CN101430285A - Electrochemical luminescence system - Google Patents
Electrochemical luminescence system Download PDFInfo
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- CN101430285A CN101430285A CNA2008102031009A CN200810203100A CN101430285A CN 101430285 A CN101430285 A CN 101430285A CN A2008102031009 A CNA2008102031009 A CN A2008102031009A CN 200810203100 A CN200810203100 A CN 200810203100A CN 101430285 A CN101430285 A CN 101430285A
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- luminophore
- electrochemiluminescence
- phosphate buffer
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Abstract
The invention discloses an electrochemical luminescent system, comprising tin ion or the compound thereof which is used as strong reducing agent, an illuminophore which can form excited state and illuminate by redox reaction and an electrolyte buffer system which is used as reducer and applies the redox reaction towards the illuminophore. The invention also discloses an electrochemical luminescence method of the luminescent system. The invention has the advantage that the constructed electrochemical luminescent system has the characteristics of high sensitivity, wide pH working range, component and product without toxic hazard to human body and environment, etc.
Description
Technical field
The present invention relates to a kind of electrochemical luminescence system.
Background technology
Electrochemiluminescence (ECL) is the product that electrochemical techniques combine with chemiluminescence, be meant by applying certain voltage and carry out electrochemical reaction, produce some electric living beings at electrode surface, form excited state by electron transport between these electric living beings or between some component in electric living beings and the system then, turn back to ground state and a kind of luminescence phenomenon of producing by excited state.Characteristics such as electrochemiluminescence has highly sensitive, and the range of linearity is wide, reacts controlled, and instrument and equipment is simple, and is simple to operate.Because the electrochemiluminescence group can be followed many materials such as amino acid, amine and alcohols generation coreaction, also can be used as luminous marker and biomacromolecule such as nucleic acid and protein etc. and carry out coupling, so be widely used in genetic test, immunodiagnosis, food security, a plurality of fields such as Pharmaceutical Analysis and environmental monitoring.
At present, in the electrochemiluminescence reactive system of redox mechanism, comprise two kinds of core components, luminophore and co-reactants.The main applied metal chelate of luminophore is as tris (bipyridine) ruthenium [Ru (bpy)
3 2+] etc., owing to its electrochemical reversible, can repeat to excite, the luminescence efficiency height, characteristics such as detection sensitivity height have become research and have used maximum electrochemiluminescence active substances.Co-reactant mainly is several organic compounds, be in early days oxalates (Bard A.J., et al., J.Am.Chem.Soc.1977,99,5399-5403), but it can only be applied to organic and acid solution system; Be tripropyl amine (TPA) (TPrA) (Leland J.K., et al., J.Electrochem.Soc.1990,137,3127-3131 afterwards; WO9005296), it can be used for water solution system, and its sensitivity is very high, has obtained using widely.But there is intrinsic defective in the tripropyl amine (TPA) system, and at first, its use pH scope is less, and is luminous very weak in acid solution, is subjected to certain limitation on versatility.Secondly, it is a kind of poisonous volatile material, can produce murder by poisoning to human body and environment like this.Therefore, develop the shortcoming that a kind of pH of application wide ranges, nonhazardous and highly sensitive co-reactant can overcome existing electrochemical luminescence system, and can expand the purposes of electrochemiluminescence technology.
Summary of the invention
Technical matters to be solved by this invention provides a kind of electrochemical luminescence system, can realize the qualitative and quantitative measurement to the trace analysis thing, can realize the high sensitive electrochemical luminesceence analysis in comprising physiological and unphysiologic wide region pH solution.
In order to solve above technical matters, the invention provides a kind of electrochemical luminescence system, comprising: tin ion or its compound as strong reductant; One can form excited state and luminous tris (bipyridine) ruthenium luminophore by redox reaction; And one implement the phosphoric acid electrolyte buffer system of redox reaction as reductive agent and luminophore.
The present invention also provides a kind of composite reagent or kit of the electrochemiluminescence analysis to object to be measured, and described composite reagent or kit comprise: as tin ion or its compound of strong reductant; The tris (bipyridine) ruthenium luminophore of thing serves as a mark; Reductive agent and luminophore are implemented the phosphoric acid solution system of redox reaction.
The present invention also provides a kind of electrochemiluminescence analysis method: can be by the material of tris (bipyridine) ruthenium luminophore mark with a kind of itself or its analog or its part, with tin ion or its compound be that co-reactant carries out redox reaction, carry out luminesceence analysis by electrochemical method.
Advantage of the present invention is that constructed electrochemical luminescence system has highly sensitive characteristics, can realize the qualitative and quantitative measurement to the trace analysis thing; Constructed system can realize the high sensitive electrochemical luminesceence analysis in comprising physiological and unphysiologic wide region pH solution; The component of this system and product do not have toxic action to human body and environment.
Description of drawings
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
Fig. 1 is cyclic voltammetric (CV) curve map;
Fig. 2 is electrochemiluminescence (ECL) curve map;
Fig. 3 is the electrochemiluminescence response curve in the different acidity sample environment;
Fig. 4 is different Ru (bpy)
3 2+The electrochemiluminescence response curve map of concentration;
Fig. 5 is the electrochemiluminescence response curve of different co-reactant concentration;
Fig. 6 contains other metallic ion of 0.1mM or TPrA electrochemiluminescence intensity and the Ru (bpy) that has only in the solution
3 2+Solution is histogram relatively.
Embodiment
Electrochemiluminescence program of the present invention is: the tin ion of usefulness strong reducing property or its compound are as the co-reactant of luminescence system, luminophore is in higher valence state by electrochemical redox reaction is oxidized, become excited state by the divalent tin ion reduction then, the process of getting back to ground state from unsettled excited state, send electromagnetic radiation, produce luminescence-producing reaction, this luminous can being caught by photodetector is through output signal after the digital-to-analog conversion.
Material of the present invention:
Two hydrated stannous chloride (SnCl
2.2H
2O, national medical group analyzes pure); Six hydration dichloride bipyridyl ruthenium (Ru (bpy)
3.Cl
2.6H
2O, Fluka); Other reagent is all available from medical group of country (analyzing pure or above rank).Used water is secondarily purified water.
SnCl
2The configuration of aqueous solution: take by weighing a certain amount of SnCl
2Solid earlier with the concentrated hydrochloric acid dissolving, is diluted to the initial soln of 0.05M again with secondary water.
Electrolyte buffer liquid: the phosphate buffer (PB) that disposes 0.01M, 0.05M, 0.1M, 0.5M, 1M respectively.
Control material:
Tripropyl amine (TPA) (C9H21N, national medical group, chemical pure).
Instrument:
Electrochemical reaction is by electrochemical workstation (CHI430C, Shanghai occasion China company) control.Three-electrode system (Shanghai occasion China company): diameter is that the glass-carbon electrode of 3mm is a working electrode, and Ag/AgCl (3M KCl) is a contrast electrode, and the pt silk is to electrode.Cyclic voltammetry: 0 ~ 1.3V; Sweep speed: 0.1mV/s.The electrochemiluminescence signal that is produced is gathered by photon metering probe (CH151, Binsong Photon Technology Co., Ltd. Beijing).
Glass-carbon electrode cleans: polish on 0.3 and 0.05 micron alumina powder respectively earlier, use secondary water and ethanol ultrasonic cleaning again.
Variable concentrations (0,0.1mM, SnCl 0.5mM)
2Ru (bpy) with 0.05mM
3 2+Solution mixes, place the 0.1M phosphate buffer (PB, pH=7.4) in, add electrolytic cell.Cyclic voltammetry is carried out galvanochemistry scanning, sweep limit: 0-1.3V; Sweep speed: 0.1V/s.Work as SnCl
2Concentration is 0 (promptly to have only Ru (bpy)
3 2+) time, near 1.15V point position, a pair of reversible electrochemical oxidation/reduction peak (shown in Fig. 1 curve 1) being arranged, the electrochemiluminescence counting is 0 (among Fig. 2 shown in the curve 1).In system, contain 0.1mM SnCl
2The time, at the catalytic current (shown in Fig. 1 curve 2) of 1.15V point position generation 6 μ A, the electrochemiluminescence maximum count is 250000 (shown in Fig. 2 curves 2).In system, contain 0.5mM SnCl
2, catalytic current is 13 μ A (shown in Fig. 1 curves 3), the electrochemiluminescence maximum count is 600000 (shown in Fig. 2 curves 3).
In Fig. 1 and Fig. 2, and employing 0.01M phosphate buffer (PB, pH=7.4); Sweep limit is 0-1.3V; Sweep speed is 0.1V/s.Curve 1:0.05mM Ru (bpy)
3 2+Curve 2:0.05mMRu (bpy)
3 2++ 0.1mM SnCl
2Curve 3:0.05mM Ru (bpy)
3 2++ 0.5mM SnCl
2
Respectively with 0.1mM SnCl
2With the Ru (bpy) of 0.1mM tripropyl amine (TPA) (TPrA) (material in contrast) with 1 μ M
3 2+Solution mixes, and places the electrolyte buffer liquid of pH=3/4/5/6/7/8/9, adds electrolytic cell.Cyclic voltammetry is carried out galvanochemistry scanning, sweep limit: 0-1.3V; Sweep speed: 0.1V/s.
When having co-reactant in the system, (do not have only Ru (bpy)
3 2+) time, the electrochemiluminescence counting is 0 (shown in Fig. 3 curve 1).In system, contain 0.1mM SnCl
2, during pH=3/4/5/6/7/8/9,1 μ MRu (bpy)
3 2+Electrochemiluminescence counting be respectively 750/4300/61900/100000/110600/110700/115600 (shown in Fig. 3 curve 3).In system, contain 0.1mM TPrA, during pH=3/4/5/6/7/8/9,1 μ M Ru (bpy)
3 2+Electrochemiluminescence counting be respectively 40/360/1100/4300/13600/39600/40500 (shown in Fig. 3 curve 2).
Among Fig. 3, adopt 0.05M phosphate buffer (PB); Sweep limit: 0 ~ 1.3V, sweep speed: 0.1V/s.1 μ M Ru (bpy)
3 2+Represent with (▲); 1 μ M Ru (bpy)
3 2++ 0.1mM TPrA represents with (●); 1 μ M Ru (bpy)
3 2++ 0.1mM SnCl
2Represent with (■).
Respectively with 0.5mM SnCl
2With 0.5mM TPrA (material in contrast) and concentration be the Ru (bpy) of 1pM/10pM/100pM/1nM/10nM
3 2+Solution mixes, and places the electrolyte buffer liquid of pH=7.4, adds electrolytic cell.Cyclic voltammetry is carried out galvanochemistry scanning, sweep limit: 0-1.3V; Sweep speed: 0.1V/s.In system, contain 0.5mM SnCl
2The time, the Ru of 1pM/10pM/100pM/1nM/10nM (bpy)
3 2+Electrochemiluminescence counting be respectively 150/500/1100/1900/8700 (Fig. 4).When containing 0.5mM TPrA in the system, the Ru of 1pM/10pM/100pM/1nM/10nM (bpy)
3 2+Electrochemiluminescence counting be respectively 10/140/390/750/4400 (Fig. 4).
Among Fig. 4, and employing 0.1M phosphate buffer (PB, pH=7.4); Sweep limit: 0 ~ 1.3V, sweep speed: 0.1V/s.0.5mM SnCl
2+ Ru (bpy)
3 2+Represent with (■); 0.5mM TPrA+Ru (bpy)
3 2+Represent with (●).
Concentration is the SnCl of 2 μ M/5 μ M/10 μ M/50 μ M/100 μ M/500 μ M/1000 μ M respectively
2And TPrA (material in contrast) and 1 μ M Ru (bpy)
3 2+Solution mixes, and places the electrolyte buffer liquid of pH=7.4, adds electrolytic cell.Cyclic voltammetry is carried out galvanochemistry scanning, sweep limit: 0-1.3V; Sweep speed: 0.1V/s.SnCl in system
2When concentration is respectively 2 μ M/5 μ M/10 μ M/50 μ M/100 μ M/500 μ M/1000 μ M, 1 μ M Ru (bpy)
3 2+Electrochemiluminescence counting be respectively 4500/8500/24000/51000/90600/113200/343300/478300; When TPrA concentration in the system is respectively 2 μ M/5 μ M/10 μ M/50 μ M/100 μ M/500 μ M/1000 μ M, 1 μ MRu (bpy)
3 2+Electrochemiluminescence counting be respectively 1500/2100/2650/4800/10700/25000/64800/84700 (Fig. 5).
Among Fig. 5, and employing 0.5M phosphate buffer (PB, pH=7.4); Sweep limit: 0 ~ 1.3V, sweep speed: 0.1V/s.1 μ M Ru (bpy)
3 2++ SnCl
2Represent with (■); 1 μ M Ru (bpy)
3 2++ TPrA represents with (●).
With concentration respectively the metallic ion Sn of 0.1mM
2+/ Cd
2+/ Cr
3+/ Cu
2+/ Hg
2+/ Mg
2+/ Mn
2+/ Pb
2+/ Zn
2+/ Fe
3+With 0.1mM TPrA (with Sn
2+Ion in addition and TPrA be material in contrast) and 1 μ M Ru (bpy)
3 2+Solution mixes, and places the electrolyte buffer liquid of pH=7.4, adds electrolytic cell.Cyclic voltammetry is carried out galvanochemistry scanning, sweep limit: 0-1.3V; Sweep speed: 0.1V/s.In system, be respectively the Sn of 0.1mM
2+/ TPrA/Cd
2+/ Cr
3+/ Cu
2+/ Hg
2+/ Mg
2+/ Mn
2+/ Pb
2+/ Zn
2+/ Fe
3+The time, 1 μ M Ru (bpy)
3 2+The ratio (IECL/I of electrochemiluminescence counting and background signal
0) be respectively 37.63/13.04/0.89/0.85/0.93/0.95/1.04/0.93/1.07/0.92/0.89 (Fig. 6)
Among Fig. 6, adopt 1 μ m Ru (bpy)
3 2+, 1M pH=7.4PB aqueous solution.Sweep limit: 0-1.3V, sweep speed: 0.1V/s.
From embodiment 1 to embodiment 5, can confirm Sn
2+Co-reactant as electrochemiluminescsystem system has unique luminescence phenomenon, and this characteristic is that general heavy metal ion does not possess; And it comprises that luminous overall characteristic is better than traditional co-reactant tripropyl amine (TPA).
The present invention can be used to make up a kind of Gneral analysis technology: any material, as long as itself or its analog or its part can be by the luminophore marks, can be that the redox reaction of co-reactant realizes luminesceence analysis by galvanochemistry startup and tin ion or its compound.This kind analytical technology promptly can be homogeneous analysis, also can be heterogeneous analysis; Promptly can be competition analysis, also can be non-competing analysis.
The present invention can be used to make up a kind of composite reagent or kit, to realize the electrochemiluminescence analysis to object to be measured.This reagent and kit comprise: as tin ion or its compound of strong reductant; The luminophore of thing serves as a mark; Reductive agent and luminophore are implemented the solution system of redox reaction.
Claims (13)
1, a kind of electrochemical luminescence system is characterized in that, comprising: tin ion or its compound as strong reductant; One can form excited state and luminous tris (bipyridine) ruthenium luminophore by redox reaction; And one implement the phosphoric acid electrolyte buffer system of redox reaction as reductive agent and luminophore.
2, electrochemical luminescence system as claimed in claim 1 is characterized in that, described tin compound is SnCl
2
As the described electrochemiluminescsystem system of claim 1-2, it is characterized in that 3, described electrolyte buffer system is the 0.01-1M phosphate buffer.
4, electrochemical luminescence system as claimed in claim 3 is characterized in that, described electrolyte buffer system is the phosphate buffer of 0.01M, 0.05M, 0.1M, 0.5M or 1M.
5, electrochemical luminescence system as claimed in claim 3 is characterized in that, described phosphoric acid buffer liquid acidity is pH4～pH10.
6, a kind of method of electrochemiluminescence comprises:
Step 1, with tin ion or its compound and the Ru (bpy) of strong reductant
3 2+Solution mixes, and places phosphate buffer, adds electrolytic cell then;
Step 2, carry out galvanochemistry scanning with cyclic voltammetry;
Step 3, collection photon and metering.
7, method as claimed in claim 6 is characterized in that, described tin compound is SnCl
2
As the described method of claim 6-7, it is characterized in that 8, the concentration of described phosphate buffer is at 0.01-1M.
9, method as claimed in claim 8 is characterized in that, the concentration of described phosphate buffer is 0.01M, 0.05M, 0.1M, 0.5M or 1M.
10, method as claimed in claim 8 is characterized in that, the acidity of described phosphate buffer is pH4～pH10.
11, a kind of composite reagent or kit of the electrochemiluminescence analysis to object to be measured, described composite reagent or kit comprise: as tin ion or its compound of strong reductant; The tris (bipyridine) ruthenium luminophore of thing serves as a mark; Reductive agent and luminophore are implemented the phosphoric acid solution system of redox reaction.
12, a kind of electrochemiluminescence analysis method: can be by the material of tris (bipyridine) ruthenium luminophore mark with a kind of itself or its analog or its part, with tin ion or its compound be that co-reactant carries out redox reaction, carry out luminesceence analysis by electrochemical method.
13, as method as described in the claim 12, it is characterized in that this kind analytical approach promptly can be homogeneous analysis, also can be heterogeneous analysis; Promptly can be competition analysis, also can be non-competing analysis.
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| CN2008102031009A CN101430285B (en) | 2008-11-21 | 2008-11-21 | Electrochemical luminescence system |
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| CN2008102031009A CN101430285B (en) | 2008-11-21 | 2008-11-21 | Electrochemical luminescence system |
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| CN101430285B CN101430285B (en) | 2011-01-26 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102650598A (en) * | 2011-02-24 | 2012-08-29 | 通用电气公司 | Method for detecting tin |
| CN102727213A (en) * | 2012-06-20 | 2012-10-17 | 浙江大学 | Method for manifesting latent fingerprints on basis of electrochemical luminescence marker |
-
2008
- 2008-11-21 CN CN2008102031009A patent/CN101430285B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102650598A (en) * | 2011-02-24 | 2012-08-29 | 通用电气公司 | Method for detecting tin |
| US8465979B2 (en) | 2011-02-24 | 2013-06-18 | General Electric Company | Method for detecting tin |
| CN102650598B (en) * | 2011-02-24 | 2016-03-09 | 通用电气公司 | For detecting the method for tin |
| CN102727213A (en) * | 2012-06-20 | 2012-10-17 | 浙江大学 | Method for manifesting latent fingerprints on basis of electrochemical luminescence marker |
| CN102727213B (en) * | 2012-06-20 | 2014-06-04 | 浙江大学 | Method for manifesting latent fingerprints on basis of electrochemical luminescence marker |
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