CN107870214A - The assay method of formaldehyde derivatives in a kind of water - Google Patents
The assay method of formaldehyde derivatives in a kind of water Download PDFInfo
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- CN107870214A CN107870214A CN201711117008.6A CN201711117008A CN107870214A CN 107870214 A CN107870214 A CN 107870214A CN 201711117008 A CN201711117008 A CN 201711117008A CN 107870214 A CN107870214 A CN 107870214A
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- water
- formaldehyde derivatives
- assay method
- formaldehyde
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
Abstract
The invention discloses a kind of assay method of formaldehyde derivatives in water, this method includes, blend step：4 6mL water samples are taken, 4 6mL nessler reagents is added, heating water bath after mixing, obtains deriving the aqueous solution；Determination step：The aqueous solution will be derived by filter membrane, then carry out liquid phase tandem mass spectrometer measure.The method of the present invention derives formaldehyde derivatives in liquid phase tandem mass spectrometry measure water using acetylacetone,2,4-pentanedione, and for this method relative to existing method, reagent price is cheap, and effectively eliminates because the false positive that background is brought.
Description
Technical field
The present invention relates to a kind of assay method of formaldehyde derivatives in test chemical field, more particularly to water.
Background technology
Formaldehyde, there is strong carcinogenesis, and the sodium formaldehyde sulfoxylate, the formalin etc. that are used in daily life can discharge first
Aldehyde, into environment, harm is produced to human body.
The assay method of formaldehyde in water, after typically being derived using acetylacetone,2,4-pentanedione, determined by ultraviolet spectrophotometry or dinitro
Hplc determination after base phenylhydrazine derives.
But column defects in the presence of existing method：
Acetylacetone,2,4-pentanedione derivative-ultraviolet spectrophotometry is easily produced false positive by ambient interferences, and dinitrophenylhydrazine
Recursive rule reagent price is expensive.
The content of the invention
For overcome the deficiencies in the prior art, it is an object of the invention to provide a kind of measure side of formaldehyde derivatives in water
Method, this method is using formaldehyde derivatives in acetylacetone,2,4-pentanedione derivative-liquid phase tandem mass spectrometry measure water, and this method is relative to existing side
Method, reagent price is cheap, and effectively eliminates because the false positive that background is brought.
The purpose of the present invention adopts the following technical scheme that realization：
The assay method of formaldehyde derivatives in a kind of water, including,
Blend step：4-6mL water samples are taken, 4-6mL nessler reagents is added, heating water bath after mixing, obtains deriving the aqueous solution；
Determination step：The aqueous solution will be derived by filter membrane, then carry out liquid phase tandem mass spectrometer measure.
Further, the nessler reagent is formulated by 1g ammonium acetates, 0.3g acetic acid, 0.05g acetylacetone,2,4-pentanediones.
Further, the temperature of the heating water bath is 55-65 DEG C.
Further, the time of the heating water bath is 50-70min.
Further, the aperture of the filter membrane is 0.45 μm.
Further, the liquid phase chromatogram condition is：
Waters ACQUITY UPLC BEH C18Column chromatography post, 50mm × 2.1mm, 1.7 μm；40 DEG C of column temperature；Sample size 1
μL；Flow velocity is 0.3mL/min；Mobile phase A is the aqueous formic acid that concentration is 0.1%, and B is acetonitrile.
Further, gradient elution program is：0.00-1.00min, 85%-85%A；1.00-2.00min 85%-
15%A；2.00-3.00min 15%-15%A；3.00-4.00min 15%-85%A；4.00-5.00min 85%-85%
A。
Further, Mass Spectrometry Conditions are：
Electric spray ion source；Cation scans；Capillary voltage 0.5kV；150 DEG C of ion source temperature；Remove solvent gas 500
℃；Remove solvent stream amount (nitrogen) 800L/h；Gas curtain throughput 50L/h；Multiple-reaction monitoring (MRM) mode detection.
Further, the characteristic ion mass spectrometry parameters of formaldehyde derivatives are 194/194,194/150,194/108.It is quantitative from
Son is 194/150.
Compared with prior art, the beneficial effects of the present invention are：
(1) in water of the present invention formaldehyde derivatives assay method, this method uses acetylacetone,2,4-pentanedione derivative-liquid phase tandem mass spectrum
Formaldehyde derivatives in method measure water, for this method relative to existing method, reagent price is cheap, and effectively eliminates because the back of the body
The false positive that scape is brought；
(2) in method of the invention, 1g ammonium acetates, 0.3g acetic acid, 0.05g acetylacetone,2,4-pentanediones composition nessler reagent, with formaldehyde
Generation hantzsch reacts, and generates dihydropyridine compound, experiments verify that, 1g ammonium acetates, 0.3g acetic acid, 0.05g levulinics
The concentration ratio of ketone is able to efficiently generate target product dihydropyridine compound；
(3) in method of the invention, 60 DEG C of water-baths can effectively improve the yield of target product dihydropyridine compound
With the time for reducing reaction.
Brief description of the drawings
Fig. 1 is the chromatogram of the formaldehyde derivatives of the present invention；
Fig. 2 is 20 μ g/L signal to noise ratio figure.
Embodiment
Below, with reference to accompanying drawing and embodiment, the present invention is described further, it is necessary to which explanation is, not
Under the premise of afoul, new implementation can be formed between various embodiments described below or between each technical characteristic in any combination
Example.
The assay method of formaldehyde derivatives in a kind of water, including,
Blend step：4-6mL water samples are taken, 4-6mL nessler reagents is added, heating water bath after mixing, obtains deriving the aqueous solution；
Determination step：The aqueous solution will be derived by filter membrane, then carry out liquid phase tandem mass spectrometer measure.
As the mode that further carries out, nessler reagent prepared by 1g ammonium acetates, 0.3g acetic acid, 0.05g acetylacetone,2,4-pentanediones and
Into.
As the mode that further carries out, the temperature of heating water bath is 55-65 DEG C.
As the mode that further carries out, the time of heating water bath is 50-70min.
As the mode that further carries out, the aperture of filter membrane is 0.45 μm.
As the mode that further carries out, liquid phase chromatogram condition is：
Waters ACQUITY UPLC BEH C18Column chromatography post, 50mm × 2.1mm, 1.7 μm；40 DEG C of column temperature；Sample size 1
μL；Flow velocity is 0.3mL/min；Mobile phase A is the aqueous formic acid that concentration is 0.1%, and B is acetonitrile.
As the mode that further carries out, gradient elution program is：0.00-1.00min, 85%-85%A；1.00-
2.00min 85%-15%A；2.00-3.00min 15%-15%A；3.00-4.00min 15%-85%A；4.00-
5.00min 85%-85%A.
As the mode that further carries out, Mass Spectrometry Conditions are：
Electric spray ion source；Cation scans；Capillary voltage 0.5kV；150 DEG C of ion source temperature；Remove solvent gas 500
℃；Remove solvent stream amount (nitrogen) 800L/h；Gas curtain throughput 50L/h；Multiple-reaction monitoring (MRM) mode detection.
As the mode that further carries out, the characteristic ion mass spectrometry parameters of formaldehyde derivatives are 194/194,194/150,
194/108.Quota ion is 194/150.
Embodiment 1：
The assay method of formaldehyde derivatives in a kind of water, including,
Blend step：4mL water samples are taken, 4mL nessler reagents is added, 55 DEG C of heating water bath 70min after mixing, obtains deriving water
Solution；Nessler reagent is formulated by 1g ammonium acetates, 0.3g acetic acid, 0.05g acetylacetone,2,4-pentanediones；
Determination step：The derivative aqueous solution is crossed into 0.45 μm of filter membrane, then carries out liquid phase tandem mass spectrometer measure.
Liquid phase chromatogram condition is：
Waters ACQUITY UPLC BEH C18Column chromatography post, 50mm × 2.1mm, 1.7 μm；40 DEG C of column temperature；Sample size 1
μL；Flow velocity is 0.3mL/min；Mobile phase A is the aqueous formic acid that concentration is 0.1%, and B is acetonitrile.
Gradient elution program is：0.00-1.00min, 85%-85%A；1.00-2.00min 85%-15%A；2.00-
3.00min 15%-15%A；3.00-4.00min 15%-85%A；4.00-5.00min 85%-85%A.
Mass Spectrometry Conditions are：
Electric spray ion source；Cation scans；Capillary voltage 0.5kV；150 DEG C of ion source temperature；Remove solvent gas 500
℃；Remove solvent stream amount (nitrogen) 800L/h；Gas curtain throughput 50L/h；Multiple-reaction monitoring (MRM) mode detection.
The characteristic ion mass spectrometry parameters of formaldehyde derivatives are 194/194,194/150,194/108.Quota ion is 194/
150。
Embodiment 2：
The assay method of formaldehyde derivatives in a kind of water, including,
Blend step：5mL water samples are taken, 5mL nessler reagents is added, 60 DEG C of heating water bath 60min after mixing, obtains deriving water
Solution；Nessler reagent is formulated by 1g ammonium acetates, 0.3g acetic acid, 0.05g acetylacetone,2,4-pentanediones；
Determination step：The derivative aqueous solution is crossed into 0.45 μm of filter membrane, then carries out liquid phase tandem mass spectrometer measure.
Liquid phase chromatogram condition is：
Waters ACQUITY UPLC BEH C18Column chromatography post, 50mm × 2.1mm, 1.7 μm；40 DEG C of column temperature；Sample size 1
μL；Flow velocity is 0.3mL/min；Mobile phase A is the aqueous formic acid that concentration is 0.1%, and B is acetonitrile.
Gradient elution program is：0.00-1.00min, 85%-85%A；1.00-2.00min 85%-15%A；2.00-
3.00min 15%-15%A；3.00-4.00min 15%-85%A；4.00-5.00min 85%-85%A.
Mass Spectrometry Conditions are：
Electric spray ion source；Cation scans；Capillary voltage 0.5kV；150 DEG C of ion source temperature；Remove solvent gas 500
℃；Remove solvent stream amount (nitrogen) 800L/h；Gas curtain throughput 50L/h；Multiple-reaction monitoring (MRM) mode detection.
The characteristic ion mass spectrometry parameters of formaldehyde derivatives are 194/194,194/150,194/108.Quota ion is 194/
150。
Embodiment 3：
The assay method of formaldehyde derivatives in a kind of water, including,
Blend step：6mL water samples are taken, 6mL nessler reagents is added, 65 DEG C of heating water bath 55min after mixing, obtains deriving water
Solution；Nessler reagent is formulated by 1g ammonium acetates, 0.3g acetic acid, 0.05g acetylacetone,2,4-pentanediones；
Determination step：The derivative aqueous solution is crossed into 0.45 μm of filter membrane, then carries out liquid phase tandem mass spectrometer measure.
Liquid phase chromatogram condition is：
Waters ACQUITY UPLC BEH C18Column chromatography post, 50mm × 2.1mm, 1.7 μm；40 DEG C of column temperature；Sample size 1
μL；Flow velocity is 0.3mL/min；Mobile phase A is the aqueous formic acid that concentration is 0.1%, and B is acetonitrile.
Gradient elution program is：0.00-1.00min, 85%-85%A；1.00-2.00min 85%-15%A；2.00-
3.00min 15%-15%A；3.00-4.00min 15%-85%A；4.00-5.00min 85%-85%A.
Mass Spectrometry Conditions are：
Electric spray ion source；Cation scans；Capillary voltage 0.5kV；150 DEG C of ion source temperature；Remove solvent gas 500
℃；Remove solvent stream amount (nitrogen) 800L/h；Gas curtain throughput 50L/h；Multiple-reaction monitoring (MRM) mode detection.
The characteristic ion mass spectrometry parameters of formaldehyde derivatives are 194/194,194/150,194/108.Quota ion is 194/
150。
Compliance test result
First, by taking embodiment 2 as an example, the chromatogram of formaldehyde derivatives is as shown in Figure 1.It will be seen from figure 1 that after formaldehyde-derived
The ms fragment response of the characteristic ion of product is high, and peak type is symmetrical, and effectively the derivative of formaldehyde in water can be determined
Property quantifies.
2nd, the range of linearity and detection limit
20 μ g/L, 50 μ g/L, 100 μ g/L, 200 μ g/L, 500 μ g/L first are configured to 10mg/L formaldehyde standard liquid
Each 10mL of aldehyde standard curve liquid, the above-mentioned solution of 5mL is taken respectively, add 5mL and contain 1g ammonium acetates, 0.3g acetic acid, 0.05g levulinics
The aqueous solution of ketone, the water-bath 60min in 60 DEG C of water-baths.Liquid phase tandem mass spectrometer determines after derivative.As a result show, with characteristic ion
194/150 is used as quota ion, the mass concentration of formaldehyde standard liquid in the μ g/L-500 μ g/L of concentration range 20 with Qi Feng faces
Good linear relationship is presented in product, and its correlation coefficient r is 0.9995.
With reference to figure 2, detection limit is typically using method detection limit as its detection limit, and when concentration is 20 μ g/L, signal to noise ratio is
311 times, according to 10 times of signal to noise ratio as its method detection limit, calculate its detection and be limited to 0.7 μ g/L.
3rd, the rate of recovery and precision
The water sample of formaldehyde is not contained from the method measure for passing through embodiment 1-3 respectively.
Three groups of samples add basic, normal, high three concentration of 50 μ g/L, 100 μ g/L, 200 μ g/L respectively, according to the reality of the present invention
The method for applying example 2 is added rate of recovery experiment, determines its TIANZHU XINGNAO Capsul.Parallel determination three above concentration 3 times, calculates it
Precision is relative standard deviation (RSD).The gained rate of recovery the results are shown in Table shown in 1 with precision.
The rate of recovery of table 1 and Precision Experiment result
Above-mentioned embodiment is only the preferred embodiment of the present invention, it is impossible to the scope of protection of the invention is limited with this,
The change and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed scope.
Claims (9)
- A kind of 1. assay method of formaldehyde derivatives in water, it is characterised in that including,Blend step：4-6mL water samples are taken, 4-6mL nessler reagents is added, heating water bath after mixing, obtains deriving the aqueous solution；Determination step：The aqueous solution will be derived by filter membrane, then carry out liquid phase tandem mass spectrometer measure.
- 2. the assay method of formaldehyde derivatives in water as claimed in claim 1, it is characterised in that the nessler reagent is by 1g second Sour ammonium, 0.3g acetic acid, 0.05g acetylacetone,2,4-pentanediones are formulated.
- 3. the assay method of formaldehyde derivatives in water as claimed in claim 1, it is characterised in that the temperature of the heating water bath For 55-65 DEG C.
- 4. the assay method of formaldehyde derivatives in water as claimed in claim 1, it is characterised in that the time of the heating water bath For 50-70min.
- 5. the assay method of formaldehyde derivatives in water as claimed in claim 1, it is characterised in that the aperture of the filter membrane is 0.45μm。
- 6. the assay method of formaldehyde derivatives in water as claimed in claim 1, it is characterised in that the liquid phase chromatogram condition For：Waters ACQUITY UPLC BEH C18Column chromatography post, 50mm × 2.1mm, 1.7 μm；40 DEG C of column temperature；The μ L of sample size 1； Flow velocity is 0.3mL/min；Mobile phase A is the aqueous formic acid that concentration is 0.1%, and B is acetonitrile.
- 7. the assay method of formaldehyde derivatives in water as claimed in claim 6, it is characterised in that gradient elution program is： 0.00-1.00min, 85%-85%A；1.00-2.00min 85%-15%A；2.00-3.00min 15%-15%A；3.00- 4.00min 15%-85%A；4.00-5.00min 85%-85%A.
- 8. the assay method of formaldehyde derivatives in water as claimed in claim 1, it is characterised in that Mass Spectrometry Conditions are：Electric spray ion source；Cation scans；Capillary voltage 0.5kV；150 DEG C of ion source temperature；Remove 500 DEG C of solvent gas；Go Solvent stream amount 800L/h；Gas curtain throughput 50L/h；Multiple-reaction monitoring pattern detects.
- 9. the assay method of formaldehyde derivatives in water as claimed in claim 8, it is characterised in that the feature of formaldehyde derivatives from Sub- mass spectrometry parameters are 194/194,194/150,194/108；Quota ion is 194/150.
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| CN109613142A (en) * | 2019-01-14 | 2019-04-12 | 南京市产品质量监督检验院 | The method that gas chromatography measures free formaldehyde content in coating or adhesive |
| CN109884231A (en) * | 2019-01-28 | 2019-06-14 | 广州京诚检测技术有限公司 | The measuring method of Famoxate in a kind of water |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109884231A (en) * | 2019-01-28 | 2019-06-14 | 广州京诚检测技术有限公司 | The measuring method of Famoxate in a kind of water |
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Application publication date: 20180403 |