CN100585387C - Environment friendly high sensitive electrochemical method of luminescence detection - Google Patents
Environment friendly high sensitive electrochemical method of luminescence detection Download PDFInfo
- Publication number
- CN100585387C CN100585387C CN200510016848A CN200510016848A CN100585387C CN 100585387 C CN100585387 C CN 100585387C CN 200510016848 A CN200510016848 A CN 200510016848A CN 200510016848 A CN200510016848 A CN 200510016848A CN 100585387 C CN100585387 C CN 100585387C
- Authority
- CN
- China
- Prior art keywords
- amine
- electrochemical
- ruthenium
- luminescence
- concentration
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
A high sensitive electrochemical luminous detection method of environment friendly technique uses ruthenium complex as luminous substance and amine as coreactant in electrochemical luminous system. The method is widely used in immune analysis and nulein analysis.
Description
Technical field
The present invention relates to a kind of eco-friendly high sensitive electrochemical luminescent detection techniques field.
Background technology
Electrochemiluminescence is the product that chemiluminescence and electrochemical method mutually combine, be meant by electrochemical method to produce some special materials, further react and a kind of luminescence phenomenon of generation between these electric living beings or between electric living beings and other material then.Electrochemiluminescence analysis method highly sensitive, the range of linearity is wide, and controllability is strong, and selectivity is good, and device is simple, is subjected to people's attention day by day.Nineteen twenty-seven, it is found that the Grignard compound is applied current potential can be produced luminous.During the electrolysis luminol, find all has luminescence phenomenon to nineteen twenty-nine Harvey on negative electrode and anode in alkaline solution, has opened the prelude of electrochemiluminescence research.The eighties is found the luminous mensuration of oxalic acid, aminated compounds, amino acid, NADH, pyruvic acid and the hypersensitive mensuration of pyridine ruthenium of can be used for of pyridine ruthenium electrochemical.During this period, electrochemiluminescence begins to separate the technology coupling with Flow Injection Analysis (FIA), high performance liquid chromatography (HPLC) and Capillary Electrophoresis (CE) etc., has improved the reappearance and the stability of luminous signal, for its practical application is laid a good foundation.The nineties, electrochemiluminescence begin to be used for the Single Molecule Detection of immunoassay, pcr analysis and DNA.Research at present and most widely used be pyridine ruthenium electrochemical luminescence system because it has outstanding advantages such as good water solubility, luminescence efficiency height, stable performance and electrochemical reversible.
The luminesceence analysis of pyridine ruthenium electrochemical is labelled immune analysis of new generation and nucleic acid determination technology.Prior art is based on tripropyl amine (TPA) and the pyridine ruthenium label generation electrochemiluminescence of low concentration of concentration about up to 100mM and reacts and carry out bioanalysis, is that a few is applied to one of electroanalytical technique of practical measurement.But there is following main weak point in pyridine ruthenium/tripropyl amine (TPA) electrochemiluminescsystem system.First and third propylamine oxidation rate on electrode is slower, causes electrochemiluminescence intensity lower, has limited the sensitivity that detects; The second, very the tripropyl amine (TPA) of high concentration could be realized highly sensitive detection; Three, tripropyl amine (TPA) solubleness in neutral solution is not so good, and generally will adopting very, high concentrations of phosphoric acid salt just can make the tripropyl amine (TPA) up to 100mM dissolve in neutral phosphate buffered solution; At last, the tripropyl amine (TPA) volatility is bigger, has bigger peculiar smell and certain toxicity.Therefore pressing for searching has the material of excellent properties more than tripropyl amine (TPA).
The pyridine ruthenium not only can with tripropyl amine (TPA) generation electrochemiluminescence reaction, can also with other a large amount of amine substance electrochemiluminescence rules.First kind of situation is the concentration that bipyridyl ruthenium concentration is close to or higher than amine substance.In this case, the structure of amine is to the more also comparison system of the research of the influence of electrochemiluminescence.At this moment, bipyridyl ruthenium catalytic oxidation amine is very big to electrochemiluminescence contribution, and contain usually the class of electron withdraw group luminous a little less than.Second kind of situation is the concentration of the concentration of bipyridyl ruthenium well below amine.Only there is one piece of document (J.Electrochem.Soc.1990,137,3127) to compare the electrochemiluminescence intensity of several amine roughly at present, but do not sum up luminescence law.This article finds that the electrochemiluminescence intensity of tripropyl amine (TPA) is better than other several amine, and bipyridyl ruthenium/tripropyl amine (TPA) electrochemiluminescsystem system can be used for immunoassay.Many pieces of documents have carried out deep research to the electrochemiluminescence mechanism of bipyridyl ruthenium/tripropyl amine (TPA) system subsequently.Discovery plays important effect (Anal.Chem.2000 in the Direct Electrochemistry oxidation of tripropyl amine (TPA) on electrode under the situation of the concentration of tripropyl amine (TPA) of the concentration of bipyridyl ruthenium, 72.3223), bipyridyl ruthenium catalytic oxidation tripropyl amine (TPA) is less relatively to the electrochemiluminescence contribution.Can strengthen electrochemiluminescence intensity by adding the Direct Electrochemistry oxidations of promotion tripropyl amine (TPA) on electrode such as surfactant.
Summary of the invention
It is bigger to the purpose of this invention is to provide a kind of luminous intensity, sensitive more, and the electrochemical luminescence method friendly more to environment provides the method that is applied to immune electrochemiluminescence analysis and the analysis of other important substance.
The present invention is a kind of eco-friendly high sensitive electrochemical method of luminescence detection, this luminescence system is that the complex compound bipyridyl ruthenium with ruthenium is a luminescent substance, with amine is co-reactant, with the surfactant is improvement reagent, in buffer solution, mix, analyze with the electrochemical method stimulated luminescence, it is characterized in that, the basic structure of co-reactant amine is (R
1) (R
2) N (R
3), R wherein
1, R
2, R
3Be alkyl, and have hydroxyl, carboxyl, amido or sulfonic group at least one alkyl with two to five carbon;
(R of the present invention
1) (R
2) N (R
3) be the di-n-butyl monoethanolamine;
Improvement reagent of the present invention is surfactant, is selected from triton x-100, Tween-20 or sodium dodecylsulphonate; Amine working concentration scope of the present invention is 0.05-50mM; Buffer solution of the present invention is phosphate buffered solution or the borate buffer solution of pH at 5-9;
Potential range of the present invention is 1.1-1.5V.
Outstanding advantage of the present invention be this system luminescence efficiency height, highly sensitive, the range of linearity is wide, the coreaction reagent concentration is low, environmental friendliness, favorable reproducibility and stable reagent.Utilize the range of linearity of this system detection material wide, detectability is low, can be widely used in immunoassay, foranalysis of nucleic acids.The very low and concentration di-n-butyl monoethanolamine of pyridine ruthenium concentration only is under the situation of 20mM, just can realize than adopting the sensitive more detection of tripropyl amine (TPA), under the same terms at pyridine ruthenium/di-n-butyl monoethanolamine on the gold electrode even stronger more than 10 times, strong more than 30 times on the platinum electrode than the intensity of pyridine ruthenium/tripropyl amine (TPA) electrochemiluminescence.
Description of drawings
Accompanying drawing 1 is to utilize pyridine ruthenium/di-n-butyl ethanol system electrochemiluminescence to measure the synoptic diagram of pyridine ruthenium content.
Accompanying drawing 2 is pH synoptic diagram that influence to pyridine ruthenium/di-n-butyl ethanol system electrochemiluminescence.
The subordinate list explanation
Table 1 is the luminous intensity contrast that has the various amine of different structure or functional group and the electrochemiluminescsystem system that the pyridine ruthenium is formed.
| Amine | Luminous intensity (a.u.) |
| The di-n-butyl monoethanolamine | 381 |
| Triethanolamine | 174 |
| Tripropyl amine (TPA) | 62 |
| N, N-diethyl-N '-methyl ethyleneamines | 28 |
| Triacetamide | 21 |
| Diethylpropanolamine | 13 |
Embodiment
Embodiment 1: fixedly di-n-butyl monoethanolamine concentration is 25mM, buffer solution is the 0.1M phosphate of pH 7.5, the pyridine ruthenium that adds 1fM, with the gold is working electrode, current potential is got on the rank that apply 1.35V, applies suitable luminous detection high pressure simultaneously, utilizes luminous signal to detect the pyridine ruthenium, replication three times, the mean intensity that obtains pyridine ruthenium luminous signal is 47.41.
Embodiment 2: fixedly di-n-butyl monoethanolamine concentration is 0.05mM, pyridine ruthenium concentration is 1 μ M, buffer solution is the 0.1M phosphate of pH 5, with the gold is working electrode, current potential is got on the rank that apply 1.5V, applies suitable luminous detection high pressure simultaneously, utilizes luminous signal to detect the pyridine ruthenium, replication three times, the luminous signal mean intensity that obtains is 52.4.
Embodiment 3: fixedly the concentration of di-n-butyl monoethanolamine is 1mM, pyridine ruthenium concentration is 1mM, be dissolved in pH9 the 0.1M phosphate buffered solution in, with the gold is working electrode, electrode potential from the 0V cyclic voltammetry scan to 1.1V, apply suitable luminous detection high pressure simultaneously, replication three times, the luminous signal mean intensity that obtains is 1.26 * 10
6
Embodiment 4: fixedly di-n-butyl monoethanolamine concentration is 10mM, pyridine ruthenium concentration is 1 μ M, buffer solution is the 0.1M borate of pH 9, with the gold is working electrode, current potential is got on the rank that apply 1.5V, applies suitable luminous detection high pressure simultaneously, utilizes luminous signal to detect the pyridine ruthenium, replication three times, the luminous signal mean intensity that obtains is 1.1 * 10
6
Embodiment 5: fixedly pyridine ruthenium concentration is 1 μ M, and buffer solution is the 0.1M phosphate of pH 7.5, adds the various amine that contain different structure or functional group, and fixedly the concentration of amine is 25mM.With the gold is working electrode, and assay method is with embodiment 1, every kind of amine replication three times, and its average result is face form 1 as follows.
Claims (4)
1. eco-friendly high sensitive electrochemical method of luminescence detection, this luminescence system is that the complex compound bipyridyl ruthenium with ruthenium is a luminescent substance, with amine is co-reactant, with the surfactant is improvement reagent, in buffer solution, mix, analyze with the electrochemical method stimulated luminescence, it is characterized in that, described amine is the di-n-butyl monoethanolamine.
2. electrochemical luminous detection method according to claim 1 is characterized in that described improvement reagent is selected from triton x-100, Tween-20 or sodium dodecylsulphonate.
3. electrochemical luminous detection method according to claim 1 and 2 is characterized in that described amine working concentration scope is 0.05-50mM.
4, electrochemical luminous detection method according to claim 1 and 2 is characterized in that described buffer solution is phosphate buffered solution or the borate buffer solution of pH at 5-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510016848A CN100585387C (en) | 2005-06-03 | 2005-06-03 | Environment friendly high sensitive electrochemical method of luminescence detection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510016848A CN100585387C (en) | 2005-06-03 | 2005-06-03 | Environment friendly high sensitive electrochemical method of luminescence detection |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1696666A CN1696666A (en) | 2005-11-16 |
| CN100585387C true CN100585387C (en) | 2010-01-27 |
Family
ID=35349488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200510016848A Expired - Fee Related CN100585387C (en) | 2005-06-03 | 2005-06-03 | Environment friendly high sensitive electrochemical method of luminescence detection |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100585387C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104698164B (en) * | 2015-02-13 | 2017-03-15 | 中山市创艺生化工程有限公司 | A kind of Electrogenerated chemiluminescent immunoassay instrument buffer and preparation method thereof |
| CN105929010A (en) * | 2016-04-14 | 2016-09-07 | 福建师范大学 | Eosin Y based electrochemiluminescence sensor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6451225B1 (en) * | 1986-04-30 | 2002-09-17 | Igen International, Inc. | Electrochemiluminescent reaction utilizing amine-derived reductant |
| CN1392411A (en) * | 2002-08-06 | 2003-01-22 | 华南师范大学 | In situ electrochemical luminous detection method and device |
| CN1544657A (en) * | 2003-11-25 | 2004-11-10 | 华南师范大学 | Method and device for detecting genes utilizing electrochemical luminescence PCR |
| US6881589B1 (en) * | 1987-04-30 | 2005-04-19 | Bioveris Corporation | Electrochemiluminescent localizable complexes for assay compositions |
-
2005
- 2005-06-03 CN CN200510016848A patent/CN100585387C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6451225B1 (en) * | 1986-04-30 | 2002-09-17 | Igen International, Inc. | Electrochemiluminescent reaction utilizing amine-derived reductant |
| US6881589B1 (en) * | 1987-04-30 | 2005-04-19 | Bioveris Corporation | Electrochemiluminescent localizable complexes for assay compositions |
| CN1392411A (en) * | 2002-08-06 | 2003-01-22 | 华南师范大学 | In situ electrochemical luminous detection method and device |
| CN1544657A (en) * | 2003-11-25 | 2004-11-10 | 华南师范大学 | Method and device for detecting genes utilizing electrochemical luminescence PCR |
Non-Patent Citations (3)
| Title |
|---|
| Electrogenerated chemiluminescence. 66.The Role of Direct.on the Emission Intensity. Yanbing Zu and Allen J.Bard.Anal.Chem,Vol.72 No.14. 2000 * |
| 三邻菲咯啉合亚钌－亚硫酸根－过二硫酸钾化学发光法测定空气中的二氧化硫. 吴风武等.分析化学，第28卷第6期. 2000 * |
| 取代基对胺化合物联吡啶钌电致化学发光影响的研究. 陈曦等.化学学报，第60卷第9期. 2002 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1696666A (en) | 2005-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Environmentally Friendly and Highly Sensitive Ruthenium (II) Tris (2, 2'-bipyridyl) Electrochemiluminescent System Using 2-(Dibutylamino) ethanol as Co-ReactantFNR HREF=" nss"> FN ID=" nss"> We thank Prof. | |
| CN104931570B (en) | A kind of preparation method of the heavy metal ion electrochemical sensor based on aptamer and application | |
| CN101354352B (en) | Sensor for detecting ammonium based on iridium complex electrogenerated chemiluminescence method | |
| Zhang et al. | Ethynyl and π-stacked thymine–Hg2+–thymine base pairs enhanced fluorescence quenching via photoinduced electron transfer and simple and sensitive mercury ion sensing | |
| CN102375020A (en) | Method for detecting mercury ions through gold electrode modified by polythymidine DNA | |
| CN105044171A (en) | Production method and application of nano-platinum doped/enzyme modified carbon paste electrode | |
| Huang et al. | Capillary electrophoresis with end-column electrochemiluminescence for the analysis of chloroquine phosphate and the study on its interaction with human serum albumin | |
| Bobbitt et al. | Chemiluminescent detection of amines and amino acids using in situ generated Ru (bpy) 33+ following separation by capillary electrophoresis | |
| CN103217468B (en) | Preparation method and application of current type electrochemical sensor for detecting bisphenol A | |
| CN101285793A (en) | Method for simultaneously determining dopamine and ascorbic acid by utilizing modified glassy carbon electrode | |
| CN100585387C (en) | Environment friendly high sensitive electrochemical method of luminescence detection | |
| CN104422686A (en) | Method for determining aflatoxin | |
| CN102565174A (en) | Ionic liquid polyaniline modified electrode-electro chemical analysis system | |
| CN104155289B (en) | A kind of solid-state electrochemistry illumination sensor detecting mercury ion and its preparation method and application | |
| CN103558210B (en) | A kind of method combining fixed ion type complex of iridium based on covalent bond | |
| Zheng et al. | Flow injection chemiluminescence determination of captopril with in situ electrogenerated Mn3+ as the oxidant | |
| CN103257176A (en) | Method for simultaneously detecting three isomers of benzenediol on basis of sensor of thionine functionalized carbon nanotube | |
| CN101310176B (en) | Method for determination of amount of double-stranded DNA and kit for the determination | |
| CN102128865A (en) | Method for detecting phenol compounds by using horseradish peroxidase-modified electrode | |
| CN104569119A (en) | Method for synergically enriching and detecting naphthol isomers | |
| CN103196898B (en) | Method for determining trace levamisole by bipyridine ruthenium electrochemiluminescence method | |
| CN102520034B (en) | Method for electrochemically measuring content of hydroperoxides in emulsion | |
| CN101532961B (en) | Method for detecting electrochemical luminescence | |
| CN104965014B (en) | The preparation method of the compound carbon paste electrode of quantum dot/enzyme for detecting SAM | |
| CN104020159B (en) | A kind of method for detecting tetracarboxylic phenyl porphyrin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHANGZHOU INSTITUTE OF ENERGY STORAGE MATERIALS + Free format text: FORMER OWNER: CHANGCHUN INST. OF APPLIED CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20140929 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 130022 CHANGCHUN, JILIN PROVINCE TO: 213000 CHANGZHOU, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20140929 Address after: Changzhou City, Jiangsu province Hehai road 213000 No. 9 Patentee after: Changzhou Institute of Energy Storage Materials & Devices Address before: 130022 Changchun people's street, Jilin, No. 5625 Patentee before: Changchun Institue of Applied Chemistry, Chinese Academy of Sciences |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100127 Termination date: 20190603 |