CN100434448C - Modified electrode face finish material based on sodium carboxymethyl cellulose, and preparation method - Google Patents
Modified electrode face finish material based on sodium carboxymethyl cellulose, and preparation method Download PDFInfo
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- CN100434448C CN100434448C CNB2005100867968A CN200510086796A CN100434448C CN 100434448 C CN100434448 C CN 100434448C CN B2005100867968 A CNB2005100867968 A CN B2005100867968A CN 200510086796 A CN200510086796 A CN 200510086796A CN 100434448 C CN100434448 C CN 100434448C
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- mucine
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- pyridines
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Abstract
This invention relates to an electrode-surface-modifying material based on carboxymethyl cellulose sodium modification. The electrode-surface-modifying material is Os-complexed carboxymethyl cellulose sodium grafted poly (vinyl pyridine) (Os-CMCNa-g-PVP). The material has high redox performance and high electrical conductivity, and can be used as an electrode-surface-modifying material for biosensors.
Description
Technical field
The present invention relates to a kind of electrode face finish material based on the Xylo-Mucine modification.
Background technology
The frontier on artificial control electrode surface has been started in the appearance of modified electrode.The polymer materials that wherein is used for modified electrode is because of characteristics broad research and application the most such as it is stable, efficient, sensitivities.This polymer materials has oxidation, reduction and conductive characteristic, mainly the oxidation-reduction type conductive polymers that forms based on metal complex.At present, wherein using is osmium metal complex polyvinylpyridine more widely, Robert J.Forster and Johannes G..Vos has reported its synthetic method and has been used for character [Synthesis such as the electrochemistry on modified electrode surface, photochemistry, Characterization, and Properties of a Series ofOsmium-and Ruthenium-Containing Metallopolymers.Macromolecules 23,4372～4377 (1990)].Afterwards, Brian A.Gregg and Adam Heller has reported that preparation comprises oxidation-reduction type conducting polymer thin film [the Redox polymer films containing enzymes.1.aredox-conducting epoxy cement:synthesis of enzyme, characterization, and electrocatalyticoxidation of hydroquinone.Journal of Physical Chemistry 95,5970～5975 (1991)], and be widely used in Study on Biosensor [Redox polymer filmscontaining enzymes.1.a redox-conducting epoxy cement:synthesis.characterization on this basis, and electrocatalytic oxidation of hydroquinone.Journal ofPhysical Chemistry 95,5970～5975 (1991)].Though this polymer materials that is used for electrode modification has redox conductive characteristic preferably, susceptibility is limited with stability when being used to detect hydrogen peroxide and L-glutamic acid etc.
Summary of the invention
A purpose of the present invention is to provide a kind of electrode modified material of the osmium metal complex polymkeric substance based on the Xylo-Mucine modification.
Another object of the present invention is to utilize electrode modified material, detect hydrogen peroxide (H based on the osmium metal complex polymkeric substance of Xylo-Mucine modification
2O
2) and L-glutamic acid etc., improve the susceptibility and stability that detect.
A further object of the present invention is to provide a kind of preparation method of the electrode face finish material based on the Xylo-Mucine modification.
Electrode face finish material based on the Xylo-Mucine modification of the present invention is an osmium metal complex Xylo-Mucine grafted polyethylene yl pyridines multipolymer (Os-CMCNa-g-PVP), and its structural formula is:
Wherein:
Bpy is
R is H or CH
2COONa;
N, m, p represent the polymerization degree, m-p+p=m, and (m-p): p=1: 3～1: 20;
N is the polymerization degree of main chain Xylo-Mucine (CMCNa), and p is the unitary polymerization degree of quaternised vinyl pyridine in the branched polyethylene yl pyridines (PVP); M-p is the unitary polymerization degree of vinyl pyridine of complexing osmium metallic compound in the branched polyethylene yl pyridines (PVP), and promptly the total polymerization degree m of branched polyethylene yl pyridines (PVP) deducts wherein quaternized unitary polymerization degree p; N, m, p can calculate by the molecular weight of CMCNa, the molecular weight of PVP.
Its main chain is Xylo-Mucine (CMCNa), and weight-average molecular weight is 50000～500000, and substitution value is 0.5～2.5, and structural formula is:
Its side chain is polyvinylpyridine (PVP), and weight-average molecular weight is 10000～100000, and structural formula is:
M is the total polymerization degree of branched polyethylene yl pyridines (PVP);
The preparation method of the electrode face finish material based on the Xylo-Mucine modification of the present invention may further comprise the steps:
(1) under 25～50 degrees centigrade and nitrogen protection, in distilled water, Xylo-Mucine (CMCNa) is fully dissolved, add the reaction of ceric ammonium nitrate and vinyl pyridine (4-VP), synthetic Xylo-Mucine grafted polyethylene yl pyridines multipolymer (CMCNa-g-PVP), wherein the mass ratio of CMCNa and 4-VP is 1: 1～1: 3, and the mass ratio of CMCNa and ceric ammonium nitrate is 10: 1～20: 1; After reacting 3～6 hours, add Resorcinol aqueous solution termination reaction; Reaction mixture precipitation, filtration, extracting, drying obtain Xylo-Mucine grafted polyethylene yl pyridines multipolymer CMCNa-g-PVP.
(2) the Xylo-Mucine grafted polyethylene yl pyridines multipolymer (CMCNa-g-PVP) that step (1) is obtained connects pyridine dichloro osmium (Os (bpy) with osmium metallic compound two
2Cl
2) be in ethylene glycol, under 100～150 degrees centigrade, to carry out complex reaction in 1: 2～1: 10 by mass ratio; The reaction postcooling is to room temperature, add N again, N '-dimethyl formamide (N, N '-dimethylformamide:DMF) is 2-bromine ethamine hydrogen bromide (2-bromoethylaminehydrobromide) reaction of 5～10 times of CMCNa-g-PVP quality with quality, to react the mixed liquid precipitate in back, separation, drying, obtain osmium metal complex Xylo-Mucine grafted polyethylene yl pyridines multipolymer (Os-CMCNa-g-PVP).
The present invention utilizes osmium metal complex Xylo-Mucine grafted polyethylene yl pyridines multipolymer to detect the method for hydrogen peroxide and glutamic acid solution:
(1) takes by weighing a certain amount of Os-CMCNa-g-PVP and be dissolved in the distilled water, fully dissolve, be made into the aqueous solution of 5～20 grams per liters;
(2) take by weighing a certain amount of horseradish peroxidase, be dissolved in volume ratio and be in the sodium periodate aqueous solution of 2: 1 the sodium bicarbonate aqueous solution of 0.1 mol and 10 grams per liters, be made into the solution of 10～20 grams per liter horseradish peroxidase, lucifuge leave standstill 2～3 hours stand-by;
(3) aqueous solution of configuration polyethyleneglycol diglycidylether (PEGDGE) 1～3 grams per liter;
(4) it is an amount of to get step (1), (2), (3) solution respectively, is made into mixing solutions in 5: 1: 6 by volume, and thorough mixing is even.Get this mixing drop and be applied to working electrode surface, the seasoning film forming just can be used to detect hydrogen peroxide (H
2O
2) concentration.And cooperate to add L-GLOD, can be used to detect the concentration of L-glutamic acid.
Electrode modified material based on the Xylo-Mucine modification of the present invention has good oxidation, reduction, conductive characteristic, can be used as the electrode face finish material of biosensor etc.
Description of drawings
Fig. 1. the embodiment of the invention 1 is used for hydrogen peroxide (H
2O
2) when detecting, H
2O
2Concentration and the linear relationship that detects current value.Wherein X-coordinate is H
2O
2Concentration C, its unit: 10
-6Mol; Ordinate zou is for detecting current value I, its unit: 10
-9Ampere.
Fig. 2. the embodiment of the invention 2 when being used for L-glutamic acid and detecting, aminoglutaric acid concentration and the linear relationship that detects current value.Wherein X-coordinate is aminoglutaric acid concentration C, its unit: 10
-6Mol; Ordinate zou is for detecting current value I, its unit: 10
-9Ampere.
Embodiment
Embodiment 1:
(1) preparation of Os-CMCNa-g-PVP
Take by weighing 1 gram Xylo-Mucine, its weight-average molecular weight is 90000, and substitution value is 0.7, joins in 36 ml distilled waters, and the drum nitrogen protection is stirred to dissolving fully in 30 degrees centigrade of Water Tanks with Temp.-controlled.Configuration contains 4 milliliters of the 1 mol salpeter solutions of 110 milligrams of ceric ammonium nitrates then, joins in the aqueous solution of Xylo-Mucine, and stirring reaction is 30 minutes under the nitrogen.Add 2 milliliters of 4-vinylpridines again, stirring reaction is 3 hours under the nitrogen.Afterwards, add 0.5 milliliter of 5% Resorcinol aqueous solution termination reaction.Reaction mixture precipitation, filtration, extracting, drying obtain derivatived cellulose grafted polyethylene yl pyridines multipolymer CMCNa-g-PVP.Its side chain is that the weight-average molecular weight of polyvinylpyridine is 80000.
Get 200 milligrams of CMCNa-g-PVP graft copolymers, 50 milligram of two pyridine dichloro osmium (Os (bpy) of company
2Cl
2) join in 30 milliliters of ethylene glycol, be heated with stirring to 140 degrees centigrade of reactions 24 hours under the nitrogen.Reaction mixture is cooled to room temperature then, adds 50 milliliters of DMF and 1.6 gram 2-bromine ethamine hydrogen bromides (2-bromoethylamine hydrobromide) respectively, in 80 degrees centigrade of constant temperature stirring reactions 24 hours.At last, will react the mixed liquid precipitate in back, separation, drying, promptly obtain osmium complexing Xylo-Mucine grafted polyethylene yl pyridines multipolymer Os-CMCNa-g-PVP.
(2) utilize Os-CMCNa-g-PVP to detect the concentration of hydrogen peroxide
A. take by weighing 100 milligrams of Os-CMCNa-g-PVP, join in 10 ml distilled waters, fully dissolve, be made into the aqueous solution of 10 grams per liters;
B. take by weighing 10 milligrams horseradish peroxidase, join in the sodium bicarbonate aqueous solution of 0.5 milliliter of 0.1 mol, fully dissolving, and then add the sodium periodate aqueous solution of 0.25 milliliter of 10 grams per liter, lucifuge leave standstill 2～3 hours stand-by;
C. take by weighing 100 milligrams of polyethyleneglycol diglycidylethers, join fully dissolving in 100 ml waters;
D. the solution of getting step a, b, c respectively is an amount of, is made into mixing solutions in 5: 1: 6 by volume, and thorough mixing is even.Get this mixed solution 0.5 microlitre and drip and be applied to electrode surface, the seasoning film forming is used for detecting hydrogen peroxide (H
2O
2) concentration.
Embodiment 2:
(1) preparation process of Os-CMCNa-g-PVP is with embodiment 1
Take by weighing 1 gram Xylo-Mucine, its weight-average molecular weight is 250000, and substitution value is 1.2, joins in 36 ml distilled waters, and the drum nitrogen protection is stirred to dissolving fully in 30 degrees centigrade of Water Tanks with Temp.-controlled.Configuration contains 4 milliliters of the 1 mol salpeter solutions of 150 milligrams of ceric ammonium nitrates then, joins in the aqueous solution of Xylo-Mucine, and stirring reaction is 30 minutes under the nitrogen.Add 3 milliliters of 4-vinylpridines again, stirring reaction is 5 hours under the nitrogen.Afterwards, add 0.5 milliliter of 5% Resorcinol aqueous solution termination reaction.Reaction mixture precipitation, filtration, extracting, drying obtain derivatived cellulose grafted polyethylene yl pyridines multipolymer CMCNa-g-PVP.Its side chain is that the weight-average molecular weight of polyvinylpyridine is 50000.
Get 200 milligrams of CMCNa-g-PVP graft copolymers, 25 milligram two and connect pyridine dichloro osmium and join in 30 milliliters of ethylene glycol, be heated with stirring to 140 degrees centigrade of reactions 24 hours under the nitrogen.Reaction mixture was cooled to room temperature then, adds 50 milliliters of DMF and 1.6 gram 2-bromine ethamine hydrogen bromides respectively, in 80 degrees centigrade of constant temperature stirring reactions 24 hours.At last, will react the mixed liquid precipitate in back, separation, drying, promptly obtain osmium complexing Xylo-Mucine grafted polyethylene yl pyridines multipolymer Os-CMCNa-g-PVP.
(2) utilize Os-CMCNa-g-PVP to detect the concentration of L-glutamic acid:
A. step is with embodiment 1.
B. step is with embodiment 1.
C. take by weighing 200 milligrams of polyethyleneglycol diglycidylethers, join fully dissolving in 100 ml waters;
D. get 37.5,0.75,4.5 milliliter of the solution of step a, b, c respectively, be made into mixing solutions, thorough mixing is even.
E. take by weighing 10 milligrams of L-GLODs, join in the mixing solutions of steps d, fully dissolving evenly.This mixed solution 0.5 microlitre drips and is applied to electrode surface, and the seasoning film forming is used for detecting the concentration of L-glutamic acid.
Solution with resulting Os-CMCNa-g-PVP polymkeric substance and horseradish peroxidase are made into is used for hydrogen peroxide (H by electrochemical analysis
2O
2) and L-glutamic acid when detecting (as Fig. 1, Fig. 2), proved that it has good oxidation, reduction, conductive characteristic, have excellent sensitivity and stability, can be used for the electrode face finish material of needs such as biosensor.
Claims (2)
1. electrode face finish material based on the Xylo-Mucine modification, it is characterized in that: described material is an osmium metal complex Xylo-Mucine grafted polyethylene yl pyridines multipolymer, and its structural formula is:
Wherein:
Bpy is
R is H or CH
2COONa;
N, m, p represent the polymerization degree, m-p+p=m, and (m-p): p=1: 3～1: 20;
N is the polymerization degree of main chain Xylo-Mucine, and p is the unitary polymerization degree of quaternised vinyl pyridine in the branched polyethylene yl pyridines; M-p is the unitary polymerization degree of vinyl pyridine of complexing osmium metallic compound in the branched polyethylene yl pyridines;
Its main chain is an Xylo-Mucine, and weight-average molecular weight is 50000～500000, and substitution value is 0.5～2.5, and structural formula is:
Its side chain is a polyvinylpyridine, and weight-average molecular weight is 10000～100000, and structural formula is:
M is the total polymerization degree of branched polyethylene yl pyridines.
2. the preparation method of the electrode face finish material based on the Xylo-Mucine modification according to claim 1 is characterized in that this method may further comprise the steps:
(1) under 25～50 degrees centigrade and nitrogen protection, in distilled water, Xylo-Mucine is fully dissolved, add the reaction of ceric ammonium nitrate and vinyl pyridine, synthetic Xylo-Mucine grafted polyethylene yl pyridines multipolymer, wherein the mass ratio of Xylo-Mucine and vinyl pyridine is 1: 1～1: 3, and the mass ratio of Xylo-Mucine and ceric ammonium nitrate is 10: 1～20: 1; After reacting 3～6 hours, add Resorcinol aqueous solution termination reaction; Reaction mixture precipitation, filtration, extracting, drying obtain Xylo-Mucine grafted polyethylene yl pyridines multipolymer;
(2) to connect pyridine dichloro osmiums be to carry out complex reaction in 1: 2～1: 10 in ethylene glycol under 100～150 degrees centigrade by mass ratio to the Xylo-Mucine grafted polyethylene yl pyridines multipolymer that step (1) is obtained and osmium metallic compound two; The reaction postcooling is to room temperature, add N again, N '-dimethyl formamide and quality are the 2-bromine ethamine reaction of hydrogen bromide of 5～10 times of Xylo-Mucine grafted polyethylene yl pyridines copolymer qualities, to react the mixed liquid precipitate in back, separation, drying, obtain osmium metal complex Xylo-Mucine grafted polyethylene yl pyridines multipolymer.
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|---|---|---|---|---|
| CN116087286A (en) * | 2023-03-10 | 2023-05-09 | 上海微创生命科技有限公司 | Biosensor and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101931074B (en) * | 2009-12-15 | 2012-09-05 | 辽宁弘光科技集团有限公司 | Film base material compositions for lithium battery electrodes and lithium battery |
| CN102504111B (en) * | 2011-11-17 | 2013-06-12 | 中国科学院化学研究所 | Electrode surface modification material, preparation method thereof and application thereof |
| CN103627007B (en) * | 2013-01-22 | 2016-03-23 | 中国科学院电子学研究所 | For the electrode face finish material and preparation method thereof of biosensor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4198326A (en) * | 1978-02-14 | 1980-04-15 | Lishevskaya Marina O | Method for preparing modified graft copolymers of cellulose with monovinyl monomers in the presence of a divinylbenzene modifier |
| CN1072969A (en) * | 1992-10-05 | 1993-06-09 | 中国科学院广州化学研究所 | The viscose grafting, copolymerization and modification prepares the wool-like fiber method |
| CN1186082A (en) * | 1996-12-25 | 1998-07-01 | 中国科学院长春应用化学研究所 | Preparation of polyvinyl alcohol graft copolymerized 4-vinyl pyridine |
-
2005
- 2005-11-04 CN CNB2005100867968A patent/CN100434448C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4198326A (en) * | 1978-02-14 | 1980-04-15 | Lishevskaya Marina O | Method for preparing modified graft copolymers of cellulose with monovinyl monomers in the presence of a divinylbenzene modifier |
| CN1072969A (en) * | 1992-10-05 | 1993-06-09 | 中国科学院广州化学研究所 | The viscose grafting, copolymerization and modification prepares the wool-like fiber method |
| CN1186082A (en) * | 1996-12-25 | 1998-07-01 | 中国科学院长春应用化学研究所 | Preparation of polyvinyl alcohol graft copolymerized 4-vinyl pyridine |
Non-Patent Citations (1)
| Title |
|---|
| 纤维素纤维的化学改性与反应性染色. 伏宏彬.成都纺织高等专科学校学报，第19卷第03期. 2002 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116087286A (en) * | 2023-03-10 | 2023-05-09 | 上海微创生命科技有限公司 | Biosensor and preparation method and application thereof |
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