, plastifier and anionite; 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; Anionite is dotriacontyl monomethyl ammonium chloride, dotetracontane ammonium chloride, dotriacontyl monomethyl ammonium bromide or dotetracontane base ammonium bromide.
An application for electric potential type glucose sensor, utilizes recognition component on polymer membrane electrode, cause the potential response of negative ion, and then the detection glucose of qualitative/quantitative.
Testing process comprises the following steps:
(1) at pH be 7.4 PBS buffer solution in add the recognition component of 50 μMs, record potential value is stablized to current potential;
(2) in above-mentioned solution, the glucose solution of variable concentrations is added, the situation of change of record current potential, drawing standard working curve;
(3) according to the potential response value of different glucose, the concentration value of glucose is calculated.
The structural formula of several concrete recognition component is as follows:
Cleaning Principle of the present invention: the covalent bond effect utilizing boric acid base group and c/s-diol, boronic acid derivatives recognition component containing two boric acid base groups can form ring-type and linear oligomerization borate 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 potential change before and after boric acid and glucose response, the high selectivity that can realize glucose detects.
The advantage that the present invention has: the present invention, by selecting suitable two boric acid as recognition component, utilizes the oligomerization of boric acid and glucose, reduces the design difficulty of glucose identity, improve the selectivity of detection simultaneously; Utilize the potential response of boric acid base group itself, the present invention does not need, by means of other signal reporter molecules or group, to simplify sensor design.Compared with traditional detection method, the present invention does not need to carry out complicated recognition component, simultaneously easy and simple to handle, can realize the high selectivity of glucose without enzyme potentiometric detection.
Accompanying drawing explanation
Fig. 1 is Cleaning Principle of the present invention.
What Fig. 2 provided for the embodiment of the present invention is that recognition component detects the potential curve of glucose with 4,4'-benzene hypoboric acid.
What Fig. 3 provided for the embodiment of the present invention is that recognition component detects the potential curve of glucose with 4,4'-biphenyl hypoboric acid.
What Fig. 4 provided for the embodiment of the present invention is that recognition component detects the standard working curve of glucose with 4,4'-biphenyl hypoboric acid.
Embodiment
Embodiment 1
The present invention is that recognition component detects glucose for example with 4,4'-benzene hypoboric acid.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) potentiometric detection of glucose
Use 4, the 4'-benzene hypoboric acid of dimethyl sulfoxide preparation 50mM, being then added to pH is in the PBS buffer solution of 7.4, makes the diborated ultimate density of 4,4'-benzene be 50 μMs, 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. 2.
Embodiment 2
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, 5.76mg dotetracontane ammonium chloride 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 10mM as internal-filling liquid and activating solution activated electrode, stand-by.
(2) potentiometric detection of glucose
Use 4, the 4'-biphenyl hypoboric acid of dimethyl sulfoxide preparation 50mM, be then added to pH and add above-mentioned solution in the PBS buffer solution of 7.4, make the diborated ultimate density of 4,4'-biphenyl be 50 μMs, 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. 3, and the standard working curve of drafting is shown in Fig. 4.
Claims (7)
1. an electric potential type glucose sensor, is characterized in that: sensor is using the described boronic acid derivatives containing two boric acid base group as recognition component, using the polymkeric substance of quaternary ammonium salt doping as membrane electrode.
2. by electric potential type glucose sensor according to claim 1, it is characterized in that: the polymer membrane electrode that described recognition component adulterates at quaternary ammonium salt causes negative ion potential response, two boric acid base group and the effect of glucose generation oligomerization in recognition component, cause the change of current potential, and then the detection glucose of qualitative/quantitative.
3., by the electric potential type glucose sensor described in claim 1 or 2, it is characterized in that: described recognition component is inorganic boric acid, organic boronic or boronic acid derivatives.
4., by electric potential type glucose sensor according to claim 3, it is characterized in that: described boronic acid derivatives be containing two boronate because of lipophilicity boronic acid derivatives.
5. by electric potential type glucose sensor according to claim 4, 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.
6., by the electric potential type glucose sensor described in claim 1 or 2, it is characterized in that: described polymer membrane electrode is made up of film matrix, plastifier and anionite; 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; Anionite is dotriacontyl monomethyl ammonium chloride, dotetracontane ammonium chloride, dotriacontyl monomethyl ammonium bromide or dotetracontane base ammonium bromide.
7. an application for electric potential type glucose sensor 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.
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| CN201410380589.2A CN105319247A (en) | 2014-08-04 | 2014-08-04 | Electric potential type glucose recognition element and glucose detection method thereof |
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| CN201410380589.2A CN105319247A (en) | 2014-08-04 | 2014-08-04 | Electric potential type glucose recognition element and glucose detection method thereof |
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Citations (3)
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| 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 |
| CN102235995A (en) * | 2010-05-07 | 2011-11-09 | 中国科学院烟台海岸带研究所 | Polymer liquid film potential sensor for detecting enzymatic activity and detection method thereof |
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2014
- 2014-08-04 CN CN201410380589.2A patent/CN105319247A/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 |
| CN102235995A (en) * | 2010-05-07 | 2011-11-09 | 中国科学院烟台海岸带研究所 | Polymer liquid film potential sensor for detecting enzymatic activity and detection method thereof |
Non-Patent Citations (3)
| Title |
|---|
| HAKAN ÇIFTÇI等: "An enzyme free potentiometric detection of glucose based on a conducting polymer poly (3-aminophenyl boronic acid-co-3-octylthiophene)", 《ELECTROCHIMICA ACTA》 * |
| XUEWEI WANG等: "Reporter-Free Potentiometric Sensing of Boronic Acids and Their Reactions by Using Quaternary Ammonium Salt-Functionalized Polymeric Liquid Membranes", 《ANALYTICAL CHEMISTRY》 * |
| 陈红朵等: "基于硼酸衍生物识别的无酶电位型葡萄糖传感器", 《第十二届全国电分析化学学术会议论文集（第二分册――传感器）》 * |
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