CN102590187A - Analysis method for using magnesium-aluminium carbonate hydrotalcite to catalyze luminol-hydrogen peroxide chemiluminescence - Google Patents
Analysis method for using magnesium-aluminium carbonate hydrotalcite to catalyze luminol-hydrogen peroxide chemiluminescence Download PDFInfo
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- CN102590187A CN102590187A CN2011100053804A CN201110005380A CN102590187A CN 102590187 A CN102590187 A CN 102590187A CN 2011100053804 A CN2011100053804 A CN 2011100053804A CN 201110005380 A CN201110005380 A CN 201110005380A CN 102590187 A CN102590187 A CN 102590187A
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Abstract
The invention provides an analysis method for using magnesium-aluminium carbonate hydrotalcite to catalyze luminol-hydrogen peroxide chemiluminescence. The luminol-hydrogen peroxide chemiluminescence analysis method is automatically carried out by a BPCL ultra-weak chemiluminescence analyzer, wherein solution to be tested, testing luminous solution and ultrapure water are respectively loaded in three storage bottles, a luminol-hydrogen peroxide chemiluminescence reaction system comprises a sensitizing catalyst solution injection port, a flow cell, a photomultiplier and a BPCL tester, and the analysis method is characterized in that the magnesium-aluminium carbonate hydrotalcite is adopted as sensitizing catalyst. Compared with carbonate catalyst in catalyzing the luminol-hydrogen peroxide chemiluminescence system, the magnesium-aluminium carbonate hydrotalcite remarkably enhances the effect of catalyzing luminol-hydrogen peroxide chemiluminescence, and moreover, the magnesium-aluminium carbonate hydrotalcite has the advantages of low cost, environment-friendliness and the like, is easy to synthesize, and has a broad application prospect in environment, bioanalysis and the like.
Description
Affiliated field:
The present invention relates to the application of magnalium carbonate hydrotalcite, be specifically related to magnalium carbonate hydrotalcite is used for chemiluminescence analytical technique.
Background technology:
Chemiluminescence (Chemiluminescence; CL) be meant the optical radiation phenomenon that the molecule that has absorbed the chemical reaction ability is produced when getting back to ground state by excited state, study physical and chemical processes such as relative dynamics, thermodynamics and light emission characteristic and have important theory and using value.Chemiluminometry is a kind of trace and a trace analysis method of confirming respective components content in the reaction according to a certain moment chemiluminescence intensity or chemiluminescence total amount, have high sensitivity, the range of linearity is wide, equipment is simple, easy and simple to handle, easily be automated and analyze characteristics such as quick.
In numerous chemical illuminating reagents; Luminol (the amino phthalylhydrazine of 3-) has higher luminescent quantum productive rate because of it; Be prone to synthesize and have better water solubility; Can with multiple oxygenant generation chemiluminescence reaction, become and used one of wide chemical luminescence reagent the most, be widely used in comprising the every field of immunodiagnosis and non-immunoassay.The luminol chemiluminescence analytic approach also becomes the most deep, the most widely used one type of chemiluminescence reaction system of research.
Luminol-hydrogen peroxide chemiluminescence reaction is to use luminol luminescence system the most widely.Luminol can be by many oxygenant (as: H under alkali condition
2O
2, K
3Fe (CN)
6, NaClO, KIO
4, KMnO
4, active oxygen etc.) oxidation and send the blue light that wavelength is 425nm.But the reaction velocity of luminol oxyluminescence is slower; People often add some enzyme or organic catalyst in system, like HRPO (HRP) [Robert, W.Charles; C.Alistair; H.Anal.Chem.2003,75,4244-4249], enzyme such as microperoxisome, xanthine oxidase, hydrogen peroxidase; Metalloprotein classes such as cromoci [Yukio, N.Heather, M.J.Hisamitsu, O.Tsukasa, K.J.David, L.Biochem.2010,49,2433-2442], haemoglobin, haptoglobin; Ozone molecule, halogen, persulfate [Catherine de, V.Alain, D.Virginie, R.Francesca; Z.Francis-Andr é, W.Biochem.2004,43,3956-3968] and Fe3+ [Tom á s; P-R.Carmen, M-L.Virginia, T.Jes ú s; M.Analyst 1999,124,1517-1521], Cu
2+, Co
2+And their mineral-type catalyzer such as complex.These oxygenants, catalyst concentration are linear, can measure these materials thus.
But because there is following shortcoming in existing catalyzer: the horseradish peroxidase of enzyme, enzyme prices such as glucose oxidase be mostly in 1g units up to a hundred or more than thousands of unit, and use the pre-treatment process of these catalyzer comparatively complicated loaded down with trivial details.Heavy metal such as Cu
2+, Co
2+Deng can work the mischief to the environment or the ecosystem, and under identical conditions, many metallic ions can catalysis or are suppressed the chemiluminescence reaction of same system, and optionally measuring a certain ion has brought difficulty thereby give; Surfactant SDS, also there are pollution in SDBS, CTAB, when water body concentration is 4～10g/mL, will produces water body and pollute.Therefore the friendly type of development environment, the cheap chemiluminescent catalyzer of luminol-hydrogen peroxide are the purposes of this research.
Summary of the invention
The objective of the invention is magnalium carbonate hydrotalcite is used for the chemiluminescent analytical approach of catalysis luminol-hydrogen peroxide.This catalyzer be a kind of be easy to the preparation, low cost, environmental protection catalyzer.
Luminol-hydrogen peroxide chemiluminescence analysis method; Be to accomplish automatically, wherein have three liquid storage bottles solution to be measured, test to be housed with luminous solution and ultrapure water respectively, enhanced sensitivity catalyst solution injection port through the ultraweak chemiluminescent analyzer of BPCL type; Flow cell; Photomultiplier and BPCL tester is characterized in that, used enhanced sensitivity catalyzer is a magnalium carbonate hydrotalcite.Be preferably magnesium/al mole ratio and be 3: 1 magnalium carbonate hydrotalcite.
Luminol-hydrogen peroxide chemiluminescence analysis method concrete steps are following: with solution to be measured, test with luminous solution and the ultrapure water corresponding liquid storage bottle of packing into; Open the peristaltic pump that ultrapure water bottle connected earlier; The flow velocity of ultrapure water being pressed 1mL/min injects the chain adapter; Flushing pipe 30min, BPCL working voltage are-900V to guarantee the stable operation of the ultraweak chemiluminescent analyzer of BPCL type;
Regulate test with the peristaltic pump that luminous solution and ultrapure water bottle connected, make 3 solution in the bottle all with the flow velocity injection runner pipe of 2mL/min, after stablizing with magnalium carbonate hydrotalcite solution injected system; Be written into and mixed with luminous solution with test by ultrapure water, with the pond that circulates after superoxol to be measured mixes, the three reacts again; Produce luminous, by BPCL image data, record; And the analysis data, obtain test result.
Described solution to be measured is to adopt the calibrated solution to be measured of mark-on method with hydrogen peroxide; It is that concentration is 2 * 10 that luminous solution is used in described test
-4M luminol and 2 * 10
-3M NaOH mixed solution; Magnalium carbonate hydrotalcite solution is that concentration is the solution of 0.01～0.015g/mL.
Magnalium carbonate hydrotalcite enhanced sensitivity luminol-hydrogen peroxide chemical luminous system is main relevant with the negative ion of hydrotalcite layered structure and intercalation thereof.The laminate of hydrotalcite has a large amount of positive charges, and it can be adsorbed on luminol negative ion and the HO that forms under the alkali condition in solution
2 -Negative ion increases the anion concentration of magnalium carbonate hydrotalcite laminate, has increased magnalium carbonate hydrotalcite and anionic collision opportunity.Simultaneously, CO
3 2-Hydrolysis generates HCO
3 -And the HO that under alkali condition, generates
2 -Generate HCO
4 -, HCO
4 -Decompose and produce CO
3 -, CO
3 -Luminous with the luminol anionic reactive, so its luminous signal increases.
The invention has the beneficial effects as follows: it is made the chemiluminescence catalyzer with magnalium carbonate hydrotalcite catalyst first and is used for luminol-hydrogen peroxide chemical luminous system analysis, has high detection sensitivity.This analytical approach can be widely used in chemistry, biochemistry, immunity and the bioanalysis.Magnalium carbonate hydrotalcite catalyst also has the preparation of being easy to, and cost is low, characteristics such as environmental protection.
Description of drawings
Fig. 1 luminol-hydrogen peroxide chemiluminescence reaction installation drawing.
1: superoxol bottle to be measured; 2: the luminol solution bottle; 3: ultrapure water bottle; 4: peristaltic pump; 5: six-way valve; 6: syringe; 7: threeway; 8: flow cell; 9: waste liquid bottle; 10: photomultiplier.
Fig. 2 Mg-Al-CO
3The XRD spectra of LDHs
The blank contrast of Fig. 3 magnalium carbonate hydrotalcite enhanced sensitivity luminol-hydrogen peroxide chemical luminous system
The contrast of Fig. 4 carbonate and magnalium carbonate hydrotalcite enhanced sensitivity luminol-hydrogen peroxide chemical luminous system
Specific embodiment
Embodiment 1: utilize magnalium carbonate hydrotalcite to measure hydrogen peroxide in the tap water as the chemiluminescence catalyzer.
A prepares solution to be measured and operation liquid
The preparation method of the hydrotalcite of magnalium carbonate intercalation is: take by weighing 11.5385g Mg (NO
3)
26H
2O and 5.6272gAl (NO
3)
39H
2O adds the 60mL ultrapure water, is mixed with saline solution; Take by weighing 0.7949g Na
2CO
3With 4.8g NaOH, add the 60mL ultrapure water, be mixed with alkali lye.Dropwise splash in the four-hole bottle above-mentioned two solution and stirring, pH is at 9.8-10.0 in control, and temperature is a room temperature.After dropwising, four-hole bottle is placed 60 ℃ of water-bath crystallization 24h.Product is centrifugal and wash 3 times, and dry 24h in 70 ℃ of vacuum drying chambers is ground to powdery.Be configured to the magnalium carbonate hydrotalcite solution of 0.01～0.015g/mL.Adopt FDAC 2500VB2+PC type X-ray diffractometer (XRD) to characterize product structure, the gained result sees Fig. 2, when 2 θ are 11 °, goes out the peak, turns out to be magnalium carbonate hydrotalcite, and can know that from Fig. 2 the crystalline form of gained is better.
Access tap water, and measure as early as possible, adopt the mark-on method to measure H in the tap water
2O
2Concentration.Use tap water compound concentration respectively is 1 * 10
-6M, 2 * 10
-6M, 3 * 10
-6M, 4 * 10
-6M, 5 * 10
-6M, 6 * 10
-6The M hydrogen peroxide.The headpin of packing into;
Be 2 * 10 for concentration in No. 2 bottles
-4M luminol and 2 * 10
-3M NaOH mixed solution;
The ultrapure water of packing in No. 3 bottles.
The B instrument is prepared
With ultrapure water flushing pipe 30min, flow velocity is set to 1mL/min.Voltage is set to-900V.Guarantee the stable operation of the ultraweak chemiluminescent analyzer of BPCL type.
The C sample introduction
Control peristaltic pump flow velocity is 2mL/min, with magnalium carbonate hydrotalcite solution injected system, is written into and is mixed with luminol solution by ultrapure water; With the pond that circulates after superoxol to be measured mixes, three's reaction produces luminous again; By the BPCL image data, and record.
Record the H in the tap water
2O
2Concentration is 9.3 * 10
-7M.The recovery is 99%.
Embodiment 2:
Gather rainwater, and measure as early as possible, adopt the mark-on method to measure H in the rainwater
2O
2Concentration.Use rainwater compound concentration respectively is 2 * 10
-6M, 4 * 10
-6M, 6 * 10
-6M, 8 * 10
-6M, 10 * 10
-6Hydrogen peroxide such as M.Pack in the headpin.
Other steps are with embodiment 1.Record the H in the rainwater
2O
2Concentration is 5.93 * 10
-6M.The recovery is 102%.
Contrast test:
To be respectively that 0.375M magnesium nitrate solution, 0.125M aluminum nitrate solution replace the magnalium carbonate neatly masonry catalyzer among the embodiment 1 with concentration, carry out same operating result and see Fig. 3.Find out that by Fig. 3 the chemiluminescence intensity of its magnesium nitrate solution and aluminum nitrate solution has explained that well below the signal of magnalium carbonate hydrotalcite catalysis luminol-hydrogen peroxide chemical luminous system is the metallic ion in magnalium carbonate hydrotalcite rather than the raw material.
, carry out same operating result and see Fig. 4 for the 0.06M sodium carbonate liquor replaces the magnalium carbonate neatly masonry catalyzer among the embodiment 1 with concentration.Visible by Fig. 4, CO
3 2The effect of catalysis luminol-hydrogen peroxide chemical luminous system compare and can ignore with the catalytic effect of magnalium carbonate hydrotalcite.
Claims (3)
1. one kind with the chemiluminescent analytical approach of the hydrotalcite catalyzed luminol-hydrogen peroxide of magnalium carbonate, and luminol-hydrogen peroxide chemiluminescence analysis method is to accomplish automatically through the ultraweak chemiluminescent analyzer of BPCL type; Wherein there are three liquid storage bottles solution to be measured, test to be housed respectively with luminous solution and ultrapure water; Enhanced sensitivity catalyst solution injection port, flow cell, photomultiplier and BPCL tester; It is characterized in that the enhanced sensitivity catalyst solution is a magnalium carbonate hydrotalcite solution;
Specific analytical method is: with solution to be measured, test with luminous solution and the ultrapure water corresponding liquid storage bottle of packing into; Open the peristaltic pump that ultrapure water bottle connected earlier; The flow velocity of ultrapure water being pressed 1mL/min injects the chain adapter; Flushing pipe 30min, BPCL working voltage are-900V to guarantee the stable operation of the ultraweak chemiluminescent analyzer of BPCL type;
Regulate test with the peristaltic pump that luminous solution and ultrapure water bottle connected, make 3 solution in the bottle all with the flow velocity injection runner pipe of 2mL/min, after stablizing with magnalium carbonate hydrotalcite solution injected system; Be written into and mixed with luminous solution with test by ultrapure water, with the pond that circulates after superoxol to be measured mixes, the three reacts again; Produce luminous, by BPCL image data, record; And the analysis data, obtain test result.
2. according to claim 1 with the chemiluminescent analytical approach of the hydrotalcite catalyzed luminol-hydrogen peroxide of magnalium carbonate, it is characterized in that described solution to be measured is to adopt the calibrated solution to be measured of mark-on method with hydrogen peroxide; It is that concentration is 2 * 10 that luminous solution is used in described test
-4M luminol and 2 * 10
-3M NaOH mixed solution; Magnalium carbonate hydrotalcite solution is that concentration is the solution of 0.01～0.015g/mL.
3. according to claim 1 with the chemiluminescent analytical approach of the hydrotalcite catalyzed luminol-hydrogen peroxide of magnalium carbonate, it is characterized in that described enhanced sensitivity catalyzer is that magnesium/al mole ratio is 3: 1 a magnalium carbonate hydrotalcite.
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| CN102967595A (en) * | 2012-12-03 | 2013-03-13 | 北京化工大学 | Chemical luminous sensor and method for detecting glucose by employing chemical luminous sensor |
| CN102998155A (en) * | 2012-11-23 | 2013-03-27 | 北京化工大学 | Device and method for online deduction of amino acid disulfide and determination of amino acid |
| CN104237211A (en) * | 2014-09-23 | 2014-12-24 | 中国科学院长春应用化学研究所 | Luminol chemiluminescence system and method for determining concentrations of luminol, thiourea dioxide and cobalt ion |
| CN109503577A (en) * | 2018-12-26 | 2019-03-22 | 安徽师范大学 | A kind of preparation of manganese Base Metal organogel and its application in catalysis luminol-hydrogen peroxide chemistry shines |
| CN109799230A (en) * | 2019-01-30 | 2019-05-24 | 中山大学 | The device for fast detecting and detection method of a kind of metal complex and chiral isomer |
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Cited By (9)
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| CN102998155A (en) * | 2012-11-23 | 2013-03-27 | 北京化工大学 | Device and method for online deduction of amino acid disulfide and determination of amino acid |
| CN102998155B (en) * | 2012-11-23 | 2015-04-15 | 北京化工大学 | Device and method for online deduction of amino acid disulfide and determination of amino acid |
| CN102967595A (en) * | 2012-12-03 | 2013-03-13 | 北京化工大学 | Chemical luminous sensor and method for detecting glucose by employing chemical luminous sensor |
| CN102967595B (en) * | 2012-12-03 | 2015-04-15 | 北京化工大学 | Chemical luminous sensor and method for detecting glucose by employing chemical luminous sensor |
| CN104237211A (en) * | 2014-09-23 | 2014-12-24 | 中国科学院长春应用化学研究所 | Luminol chemiluminescence system and method for determining concentrations of luminol, thiourea dioxide and cobalt ion |
| CN104237211B (en) * | 2014-09-23 | 2016-09-28 | 中国科学院长春应用化学研究所 | A kind of luminol chemiluminescence system and luminol, thiourea dioxide, the assay method of concentration of cobalt ions |
| CN109503577A (en) * | 2018-12-26 | 2019-03-22 | 安徽师范大学 | A kind of preparation of manganese Base Metal organogel and its application in catalysis luminol-hydrogen peroxide chemistry shines |
| CN109799230A (en) * | 2019-01-30 | 2019-05-24 | 中山大学 | The device for fast detecting and detection method of a kind of metal complex and chiral isomer |
| CN109799230B (en) * | 2019-01-30 | 2021-09-28 | 中山大学 | Rapid detection device and detection method for metal complex and chiral isomer |
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