CN104483430A - Ethoxyamine hydrochloride applied to formaldehyde content determination and testing method of ethoxyamine hydrochloride - Google Patents
Ethoxyamine hydrochloride applied to formaldehyde content determination and testing method of ethoxyamine hydrochloride Download PDFInfo
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- CN104483430A CN104483430A CN201410763297.7A CN201410763297A CN104483430A CN 104483430 A CN104483430 A CN 104483430A CN 201410763297 A CN201410763297 A CN 201410763297A CN 104483430 A CN104483430 A CN 104483430A
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Abstract
The invention discloses ethoxyamine hydrochloride applied to formaldehyde content determination and a testing method of ethoxyamine hydrochloride and relates to the field of formaldehyde content determination. Aiming at the deficiencies in the operation for determining the formaldehyde content by utilizing 2,4-dinitrophenylhydrazine as a derivatization agent in the prior art, a novel derivatization method having the advantages that the sample pretreatment is simple, the detection limit is low, the selectivity is good, and the sensitivity is high is provided. According to the method, the formaldehyde content is determined by virtue of a high performance liquid chromatography by utilizing the ethoxyamine hydrochloride as the derivatization agent; the dissolvability of a derived product in a mobile phase is high, so that an extraction step is omitted, and the important technical support is provided for the detection of formaldehyde.
Description
Technical field
The present invention relates to content of formaldehyde and measure field.
Background technology
At present, for the analysis of complex sample, high performance liquid chromatography is one of one the most effective the most general analytical approach.High performance liquid chromatography reaches universal degree at analysis field along with the high speed development high performance liquid chromatograph of scientific and technological level and instrument level.And high performance liquid chromatography have analysis speed fast, be widely used, the advantage such as high sensitivity.Therefore, high effective liquid chromatography for measuring is used also to be a kind of important method in the lower sample of content of formaldehyde.But, because formaldehyde does not have inherent chromophore and fluorophor, therefore, be difficult to the direct mensuration of formaldehyde in complex sample.In general, when analyzing the content of formaldehyde in sample, most of analytical approach all needs to derive.
The most popular derivating agent of existing detection formaldehyde is exactly 2,4-dinitrophenylhydrazine (DNPH), its principle is, formaldehyde is in acid condition with 2,4-dinitrophenylhydrazine is derivatized to 2,4-dinitrophenylhydrazone 60 DEG C of water-baths, extracts through organic solvent, by a series of processing procedure, finally carry out high-performance liquid chromatogram determination.Before DNPH post, the high performance liquid chromatography formaldehydogenic detection limit that spreads out is very low, but the solubleness of derivative products in mobile phase ensureing that the time that complete reaction needs is long, temperature of reaction is higher and generate is smaller, and therefore pretreatment process is more loaded down with trivial details.Having is exactly that DNPH has absorption in ultraviolet region again, can occur conditions of streaking, have a certain impact to product peak in liquid chromatography.
Summary of the invention
The object of the invention is the deficiency for above detection method, the detection content of formaldehyde detection method that a kind of sample pretreatment process is simple, detection time is short, selectivity is good, highly sensitive is provided.
The invention provides a kind of ethoxy amine hydrochloride being applied to content of formaldehyde and detecting.
Adopt high effective liquid chromatography for measuring content of formaldehyde, ethoxy amine hydrochloride is as derivating agent.
The present invention also provides a kind of assay method utilizing ethoxy amine hydrochloride described in claim 1 to detect content of formaldehyde, comprising:
1. the formaldehyde titer of variable concentrations is mixed with ethoxy amine hydrochloride derivating agent respectively, then under 205nm wavelength, carry out efficient liquid phase chromatographic analysis, by isocratic elution, map according to the peak area occurred in chromatogram and content of formaldehyde, drawing standard curve;
2. mixed with ethoxy amine hydrochloride derivating agent by liquid to be measured, then under 205nm wavelength, carry out efficient liquid phase chromatographic analysis, by isocratic elution, the peak area according to occurring in chromatogram brings typical curve into, draws liquid concentration of formaldehyde to be measured.
Described 1. in formaldehyde titer and ethoxy amine hydrochloride derivating agent mix with 2. in liquid to be measured mix with ethoxy amine hydrochloride derivating agent, incorporation time is 20min all at least.
Described 1. middle formaldehyde concentration of standard solution is at 0 ~ 150.0mgL
-1within scope.
Described ethoxy amine hydrochloride derivating agent solution can be prepared by the following method, takes ethoxy amine hydrochloride in pH value in neutral or weakly acidic phosphate buffered solution, uses buffer solution constant volume, obtain ethoxy amine hydrochloride derivating agent solution.
When carrying out liquid-phase chromatographic analysis, chromatographic column can be existing chromatographic column when carrying out liquid-phase chromatographic analysis.
Described liquid and preparation method thereof to be measured is identical with the sample treatment of existing known mensuration content of formaldehyde, obtains liquid to be measured by steam distillation, ultrasonic extraction, water soaking extraction method or ultrasonic-trichloroacetic acid method etc.
The present invention has following beneficial effect:
The method does not need through extraction, reaction temperature and, and the method detects and is limited to 0.02mgL
-1, relative standard deviation is low, is 1.1 ~ 5.5%, and recovery of standard addition is 88.0% ~ 108.0%, can as a kind of new Analysis Methods for Formaldehyde.
Accompanying drawing explanation
Fig. 1 is the ultraviolet chromatogram that formaldehyde of the present invention and ethoxy amine hydrochloride react the (ethoxymethyl) aldoxime generated;
Fig. 2 is the high-efficient liquid phase chromatogram of formaldehyde titer of the present invention;
Fig. 3 is the high-efficient liquid phase chromatogram of beer A in the embodiment of the present invention;
Fig. 4 is the high-efficient liquid phase chromatogram of beer B in the embodiment of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described.
The present invention according to principle is: formaldehyde and ethoxy amine hydrochloride can react and generate stable product (ethoxymethyl) aldoxime under neutrality or solutions of weak acidity, and reaction equation is as follows, generates intermediate product, reacts product (ethoxymethyl) aldoxime on the right of final reaction of formation formula:
Liquid-phase chromatographic analysis is carried out to (ethoxymethyl) aldoxime, occurs peak value at 205nm, as shown in Figure 1.
Embodiment one: adopt high performance liquid chromatography to measure to sample, comprise the following steps:
(1) formaldehyde standard solution is prepared, drawing standard curve
In the present embodiment, by iodimetric titration, the formaldehyde bought is demarcated, be mixed with 0 ~ 150.0mgL
-1formaldehyde titer, accurately pipetting 5.0mL formaldehyde standard solution joins in the ethoxy amine hydrochloride derivating agent of 5mL, pH=4, constantly 20min is stirred under normal temperature, solution after mixing is entered liquid chromatography analysis, its high-efficient liquid phase chromatogram as shown in Figure 2, pass through isocratic elution, qualitative according to the time, peak area quantification, the formaldehyde standard solution of variable concentrations does three times, average, map with peak area and content of formaldehyde, drawing standard curve, obtains regression equation, regression equation A=29.71C+38.38, linear relationship R
2=0.9998, A is peak area, and C is concentration of formaldehyde;
In the present embodiment, ethoxy amine hydrochloride derivating agent solution preparation process is take 0.2438g ethoxy amine hydrochloride in the phosphate buffered solution of pH=4, and with buffer solution constant volume in the volumetric flask of 500mL, obtaining concentration is 5mmolL
-1ethoxy amine hydrochloride derivating agent solution.
(2) liquid to be measured is prepared
Liquid and preparation method thereof to be measured can select the sample treatment of mensuration content of formaldehyde commonly known in the art, for illustrating, the present embodiment selects steam distillation, first with the carbon dioxide in filtration method removing beer sample, wheat juice and fermentation liquor, accurately pipette 50.0mL beer sample to move in 250mL cucurbit, add 20.0mL 1.4molL
-1phosphoric acid solution, stir with glass bar, carry out steam distillation immediately, collect distillate constant volume.Do liquid-phase chromatographic analysis after via hole diameter 0.45nm membrane filtration to use.Get liquid 5mL to be measured in the color comparison tube of 10mL, then add the above-mentioned ethoxy amine hydrochloride derivating agent of 5.0mL, react 20min under normal temperature, carry out liquid chromatogram measuring analysis;
(3) liquid chromatogram measuring
In the present embodiment, liquid phase chromatogram condition is as follows, also can select other liquid-phase chromatographic column:
Chromatographic column: Syncronis C18 post, specification is 150mm × 4.6mm I.D. 5 μm;
Mobile phase: 20.0mmolL
-1potassium dihydrogen phosphate buffer solution, pH=4.0-acetonitrile, 85:15v/v;
Column temperature: 30 DEG C;
Flow velocity is 1.0mLmin
-1;
Determined wavelength: 205nm;
Sample size: 5.0 μ L.
Sample, after chromatographic determination, obtains chromatogram, brings isocratic elution 7.78min place peak area value on chromatogram into (1) neutral line regression equation, can obtain content of formaldehyde in liquid to be measured.
In order to the feasibility of the method is described, carry out the test of formaldehyde standard solution precision, its result is as shown in table 1,
Table 1 formaldehyde standard solution Precision Experiment result
In the present embodiment, the high-efficient liquid phase chromatogram of beer sample is respectively as Fig. 3 and Fig. 4, and according to the peak area 1,2 provided, bring equation of linear regression into, result of calculation is as shown in table 2,
The recovery of standard addition experimental result of table 2 beer sample
Table 1 and table 2 result display relative standard deviation 1.1 ~ 5.5%, recovery of standard addition is 88.0% ~ 108.0%.
Above content is the further description done the present invention in conjunction with concrete embodiment, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (6)
1. the ethoxy amine hydrochloride being applied to content of formaldehyde and detecting.
2. be applied to the ethoxy amine hydrochloride that content of formaldehyde detects as claimed in claim 1, it is characterized in that: adopt high effective liquid chromatography for measuring content of formaldehyde, ethoxy amine hydrochloride is as derivating agent.
3. utilize ethoxy amine hydrochloride described in claim 1 to detect an assay method for content of formaldehyde, it is characterized in that comprising:
1. the formaldehyde titer of variable concentrations is mixed with ethoxy amine hydrochloride derivating agent respectively, then under 205nm wavelength, carry out efficient liquid phase chromatographic analysis, by isocratic elution, map according to the peak area occurred in chromatogram and content of formaldehyde, drawing standard curve;
2. mixed with ethoxy amine hydrochloride derivating agent by liquid to be measured, then under 205nm wavelength, carry out efficient liquid phase chromatographic analysis, by isocratic elution, the peak area according to occurring in chromatogram brings typical curve into, draws liquid concentration of formaldehyde to be measured.
4. the assay method detecting content of formaldehyde as claimed in claim 3, it is characterized in that: described 1. in formaldehyde titer and ethoxy amine hydrochloride derivating agent mix with 2. in liquid to be measured mix with ethoxy amine hydrochloride derivating agent, incorporation time is 20min all at least.
5. the assay method detecting content of formaldehyde as claimed in claim 4, is characterized in that: described 1. middle formaldehyde concentration of standard solution is at 0 ~ 150.0mgL
-1within scope.
6. the assay method detecting content of formaldehyde as claimed in claim 5, it is characterized in that: described ethoxy amine hydrochloride derivating agent solution can be prepared by the following method, take ethoxy amine hydrochloride in pH value in neutral or weakly acidic phosphate buffered solution, use buffer solution constant volume, obtain ethoxy amine hydrochloride derivating agent solution.
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| CN114487219A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Extracting agent and extracting method for detecting harmful substances in coating |
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| CN114487219A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Extracting agent and extracting method for detecting harmful substances in coating |
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