CN101975774A - Method for detecting hydrazine hydrate by electrochemical luminescence of terpyridyl ruthenium - Google Patents
Method for detecting hydrazine hydrate by electrochemical luminescence of terpyridyl ruthenium Download PDFInfo
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- CN101975774A CN101975774A CN 201010291351 CN201010291351A CN101975774A CN 101975774 A CN101975774 A CN 101975774A CN 201010291351 CN201010291351 CN 201010291351 CN 201010291351 A CN201010291351 A CN 201010291351A CN 101975774 A CN101975774 A CN 101975774A
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- hydrazine hydrate
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- ruthenium
- electrochemiluminescence
- bipyridine
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Abstract
The invention relates to a method for detecting hydrazine hydrate by electrochemical luminescence of terpyridyl ruthenium. The terpyridyl ruthenium serves as a luminescent material; and the hydrazine hydrate serves as one of reactants and is also a substance to be detected. The method comprises the following steps of: dissolving the terpyridyl ruthenium in phosphate buffer solution; performing cyclic voltammetry scanning in a potential range of between 0.2 and 1.8V (GC electrode) and between 0.2 and 1.6V (Pt electrode) by an electrochemical method respectively; and acquiring a generated optical signal by using a photodetector and processing data by using a computer so as to obtain a detection result. The concentration detection range of the hydrazine hydrate is between 1*10<-9>mol/L and 1*10<-5>mol/L and the lowest detection limit is 1*10<-9>mol/L. By the method, the hydrazine hydrate can be more effectively detected; the detection limit is lower; the linear range is wider; the sensitivity is high; the repeatability is high; and the test can be finished instantly. Therefore, the method is suitable for detecting all hydrazine hydrate-containing substances.
Description
Technical field
The invention belongs to a kind of high sensitive electrochemical luminous detection field, be specifically related to the method that a kind of tris (bipyridine) ruthenium electrochemiluminescence detects hydrazine hydrate.
Background technology
Hydrazine hydrate (N
2H
4H
2O) claim hydrazine hydrate again, pure product are water white oily liquids, and light ammonia flavor is arranged, and smolder in soft air, have strong basicity and hydroscopicity.Industrial general application content is the hydrazine hydrate aqueous solution of 40%--80% or the salt of hydrazine.Hydrazine hydrate liquid exists with the dipolymer form, and is miscible with water and ethanol, is insoluble to EC; It can corrode glass, rubber, leather, cork etc., at high temperature resolves into N
2, NH
3And H
2Hydrazine hydrate reduction is extremely strong, with halogen, HNO
3, KMnO
4Deng intense reaction, in air, can absorb CO
2, produce smog.Hydrazine hydrate and derivant product thereof are used in many commercial Application widely, as reductive agent, antioxidant, are used to produce medicine, gas-development agent etc.
Hydrazine hydrate belongs to the hypertoxic type material, and is the acute toxicity material, sucks this product steam, stimulates the nose and the upper respiratory tract.Liquid or steam have spread effect to eye, can cause the permanent lesion of eye.Skin there is pungency; Long-time skin contacts repeatedly, can absorb through skin to cause poisoning.The discharging of hydrazine can cause water pollution in the industrial waste water, the serious harm human health.Therefore, exploitation is a kind of simply, the hydrazine hydrate detection method has crucial meaning efficiently.
Existing hydrazine hydrate detection method mainly contains colourimetry (Li Wenzhen, Shanghai environmental science, 1988,7,19-21; Liu Zhengrong, Chinese territory health quarantine magazine, 1994,17 (5), 93-96), to dimethylamino benzaldehyde spectrophotometric method (Hua Lei, Dong Shuying, Yuan Yulu, health research, 1993,22 (2), 90-94), ultraviolet spectrophotometry (Zhang Xiaolin, Zhang Xiuying, the Shandong consecutive victories, Chinese environmental detects, and 1993,9 (5), 10-11) and electrochemical method (Xu Qin, Li Lihua, Hu Xiaoya, the assay laboratory, 2008,72 (5), 20-25), colourimetry wherein, ultraviolet spectrophotometry, electrochemical method is the method that hydrazine hydrate is detected in existing laboratory, and the detection quantitative limit of hydrazine is respectively 0.0045 mg/litre, 0.005 mg/litre, 1.0 * 10
-9Mol, and be the method that national standard detects hydrazine to dimethylamino benzaldehyde spectrophotometric method, its detection is limited to 0.003 mg/litre.But these methods or operation be trouble, or sensitivity is low, or sensing range is wide inadequately, testing process complicated operation or the like.
Tris (bipyridine) ruthenium Ru (bpy)
3 2+Electrochemiluminescence (Electrochemiluminescence, be called for short ECL) have original position response, detection sensitivity height, advantage such as the range of linearity is wide and instrument is simple, obtained widespread use in Pharmaceutical Analysis, amino acid analysis, dna probe analysis, enzyme biologic sensor field.But at present also without any such electrochemiluminescence being used for the relevant report that hydrazine hydrate detects.
Summary of the invention
The objective of the invention is at existing hydrazine hydrate detection method, propose a kind of brand-new method that detectability is lower, the detection electrochemiluminescence that the range of linearity is wideer, sensitivity is higher detects hydrazine hydrate.
Principle of the present invention is: the present invention uses tris (bipyridine) ruthenium as luminescent substance, and hydrazine hydrate also is a detected material as one of co-reactant simultaneously.Tris (bipyridine) ruthenium is dissolved in the phosphate buffer solution of pH=9, uses electrochemical method in 0.2-1.8V (GC electrode) and 0.2-1.6V (Pt electrode) potential range, it to be scanned respectively; The light signal that utilizes the photodetector collection to produce simultaneously obtains testing result through data processing.Because tris (bipyridine) ruthenium has very high luminescence efficiency, even the concentration of measured object hydrazine hydrate is very low, this method still can detect obvious electrochemiluminescence response, and the logarithm value of hydrazine hydrate concentration presents good linear relationship in the logarithm value of hydrazine hydrate adding front and back system electrochemiluminescence Strength Changes and the system, by calculating the content that can determine hydrazine hydrate in the system.
For achieving the above object, technical scheme of the present invention is the method that a kind of electrochemiluminescence detects hydrazine hydrate, and step is as follows:
(1) according to the hydrazine hydrate sample concentration, with 10
-7～10
-1The tris (bipyridine) ruthenium of mol/L and hydrazine hydrate sample to be measured join respectively in the phosphate or borate buffer solution of pH value for the 0.1M of 3-11;
(2) on any a electrochemical workstation, the solution that step (1) is disposed carries out cyclic voltammetry scan, wherein scans potential range GC electrode 0.2-1.8V, Pt electrode 0.2-1.6V;
(3) gather the light signal that electrochemical workstation scanning produces with photodetector, obtain electrochemiluminescence intensity after machine data is handled as calculated, again according to the content of the linear definite hydrazine hydrate of logarithm of logarithm that adds light intensity difference before and after the hydrazine hydrate sample and hydrazine hydrate concentration.
This method is applicable to that detecting all contains the material of hydrazine hydrate, and detection can be used any a electrochemical workstation and/or luminescence detector.Hydrazine hydrate detectable concentration scope is 1 * 10
-9Mol/L～1 * 10
-5Mol/L, lowest detection is limited to 1 * 10
-9Mol/L.
Described tris (bipyridine) ruthenium structural formula is as follows:
The invention has the beneficial effects as follows: can more effectively detect hydrazine hydrate, detectability is lower, and is highly sensitive, favorable reproducibility, and test can be finished in moment, was applicable to that detecting all contains the material of hydrazine hydrate, and all electrochemical light-emitting detectors.
Description of drawings
Fig. 1 is embodiment 1,2, utilizes tris (bipyridine) ruthenium-hydrazine hydrate electrochemiluminescsystem system to measure the detectability of hydrazine hydrate and its range of linearity on GC and Pt electrode;
Fig. 2 is embodiment 3,4, utilizes tris (bipyridine) ruthenium-hydrazine hydrate electrochemiluminescsystem system to measure the detectability of hydrazine hydrate and its range of linearity on GC and Pt electrode.
Wherein horizontal ordinate is the logarithm of hydrazine hydrate concentration, and ordinate is that the light intensity behind the adding hydrazine hydrate cuts the logarithm value that does not add the preceding light intensity of hydrazine hydrate, and promptly the ECL of mixed solution cuts the logarithm value of the ECL gained difference of tris (bipyridine) ruthenium blank.
Embodiment
Embodiment 1
Use MPI-B type electrochemiluminescence analysis instrument, the concentration that disposes tris (bipyridine) ruthenium with the 0.1M phosphate buffer of pH=9 is 1 * 10
-4The solution of mol/L, the high pressure of setting photomultiplier is 900V, and scanning voltage is at 0.2-1.8V, and sweep velocity 150mV/s, used working electrode are the GC electrode.Detect the luminous signal that does not add hydrazine hydrate solution, measured electrochemiluminescence intensity is 186080.
Use MPI-B type electrochemiluminescence analysis instrument, selecting the concentration of tris (bipyridine) ruthenium is 1 * 10
-4Mol/L adds hydrazine hydrate again and observes its influence to ECL, and the high pressure of setting photomultiplier is 900V, scanning voltage is at 0.2～1.8V, and sweep velocity 150mV/s, used working electrode are the GC electrode, buffer salt is the 0.1M phosphate buffer of pH=9, detects the luminous signal of solution.When hydrazine hydrate concentration is respectively 10
-9Mol/L, 10
-8Mol/L, 10
-7Mol/L, 10
-6Mol/L and 10
-5During mol/L, record its ECL luminous intensity and be respectively 197860,210000,226280,250620,296880, can find to strengthen gradually along with the adding ECL of hydrazine hydrate, and the logarithm of the logarithm of ECL Strength Changes value and hydrazine hydrate concentration is good linear relationship, and wherein the hydrazine hydrate concentration range is 1 * 10
-9Mol/L～1 * 10
-5Mol/L, equation of linear regression are y=6.2462+0.23779x, and linearly dependent coefficient is 0.99718, and the hydrazine hydrate lowest detection is limited to 1 * 10
-9Mol/L.The result as shown in Figure 1.Can determine the concentration of hydrazine hydrate in the system according to the changing value of ECL intensity.
Embodiment 3
Use MPI-B type electrochemiluminescence analysis instrument, the concentration that disposes tris (bipyridine) ruthenium with the 0.1M phosphate buffer of pH=9 is 1 * 10
-4The solution of mol/L, the high pressure of setting photomultiplier is 900V, and scanning voltage is at 0.2-1.6V, and sweep velocity 150mV/s, used working electrode are the Pt electrode, detect the luminous signal that does not add hydrazine hydrate solution, and measured electrochemiluminescence intensity is 4668.
Use MPI-B type electrochemiluminescence analysis instrument, selecting the concentration of tris (bipyridine) ruthenium is 1 * 10
-4Mol/L adds hydrazine hydrate again and observes its influence to ECL, and the high pressure of setting photomultiplier is 900V, and scanning voltage is at 0.2～1.6V, sweep velocity 150mV/s.Used working electrode is the Pt electrode, and buffer salt is the 0.1M phosphate buffer of pH=9, detects the luminous signal of solution.When hydrazine hydrate concentration is respectively 10
-9Mol/L, 10
-8Mol/L, 10
-7Mol/L, 10
-6Mol/L and 10
-5During mol/L, record its ECL luminous intensity and be respectively 5394,5632,6162,6530,7500, can find to strengthen gradually along with the adding ECL of hydrazine hydrate, and the logarithm of the logarithm of ECL Strength Changes value and hydrazine hydrate concentration is good linear relationship, wherein the hydrazine hydrate concentration range is 1 * 10
-9Mol/L～1 * 10
-5Mol/L, equation of linear regression are y=4.17604+0.14682x, and linearly dependent coefficient is 0.99595, and the hydrazine hydrate lowest detection is limited to 1 * 10
-9Mol/L.The result as shown in Figure 2.Can determine the concentration of hydrazine hydrate in the system according to the changing value of ECL intensity.
Claims (3)
1. a tris (bipyridine) ruthenium electrochemiluminescence detects the method for hydrazine hydrate, it is characterized in that:
(1) according to the hydrazine hydrate sample concentration, with 10
-7～10
-1The tris (bipyridine) ruthenium of mol/L and hydrazine hydrate sample to be measured join respectively in the phosphate or borate buffer solution of pH value for the 0.1M of 3-11;
(2) on electrochemical workstation, the solution that step (1) is disposed carries out cyclic voltammetry scan, wherein scans potential range GC electrode 0.2-1.8V, Pt electrode 0.2-1.6V;
(3) gather the light signal that electrochemical workstation scanning produces with photodetector, obtain electrochemiluminescence intensity after machine data is handled as calculated, again according to the content of the linear definite hydrazine hydrate of logarithm of logarithm that adds light intensity difference before and after the hydrazine hydrate sample and hydrazine hydrate concentration.
2. a kind of electrochemiluminescence according to claim 1 detects the method for hydrazine hydrate, it is characterized in that, this method is applicable to that detecting all contains the material of hydrazine hydrate.
3 a kind of electrochemiluminescences according to claim 1 detect the method for hydrazine hydrate, it is characterized in that described electrochemical workstation is any a electrochemical workstation and/or luminescence detector.
4. a kind of electrochemiluminescence according to claim 1 detects the method for hydrazine hydrate, it is characterized in that, and described tris (bipyridine) ruthenium, structural formula is as follows:
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103091305A (en) * | 2013-01-14 | 2013-05-08 | 大连理工大学 | Method for detecting quinolone antibiotic by means of electrochemical luminescence |
| CN104181212A (en) * | 2014-04-15 | 2014-12-03 | 西北大学 | Electrochemical sensor for detecting hydrazine hydrate, and its application |
| CN109001289A (en) * | 2018-07-11 | 2018-12-14 | 广西科技大学鹿山学院 | The method of bipyridyl ruthenium system electrogenerated chemiluminescence method measurement nefopam hydrochloride |
| CN114594151A (en) * | 2022-02-25 | 2022-06-07 | 北京工业大学 | Application of cysteamine as electrochemiluminescence co-reactant |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502798A (en) * | 2008-12-30 | 2009-08-12 | 西安凯立化工有限公司 | Nano ruthenium carbon-supported metal hydrogenating catalyst and method for producing the same |
-
2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502798A (en) * | 2008-12-30 | 2009-08-12 | 西安凯立化工有限公司 | Nano ruthenium carbon-supported metal hydrogenating catalyst and method for producing the same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103091305A (en) * | 2013-01-14 | 2013-05-08 | 大连理工大学 | Method for detecting quinolone antibiotic by means of electrochemical luminescence |
| CN103091305B (en) * | 2013-01-14 | 2016-06-01 | 大连理工大学 | The method of electrochemiluminescence detection quinolone antibiotic |
| CN104181212A (en) * | 2014-04-15 | 2014-12-03 | 西北大学 | Electrochemical sensor for detecting hydrazine hydrate, and its application |
| CN104181212B (en) * | 2014-04-15 | 2016-09-14 | 西北大学 | A kind of electrochemical sensor for hydrazine hydrate detection and application thereof |
| CN109001289A (en) * | 2018-07-11 | 2018-12-14 | 广西科技大学鹿山学院 | The method of bipyridyl ruthenium system electrogenerated chemiluminescence method measurement nefopam hydrochloride |
| CN114594151A (en) * | 2022-02-25 | 2022-06-07 | 北京工业大学 | Application of cysteamine as electrochemiluminescence co-reactant |
| CN114594151B (en) * | 2022-02-25 | 2023-12-01 | 北京工业大学 | Application of cysteamine as electrochemiluminescence coreactant |
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