KR20170099233A - method of simultaneous analysis for aldehydes using gas chromatography with mass spectrometry - Google Patents
method of simultaneous analysis for aldehydes using gas chromatography with mass spectrometry Download PDFInfo
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Abstract
The present invention relates to a method for simultaneous analysis of aldehydes using gas chromatography and mass spectrometry, more particularly, to derivatization with a hydrazine functional group and solid phase extraction using a head space solid phase micro-extraction (HS-SPME) And a new analytical method capable of simultaneously quantitatively analyzing a plurality of aldehydes using gas chromatography and mass spectrometry.
The simultaneous analysis method of aldehydes according to the present invention can simultaneously analyze a plurality of aldehydes including formaldehyde, acetaldehyde, glutaraldehyde and glioxal by a simple analysis procedure, It is possible to detect a trace amount of aldehydes of 0.0003 mg / L in an environmentally friendly manner.
Description
The present invention relates to a method for simultaneous analysis of aldehydes using gas chromatography and mass spectrometry, and more particularly, to a method for simultaneous determination of aldehydes by hydrazine functional groups and using headspace solid phase microextraction (HS-SPME) And a new analytical method capable of simultaneously quantitatively analyzing a plurality of aldehydes using gas chromatography and mass spectrometry.
Formaldhyde is a colorless and irritating hydrophilic gas that is soluble in polar solvents such as water and alcohol. It is also used as a disinfectant in the industry and as a food preservative. It is used for the manufacture of synthetic resins, dyes for fabrics and waterproofing agents Is widely used in various manufacturing industries such as adhesives, polymers and coatings of various chemical industries and food packaging materials and is produced as an intermediate or product. Formaldehyde is easily exposed to the environment (EPA 560 / 2-76-009, 22-80, 1976) because it is widely used in many manufacturing industries such as leather manufacturing, photographic plates, explosives, cosmetics and fungicides. The amount of formaldehyde produced in the product is much higher than the amount naturally occurring. According to the US Environmental Protection Agency (FDA), formaldehyde has been designated as a B1 carcinogen by inhalation exposure and has been designated as a monitoring item in the Japanese water law and has been set at 80 μg / L of water quality ('Water quality standard 50 items' , Japan (2007)).
In addition to formaldehyde, formaldehyde is also produced by oxidizing agents such as ozone or chlorine in the water treatment process. Acetaldehyde, Glyoxal, etc. are produced as well as formaldehyde. The structures and characteristics of aldehydes such as formaldehyde, acetaldehyde, glutaraldehyde and glyoxal are shown in Table 1 below.
(
UPAC
name)
No.
(
° C
)
(
° C
)
Formaldehyde
Acetaldehyde
Glutardialdehyde
Glyoxal, Oxaldehyde
These byproducts are substances that stimulate respiratory mucous membranes and optic nerve and are poisonous. They are substances that are managed as monitoring items in the water quality because they are harmful effects pollutants that can be easily exposed in living environment. Therefore, it is fast, .
Formaldehyde has low molecular weight and low boiling point, making it difficult to separate and analyze. Standard methods 6252 and EPA Method 556 are commonly used for liquid-liquid extraction of liquid samples with GC / ECD.
In addition, pre-treatment of the sample is required before the analysis. The pretreatment of the sample is performed by Liquid-Liquid Extraction (LLE), Solid Phase Extraction (SPE), Solid Phase Micro-Extraction (SPME), Headspace Solid- HS-SPME, and headspace solid phase micro extraction).
Among them, Micro-Extraction (SPME) and headspace solid phase micro extraction (HS-SPME) have advantages of easy analysis, low sample and solvent, and are widely applied to GC analysis. In addition, the LLE and SPE methods, which are widely used for GC and LC analysis, have the advantage of being able to control the quantitative limit that enables analysis even at low concentrations.
(GC / ECD), Gas Chromatography / Flame Ionization Detector (GC / FID), Gas Chromatography Mass Spectrometry (GC / MS), High Performance Liquid Chromatography spectrophotometer. Recently, Flow Injection Analysis (FIA) methods have also been introduced.
2,4-dinitrophenylhydrazine (DNPH) for HPLC analysis and O-2,3,4,5,6- (Pentafluorobenzyl) hydroxylamine hydrochloride for GC analysis are available for selection of analytical sensitivity and selectivity. (PFBHA) are mainly used. In the FIA method, acetoacetanilide and methyl acetoacetate are used. In addition, the method of HPLC analysis by DNPH (2,4-dinitrophenylhydrazine) derivatization has been used as a standard method by the US Environmental Protection Agency (EPA), and the head space solid phase extraction (HS-SPME) (J. of Chromato. A, 1210, 25-29, 2008).
However, the spectrophotometry of the above methods has a problem that the sensitivity is low. The 2,4-DNPH derivatization method can increase the detection limit due to the contamination of the derivatization reagent, and the reaction time is long The preprocessing time is long. The method of derivatization using PFBHA has many disadvantages such as the use of reagents for pretreatment and organic solvents for extraction and the time required for the pretreatment due to the time consuming for the reaction.
In addition, since aldehydes are low in volatility, preprocessing using headspace solid phase micro extraction (HS-SPME) is difficult.
Therefore, there is a demand for eco-friendly analysis methods that use less reagents or solvents, have less pre-processing time, and have a simple analysis procedure.
Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems occurring in the prior art, and it is an object of the present invention to provide a novel analytical method capable of easily and simultaneously quantitatively analyzing a plurality of aldehydes including formaldehyde, acetaldehyde, glutaraldehyde, And a method thereof.
In order to solve the above problems,
Preparing a derivatization pretreatment sample by adding an ionic strength enhancer, a pH adjuster, an internal standard material, and a hydrazine derivatizing material that binds to the aldehyde material contained in the sample to the sample to be detected;
A solid phase extraction step of extracting the derivatization pretreatment sample with a solid phase microextractor to produce a microextractor for measurement adsorbing the analytical substance;
The micro-extractor for measurement was injected into the inlet of a gas chromatograph
A first measuring step of desorbing the analyte to obtain a gas chromatogram of the sample; And
A second measurement step in which the desorbed measurement sample passes through a capillary separation tube and passes through a mass spectrometer to obtain a mass spectrum; A method for simultaneous analysis of aldehydes.
The simultaneous analysis method of aldehydes of the present invention
(a) a sample preparation step in which an internal standard substance and an ionic strength enhancer for increasing the ionic strength are added to the sample,
(b) a derivatization step to convert the polar group of the analyte into a compound suitable for gas chromatographic analysis,
(c) extracting with a solid phase microextractor,
(d) introducing an analyte eluted through a capillary separation tube into a mass spectrometer to detect and determine the content, and a detection and quantification step.
In the present invention, the simultaneous analysis method simultaneously detects a plurality of aldehydes including formaldehyde, acetaldehyde, glutaraldehyde, and glioxal, and performs qualitative and quantitative analysis with excellent accuracy.
In the simultaneous analysis of aldehydes according to the present invention, the hydrazine derivatizing material may be at least one selected from the group consisting of hydrazine, 2,2,2-trifluoroethyl hydrazine, and methylhydrazine. In the simultaneous analysis of aldehydes according to the present invention, the hydrazine derivatizing material is preferably 2,2,2-trifluoroethyl hydrazine.
In the simultaneous analysis method of the aldehydes of the present invention, the reaction mechanism of the aldehydes and the derivatized material, 2,2,2-trifluoroethyl hydrazine, is shown in the following
Reaction mechanism of formaldehyde with derivatized material
Reaction mechanism of acetaldehyde with derivatized material
3. Mechanism of reaction between glutaraldehyde and derivatized material
4. Mechanism of reaction between glyoxal and derivatized material
As shown in the above chemical formula, the aldehydes and 2,2,2-trifluoroethyl hydrazine, which are derivatizing materials, react with each other to generate hydrazones, and accordingly exhibit appropriate volatility. Thus, the conventional aldehydes have low volatility, It is possible to solve the problem that it is difficult to perform the pre-treatment using the solid phase extraction (HS-SPME, headspace solid phase micro extraction).
In the method for simultaneous analysis of aldehydes according to the present invention, the amount of the hydrazine derivatizing substance added is preferably from 1.0 μg to 1000 μg.
In the simultaneous analysis of aldehydes according to the present invention, it is preferable that the addition amount of the hydrazine derivatizing material is 0.00002 to 0.02 parts by weight per 100 parts by weight of the sample to be detected.
In the simultaneous analysis of aldehydes according to the present invention, it is preferable that the ionic strength increasing agent is any one selected from the group consisting of sodium chloride, sodium sulfate, sodium carbonate, sodium hydroxide, and combinations thereof.
In the simultaneous analysis of aldehydes according to the present invention, the concentration of the ionic strength increasing agent included in the derivatization pretreatment sample may be 4 to 6 wt%. When the concentration of the ionic strength increasing agent is more than 6% by weight, the extraction efficiency of one target substance is lowered. When the concentration is less than 4% by weight, the effect of increasing the ionic strength may be insignificant. The ionic strength enhancer may preferably be sodium chloride, and the extraction efficiency of 1,4-dioxane and formaldehyde may be rather low when the concentration of sodium chloride in the derivatization pretreatment sample is between 4 and 6% by weight .
In the simultaneous analysis of aldehydes according to the present invention, the pH adjuster is preferably mixed with sodium bicarbonate and potassium carbonate in a weight ratio of 3: 1. In the simultaneous analysis of aldehydes according to the present invention, the pH of the solution is preferably adjusted to 8 to 10 by the addition of the pH adjusting agent.
In the simultaneous analysis method of aldehydes according to the present invention, the internal standard material is added to determine the recovery rate, and it is preferable to include acetone-d6 and trimethylacetaldehyde.
In the simultaneous analysis method of the aldehydes of the present invention, The solid adsorbent preferably includes polydimethylsiloxane and divinylbenzene, and it is possible to use a fibrous solid adsorbent composed of the same.
In the simultaneous analysis method of aldehydes according to the present invention, it is preferable that the solid phase extraction step is performed by heating and not heating the solid phase adsorbent to the derivatization pretreatment sample.
In the simultaneous analysis of aldehydes according to the present invention, the step of extracting the solid phase is preferably carried out at 40 to 90 ° C. When the reaction temperature is lower than 40 ° C., some analytical samples may not be extracted and thus may not be detected during the analysis.
In the simultaneous analysis method of aldehydes of the present invention, the solid phase extraction step is preferably performed for 10 minutes to 60 minutes.
In the simultaneous analysis of aldehydes according to the present invention, the capillary separation tube used in the gas chromatography is a semi-polar or non-polar separation tube having a diameter of 0.2 to 0.32 mm and a length of 10 to 60 m .
In the simultaneous analysis method of aldehydes according to the present invention, the initial conditions of the vaporization conditions of the analytical sample are 30 to 50, and the rising temperature per minute is preferably 5 to 30.
In the simultaneous analysis method of aldehydes according to the present invention, it is preferable that the mass spectrometer uses a quadrupole mass spectrometer and selects and analyzes an appropriate ion for each aldehyde in a selected ion monitoring mode.
In the simultaneous analysis method of aldehydes according to the present invention, the aldehydes include formaldehyde, acetaldehyde, glutaraldehyde, or glyoxal.
The simultaneous analysis method of aldehydes according to the present invention can simultaneously analyze a plurality of aldehydes including formaldehyde, acetaldehyde, glutaraldehyde and glioxal by a simple analysis procedure, It is possible to detect a trace amount of aldehydes of 0.0003 mg / L in an environmentally friendly manner.
Figure 1 shows the temperature conditions of the solid phase extraction step in the headspace as an analytical method according to one embodiment of the present invention.
FIG. 2 shows a chromatogram of a plurality of aldehydes analyzed by an analytical method according to an embodiment of the present invention.
Hereinafter, the present invention will be described in more detail by way of examples. However, the present invention is not limited by the examples.
< Examples> Stage 1 : Derivatization Preparation of pretreatment sample
Exactly 5 mL of the analytical sample was prepared in a 10 mL headspace vial.
Sodium hydrogencarbonate and potassium carbonate were added to the vial containing the analytical sample at a weight ratio of 3: 1.
Then, sodium chloride was added as an ionic strength increasing agent, acetone-d6 and trimethylacetaldehyde were added as an internal standard, 2,2,2-trifluoroethyl hydrazine as a derivatizing agent was added, and the mixture was closed with a stopper.
< Examples> Step 2 : Extraction of solid adsorbent
The vial containing the pretreatment sample prepared in
< Examples> Step 3 : Mass Spectrometry by Gas Chromatography
The extracted fiber was injected into gas chromatography. The gas chromatograph was injected into a mass spectrometer through a capillary separator and the gas chromatogram and mass spectrum were measured.
The analysis conditions of the gas chromatography are shown in Table 3 below.
(min.)
(° C / min.)
(° C)
(min.)
< Experimental Example 1> Calibration curve of sample and calculation of concentration
Chromatograms of the selected ions were prepared, peak areas were measured from peak positions corresponding to retention times of each substance, peak areas of internal standard materials were measured, and calibration curves were generated using the ratios.
The selected ion and calibration curves and correlation coefficient, precision and accuracy, detection limit and quantitation limit are shown in Table 4 below.
Coefficient
(%)
(%)
(mg / L)
(mg / L)
Aldehyde
As shown in the chromatogram of FIG. 2, formaldehyde, acetaldehyde, glutaraldehyde, or aldehydes of glyoxal were effectively separated. Formaldehyde and acetaldehyde were similar in properties and elongated and eluted, It is confirmed that the specific masses are different from each other and can be separated by selecting the mass.
Claims (15)
A solid phase extraction step of extracting the derivatization pretreatment sample with a solid phase microextractor to produce a microextractor for measurement adsorbing the analytical substance
A first measuring step of injecting the measuring micro extractor into an inlet of a gas chromatography measuring instrument to desorb the analyte to obtain a gas chromatogram of the sample; And
And a second measurement step in which the desorbed measurement sample passes through a capillary separation tube and passes through a mass spectrometer to obtain a mass spectrum
Simultaneous analysis of aldehydes.
Wherein the hydrazine derivatizing material is at least one selected from the group consisting of hydrazine, 2,2,2-trifluoroethyl hydrazine, and methylhydrazine
Simultaneous analysis of aldehydes.
And the addition amount of the hydrazine derivatizing substance is 1.0 占 퐂 to 1000 占 퐂
Simultaneous analysis of aldehydes.
The hydrazine derivatized material
And 0.00002 to 0.02 parts by weight of a hydrazine derivatized material per 100 parts by weight of the sample to be detected
Simultaneous analysis of aldehydes.
The ionic strength enhancer may be any one selected from the group consisting of sodium chloride, sodium sulfate, sodium carbonate, sodium hydroxide, and combinations thereof
Simultaneous analysis of aldehydes.
Wherein the pH adjusting agent is a mixture of sodium hydrogencarbonate and potassium carbonate in a weight ratio of 3: 1
Simultaneous analysis of aldehydes.
Wherein said internal standard material comprises acetone-d6 and trimethylacetaldehyde
Simultaneous analysis of aldehydes.
Wherein the solid adsorbent comprises polydimethylsiloxane and divinylbenzene,
Simultaneous analysis of aldehydes.
The extraction step is a step of extracting the sample by heating so as not to contact the solid adsorbent
Simultaneous analysis of aldehydes.
Wherein the solid phase extraction step is carried out at a temperature of from 40 캜 to 90 캜
Simultaneous analysis of aldehydes.
And the solid phase extraction step is performed for 10 minutes to 60 minutes
Simultaneous analysis of aldehydes.
The capillary separation tube is a semi-polar or non-polar separation tube,
A diameter of 0.2 mm to 0.32 mm, and a length of 10 m to 60 m
Simultaneous analysis of aldehydes.
In the first measurement step for obtaining the gas chromatogram of the sample by injecting the micro-extractor for measurement into the injection port of the gas chromatograph to desorb the analyte, the initial condition of the analytical sample is 30 to 50, and the rising temperature per minute 5 to 30
Simultaneous analysis of aldehydes.
The mass spectrometer uses a quadrupole mass spectrometer to select and analyze suitable ions for each aldehyde in a selected ion monitoring mode
Simultaneous analysis of aldehydes.
Wherein said aldehydes comprise formaldehyde, acetaldehyde, glutaraldehyde, or glyoxal
Simultaneous analysis of aldehydes.
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| CN108226326A (en) * | 2017-12-15 | 2018-06-29 | 西北大学 | Purposes and method of the tetrahydroquinoxaline derivative of o-phenylenediamine in terms of the adjacent dicarbonyl compound content of detection |
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