AU2020102127A4 - Collection and determination of acrolein and other four aldehydes in workplace - Google Patents
Collection and determination of acrolein and other four aldehydes in workplace Download PDFInfo
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Abstract
The invention discloses the collection and determination of 4 aldehydes such as acrolein
in the workplace, belonging to the technical field of aldehyde detection. The test method
comprises the following steps: collecting the air sample to be tested with the absorption liquid
and filtering it with a microporous filter membrane to obtain the derivative filtrate; separating
the filtrate by liquid chromatography with an ultra-high performance liquid chromatograph,
and detecting the eluent by mass spectrometry. The invention optimizes the derivatization
condition so that the phenol-aldehyde derivative has good stability and can ensure the accuracy
of the test results. At the same time, a better separation effect is achieved by screening the
chromatographic condition and the mass spectrum condition. The method of this invention has
the advantages of good linearity, simple operation, high recovery rate and high accuracy.
-1/4
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- 60
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0 2 3 4 s 6 7 a
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Figure1I
Description
-1/4
100 Adhd
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- 60 pale qygde
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Figure1I
PATENTS ACT 1990
Collection and determination of acrolein and other four aldehydes in workplace
The invention is described in the following statement:-
Collection and determination of acrolein and other four aldehydes in workplace
The invention relates to the technical field of aldehyde detection, in particular to collection and determination of four aldehydes such as acrolein and the like in a working place.
Butadiene is an important raw material for the manufacture of synthetic rubber, synthetic resin, nylon, etc. Its main source is obtained from dehydrogenation of n-butene, but certain by-products are inevitably generated in the dehydrogenation process, wherein acetaldehyde, acrolein, methacrolein and crotonaldehyde are the most main products. These by-products not only affect the yield of butadiene, but also diffuse into the atmosphere to cause atmospheric pollution to the environment. These aldehydes, which are all highly irritating, can cause respiratory tract infection diseases, and have potential hazards such as sensitization, carcinogenesis, mutagenesis, etc. Therefore, the monitoring of acetaldehyde, acrolein, methacrolein and crotonaldehyde in the air in the place where n-butene is dehydrogenated and the surrounding environment can not only provide a scientific basis for optimizing the dehydrogenation process of n-butene, but also has important practical significance for monitoring the environment air in the work place.
The invention aims to provide collection and determination of four aldehydes such as acrolein and the like in a working place so as to solve the problems existing in the prior art, so that the stability of derivatives of acetaldehyde, acrolein, methacrolein and butenal to be detected is higher, the separation effect of the detection method is better, the method has good linearity, the operation is simple, and the recovery rate and the accuracy are higher.
In order to achieve the above object, the invention provides the following scheme:
The invention provides collection and determination of four aldehydes such as acrolein in a working place, which comprises the following steps:
(1) Preparation of sample solution: use the absorption liquid to collect the air sample to be tested, and filter it with an aqueous microporous membrane to obtain the filtrate;;
(2) liquid separation, namely carrying out liquid chromatography separation on the filtrate in the step (1) by using an ultra-high performance liquid chromatograph, wherein the used chromatographic column is A Shim-pack XR-ODS II column with the diameter of 100mm*2.mm and the diameter of 2.5 [m; mobile phase A phase is water, phase B is methanol, then gradient elution is performed, wherein the elution flow rate is 0.3mL/min, the sample injection volume is 5.0 [L, and the column temperature is 40°C;
(3) Carrying out mass spectrum analysis detection on the eluent obtained in the step (2);
The small-molecular aldehydes are acetaldehyde, acrolein, methacrolein and crotonaldehyde.
Further, the absorption solution in step (1) is a mixed solution of a phenol reagent and concentrated hydrochloric acid, wherein the concentration of the phenol reagent is 0.35-1.0 mg/L.
Further, the phenolic reagent is 3-methyl-2-benzothiazolone hydrazone hydrochloride.
Further, the pH of the absorption liquid in step (1) is 0 to 7.
Furthermore, the collecting method in the step (1) comprises the step of collecting an air sample to be measured for 5-20min at a flow rate of 0.3-1.2L/min by using a large bubble absorption tube filled with absorption liquid.
Further, in step (2), the gradient elution procedure is 0-2 min, 35% B-90% B, 2.0 5.50 min, 90% B, 5.50-6.5 min, 90% B-35% B, 6.50-7.50 min, and 35% B.
Further, in step (3), the mass spectrometry detection mode electrospray is a positive ion mode.
Further, in step (3), the ion spray voltage detected by mass spectrometry is 4.0 kV, the ion source temperature is 450° C, and the acquisition method is MRM; the atomizer pressure is 50.0 psi, the auxiliary gas pressure is 50.0 psi, the gas curtain gas pressure is 35.0 psi, the collision gas is 7.0 psi, the scanning time is 50 ms, the collision chamber outlet voltage is-10.0 V, and the collision chamber inlet voltage is-10.0 V.
The invention discloses the following technical effects:
According to the method, a phenol reagent 3-methyl-2-benzothiazolone hydrazone hydrochloride (MBTH) is used for derivatizing acetaldehyde, acrolein, methacrolein and crotonaldehyde, the derivatization reaction proceeds rapidly, more than 96% of derivatization is realized within 5 min, the obtained four kinds of MBTH-aldehyde derivatives can be kept stable within 72 hours under the conditions of room temperature to 40°C, which can ensure the accuracy of the test results; and meanwhile, a Shim-pack XR-ODS II (100mm*2.Omm, 2.5Sm) chromatographic column is adopted, a mobile phase is screened, and gradient elution is carried out, so that a better separation effect and shorter analysis time can be obtained. The detection method of the invention has the advantages of small sample consumption, short time, good method linearity, simple operation, high recovery rate, high accuracy, etc., and can not only provide scientific basis for the optimization of the dehydrogenation process of the n-butene, but also has important practical significance for the environmental air monitoring of a working place.
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the following will briefly introduce the drawings needed in the embodiments. Obviously, the drawings in the following description are only some of the invention, and other drawings can be obtained from these drawings without any creative effort.
FIG. 1 shows the effect of phenol reagent solutions at different pH values on the reaction efficiency of four aldehydes;
FIG. 2 is an MRM diagram of an MBTH-acetaldehyde derivative;
FIG. 3 is an MRM diagram of an MBTH-acrolein derivative;
FIG. 4 is an MRM diagram of an MBTH-methacrolein derivative;
FIG. 5 is an MRM diagram of an MBTH-crotonaldehyde derivative;
FIG. 6 is a schematic diagram of mass spectrometry cleavage of MBTH-aldehyde derivatives in the ESI (+) mode, RI being a hydrocarbyl group.
Various exemplary embodiments of the invention will now be described in detail. The detailed description should not be considered as a limitation to the invention, but should be understood as a more detailed description of certain aspects, features and embodiments of the invention.
It should be understood that the terms described herein is for the purpose of describing particular embodiments only and are not intended to limit the invention. In addition, for the numerical range in the invention, it should be understood that each intermediate value between the upper limit and the lower limit of the range is also specifically disclosed. Each smaller range between intermediate values within any stated value or stated range and any other stated value or intermediate values within the stated range is also included within the invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the range.
Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the field of the invention. Although the invention only describes preferred methods and materials, any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the invention. All documents mentioned in this specification are incorporated by reference for the purpose of disclosing and describing methods and/or materials related to documents. In the event of conflict with any incorporated document, the content of this manual shall prevail.
Without departing from the scope or spirit of the invention, various improvements and changes can be made to the specific embodiments of the present specification. Other embodiments derived from the description of the present inventio will be obvious to those skilled in the art from the description of the invention. The specification and embodiments of the present application are only exemplary.
As used herein, terms "comprising,""including ""having,""containing," , etc., are intended to be open terms, i. e., intended to include, but not be limited to.
The "parts" described in the invention are all based on parts by mass, unless otherwise specified.
Methanol, acetic acid, acetonitrile (HPLC grade) used in the invention were purchased from Merck, Germany; hydrochloric acid and ammonia water (superior grade pure) were purchased from Shanghai National Drug Reagent Group; acetaldehyde, acrolein, methacrolein, crotonaldehyde (content > 99.8%) were purchased from Chem Service.
EXAMPLE 1
Preparation of standard stock solutions of acetaldehyde, acrolein, methacrolein and crotonaldehyde (1.0 mg/mL):
Accurately weigh 10.0 mg of each acetaldehyde, acrolein, methacrolein and crotonaldehyde into four 10 mL volumetric flasks, respectively, dissolved with water and diluted to scale.
Preparation of a mixed standard soPreparation of a mixed standard solution of acetaldehyde, acrolein, methacrolein and crotonaldehyde (10.0 mg/L):
Accurately weigh 1.0 mL of standard stock solutions (1.0 mg/mL) of acetaldehyde, acrolein, methacrolein and crotonaldehyde, respectively, into a 100 mL volumetric flask, dissolve with methanol and dilute to scale.
Preparation of absorption liquid:
The method comprises the following steps of: accurately weighing 1.0 g of phenol reagent (3-methyl-2-benzothiazolone hydrazone hydrochloride, MBTH) in a 1 L brown volumetric flask, adding water to a constant volume to obtain 1.0 g/L of phenol reagent solution, taking 1.0 mL of phenol reagent solution, adding 1.0 mL of concentrated hydrochloric acid, diluting with water to 1000 mL to obtain 1.0 mg/L of absorption solution, wherein the pH value of the absorption solution is 1.
Preparation of absorption liquid:
The method comprises the following steps of: accurately weighing 1.0 g of phenol reagent (3-methyl-2-benzothiazolone hydrazone hydrochloride, MBTH) in a 1 L brown volumetric flask, adding water to a constant volume to obtain 1.0 g/L of phenol reagent solution, taking 1.0 mL of phenol reagent solution, adding 1.0 mL of concentrated hydrochloric acid, diluting with water to 1000 mL to obtain 1.0 mg/L of absorption solution, wherein the pH value of the absorption solution is 1.
Sample collection:
At the sampling point of n-butene dehydrogenation, use a large bubble absorption tube with 5 mL of absorption solution to collect air saSample collection:
At the sampling point of n-butene dehydrogenation, use a large bubble absorption tube with 5 mL of absorption solution to collect air samples for 20 min at a flow rate of 0.5 L/min, and filter them with a 0.22 m water phase microporous microporous filter membrane to obtain the filtrate. The filtrate is a mixture of MBTH-aldehyde derivatives.
Sample blank:
At the sampling point, open the air inlet and outlet of the large bubble absorption tube containing 5 mL of absorbing liquid, and immediately close it, and then transport and store the same product together, and perform the measurement according to the sample measurement method.
Sample Determination:
(1) liquid separation: performing liquid chromatography separation on the collected sample filtrate by using an ultra-high performance liquid chromatograph, wherein the used chromatographic column is Shim-pack XR-ODS II (100mm*2.Omm, 2.5pm); the mobile phase A is water, and the mobile phase B is methanol; and the gradient elution procedure is 0-2min, 35% B-90% B, 2.0-5.50min, 90% B, 5.50-6.5min, 90% B-35% B, 6.50-7.50min, and 35% B; and the elution flow rate is 0.3mL/min, the sample injection amount is 5.0 pL, and the column temperature is 40 DEG C.
(2) carrying out mass spectrum analysis detection on the eluent obtained in the step (1);
The mass spectrum conditions used are: ionization source: electrospray positive ion mode; ion spray voltage 4.0 kV; ion source temperature 450 °C; acquisition mode: MRM; atomizer pressure 50.0 psi; auxiliary gas pressure 50.0 psi; air curtain gas pressure 35.0 psi; collision gas 7.0 psi; scanning time 50 ms; collision chamber outlet voltage-10.0 V; collision chamber inlet voltage-10.0 V.
The MRM mass spectrum parameters of the four MBTH-aldehyde deriThe MRM mass spectrum parameters of the four MBTH-aldehyde derivatives are shown in Table 1.
Table 1
Derivatives Molecular Molecular Parent Daughter De- Collision formula weight ion ion cluster energy voltage Ql(m/z) Q3(m/z) CE(V) DP(V)
TH-acetaldehyde CioN3SH1i 205.3 206 164*,136 -120 -30,-32 derivatives
MBTH-acrolein CiiN 3SHii 217.3 218 164*,136 -90 -27,-20 derivatives MBTH-methacrolein C12 N 3SH1 3 231.3 232 164*,136 -120 -27,-31 derivatives MBTH crotonaldehyde C12N3SH13 231.3 232 164*,136 -120 -27,-22 derivatives
In mass spectrometry, the quantitative ions of MBTH-acetaldehyde derivatives are m/z 206 -* 164, the quantitative ions of MBTH-acrolein derivatives are m/z 218 -+ 164, the quantitative ions of MBTH-methacrolein derivatives are m/z 232- 164, and the quantitative ions of MBTH- crotonaldehyde derivatives are m/z 232-- 164.
StaStability detection of four MBTH-aldehyde derivatives:
After the derivatization of acetaldehyde, acrolein, methacrolein, crotonaldehyde and phenol reagent is completed, the stability of the derivative directly influences the accuracy of the determination results. Test the effect of different times (0, 1, 3, 6, 12, 24, 36, 72 hours) on the stability of the MBTH-aldehyde derivatives of acetaldehyde, acrolein, methacrolein and crotonaldehyde, at room temperature to 40°C. The results showed that the MBTH-aldehyde derivatives of acetaldehyde, acrolein, methacrolein and crotonaldehyde did not change after being left for 72 hours at room temperature to 400 C. The results showed that the above four types of MBTH -Aldehyde derivatives can remain stable within 72 hours at room temperature to 40°C, ensuring the stability of test results.
Matrix effect evaluation:
A standard mixture of acetaldehyde, acrolein, methacrolein and crotonaldehyde at 3 concentration levels (2.0, 15.0 and 80.0 pg/L, respectively, in terms of aldehyde) of the phenol reagent absorption solution were subjected to derivatization with 1.0 mg/L of the absorption solution at pH 2 for 20 min. The chromatographic peak area (S1) was measured under the same chromatographic detection conditions as in the step (1). A standard mixture of MBTH derivatives of acetaldehyde, acrolein, methacrolein and crotonaldehyde at the same concentration level were also measured under the same chromatographic detection conditions. The chromatographic peak area (S2) was measured under the same conditions. It can be seen that the matrix effect value is 88.7% 97.5%.
Table 2
Addition amount (in terms of Compounds Matrix Effect (%) aldehyde,. pg/L)
Acetaldehyde 2.0 94.5
15.0 92.7
80.0 94.6
Acrolein 2.0 92.9
15.0 97.5
80.0 96.4
Methacrolein 2.0 91.8
15.0 92.6
80.0 93.7
crotonaldehyde 2.0 91.5
15.0 88.7
80.0 96.6
Methods Linear range and detection limit:
A series of 7 standard solutions at concentration levels ranging from 1.0 pg/L to 100.0 pg/L (min terms of aldehyde) was prepared, derivatized with 1.0 mg/L of an absorption solution at pH 2 for 20 minutes, and measured according to the detection methods of step (1) and step (2). The data obtained were linear regression of peak area (y) with sample concentration (x, pg/L). The linear regression equation of aldehyde, correlation coefficient (r 2) and linear range are shown in Table 5. The results show that the MBTH-aldehyde derivatives of acetaldehyde, acrolein, methacrolein and crotonaldehyde have good linear relationship in the range of 1.0 tg/L-100.0 pg/L (in terms of aldehyde), and the correlation coefficient (r2) is more than 0.9990. By gradually diluting the labeled solution processed by the sample analysis step, the signal-to-noise ratio (S/N=3) is taken as a detection limit (LOD), and the signal-to-noise ratio (S/SN N ) is taken as a quantitative detection limit (LOLOQ according to the 1OL air sample collected. The results showed that the LOD and LOLOQf acetaldehyde, acrolein, methacrolein and crotonaldehyde were 0.3 tg/gm3mand 1.0 pg/mg respectively.
Table 3 Regression equation, linear range, correlation coefficient, detection limit LOD and quantitative detection limit LOLOQ
Linear range Correlation LODs LOQs Compounds Regression equation (.pg/L in terms of coefficient (r2) (jg/r) (jg/rn) aldehyde)
3 1.0 Acetaldehyde y=3 .4 *10 4x+2.3*10 1.0-100.0 0.9995 0.3
Acrolein y=2.8*104 x+1.6*10 3 1.0-100.0 0.9992 0.3 1.0
Methacrolein y-1.9*10t+6.1*103 1.0-100.0 0.9990 0.3 1.0
crotonaldehyde y=2.7*10 4x+4.l*10 3 1.0-100.0 0.9990 0.3 1.0
Methods Accuracy and Precision:
Three quality control (QC) samples (2.0, 15.0, 80.0 pg/L in terms of aldehyde) were prepared by adding different amounts of acetaldehyde, acrolein, methacrolein and crotonaldehyde standard stock solution to the blank absorption solution, and the recovery and precision were calculated by three repeated measurements. The results showed that the recovery was in the range of 90.6%-97.8% and the precision was in the range of 1.9%-6.4%.
Table 4 The results of standard-added recovery and precision tests (n=3)
Compounds Addition amount Measured value Recovery rate Precision
(.pg/L in terms of (pigL) (O% ) (%
) aldehyde)
Acetaldehyde 2.0 1.92±0.08 96.0 4.1
15.0 14.61±0.84 97.4 5.6
80.0 77.55±1.22 96.9 1.6
Acrolein 2.0 1.82±0.07 91.0 5.8
15.0 14.11±0.76 94.1 5.4
80.0 76.35±1.43 95.4 1.9
Methacrolein 2.0 1.91±0.10 95.5 5.2
15.0 13.6±0.43 90.6 3.2
80.0 76.89±2.41 96.1 3.1
crotonaldehyde 2.0 1.83±0.06 91.5 3.3
15.0 14.2±0.91 94.6 6.4
80.0 78.22±2.31 97.8 3.0
EXAMPLE 2
The concentration of the absorption liquid is 0.35 mg/L, the pH value is 1, and the preparation method is the same as that of Example 1;
Sample collection:
A large bubble absorption tube filled with absorption liquid is used for collecting an air sample to be detected for 5 min at a flow rate of 1.2 L/min, and the air sample is filtered by a 0.22 pm aqueous phase microporous filter membrane to obtain a filtrate, wherein the filtrate is a mixture of MBTH-aldehyde derivatives.
Sample Determination:
(1) liquid separation: performing liquid chromatography separation on the collected sample filtrate by using an ultra-high performance liquid chromatograph, wherein the used chromatographic column is Shim-pack XR-ODS II (100mm*2.Omm, 2.5 [m); the mobile phase A is water, and the mobile phase B is methanol; and the gradient elution procedure is 0-2min, 35% B-90% B, 2.0-5.50 min, 90% B, 5.50-6.5 min, 90% B-35% B, 6.50-7.50min, and 35% B; and the elution flow rate is 0.3mL/min, the sample injection amount is 5.0 [L, and the column temperature is 40 DEG C.
(2) carrying out mass spectrum analysis detection on the eluent obtained in the step (1);
Mass spectrometry conditions are the same as in Example 1.
EXAMPLE 3
The concentration of the absorption liquid is 0.5mg/L, the pH value is 7, and the preparation method is the same as that of Example 1;
Sample collection:
A large bubble absorption tube filled with absorption liquid is used for collecting an air sample to be rested for 10min at a flow rate of 0.5L/min, and the air sample is filtered by a 0.22 m aqueous phase microporous filter membrane to obtain a filtrate, wherein the filtrate is a mixture of MBTH-aldehyde derivatives.
Sample Determination:
(1) liquid separation: performing liquid chromatography separation on the collected sample filtrate by using an ultra-high performance liquid chromatograph, wherein the used chromatographic column is Shim-pack XR-ODS II (100mm*2.Omm, 2.5 [m); the mobile phase A is water, and the mobile phase B is methanol; and the gradient elution procedure is 0-2min, 35% B-90% B, 2.0-5.50 min, 90% B, 5.50-6.5 min, 90% B-35% B, 6.50-7.50 min, and 35% B; and the elution flow rate is 0.3mL/min, the sample injection amount is 5.0 [L, and the column temperature is 40 DEG C.
(2) Carrying out mass spectrum analysis detection on the eluent obtained in the step (1);
Mass spectrometry conditions are the same as in Example 1.
Effect of Phenolic Reagent Derivatization Conditions on the Derivatization:
1. Effect of Phenol Reagent Concentration level
The molar ratio of the phenol reagent to the aldehyde is 1: 1, and the reaction formula is as follows:
CH 3 CH3 I0 N H I N/ C=N-NH 2 + R H I C=N-N=-C H + H2 R1 / R1
Experiments show that the chromatographic peak height of MBTH-aldehyde derivatives obtained by reacting different concentrations (0.35-1.0 mg/L) of phenol reagent with aldehyde is almost unchanged when the excess amount of phenol reagent is kept. The actual derivatization reaction can complete the aldehyde derivatization reaction only by keeping excessive phenol reagent in the absorption liquid. In order to avoid the consumption of phenolic reagents by other aldehydes and ketones that may coexist, the phenolic reagents of the invention are in excess.
2. Effect of pH Value of Absorption Liquid on Derivatization Efficiency
The effect of 5.0 mL of 1.0 mg/L phenol reagent absorption solution at different pH values (1.0, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0) on the derivatization efficiency of 5.0 mL of 20.0. ptg/L acetaldehyde, acrolein, methacrolein and crotonaldehyde (pH value of the solution was adjusted with hydrochloric acid and ammonia water) for 5 min. As shown min FIG. 1, when the pH value is less than 2, the derivatization reaction can be completed within 5 minutes.
3. Effect of Derivatization Time on Derivatization Effect
5.0 mL of a 1.0 mg/L phenol reagent absorption solution was used for the derivatization reaction of 5.0 mL of 20.0. g/L acetaldehyde, acrolein, methacrolein and crotonaldehyde, and the efficiency of the derivatization reaction was measured. The results show that the derivatization reaction of acetaldehyde, acrolein, methacrolein and crotonaldehyde with phenol reagent can reach over 99% in 5.0 min under suitable conditions.
4. Effect of Derivatization Temperature on Derivatization Effect
The effects of different derivatization temperatures (5, 15, 25, 35 °C) on the derivatization efficiency of acetaldehyde, acrolein, methacrolein and crotonaldehyde were tested. The results show that in the solution with pH=1, the temperature will affect the reaction rate, the higher the temperature is, the faster the derivatization reaction is, the slower the derivatization reaction is at 5 °C, the derivatization reaction can reach over 96% within 5 min at 15 °C, and the derivatization reaction can be completed within 5 min at room temperature.
Selection of chromatographic separation and mass spectrometry detection conditions:
1. Influence of Chromatographic Column
The effects of five kinds of C18 chromatographic columns produced by different companies, such as Diamonsil C18(250*4.6 mm, 5 m), Platisil ODS (150 x 4.6 mm, 5 pm), Waters Xbridge C18 column (100 mmx2.1 mm, 3.5 m), Phenomenex Kinetex C18 column (50 mmx2.1 mm, 2.6 m) and Shimadzu Shim-pack XR-ODS II column (75 mmx2.0 mm, 2.2 m) on the separation and detection sensitivity of four kinds of MBTH aldehyde derivatives were tested. The results showed that the four kinds of MBTH aldehyde derivatives could be separated well on DiamonsilC C18, Platisil ODS column and Waters Xbridge C18 column, but the response value was slightly worse on mass spectrum. Formaldehyde and acetaldehyde on the Phynomex Kinetex C18 column can't reach the baseline separation, and all the four compounds to be tested have different degrees of tailing Phenomenex, which affects the accurate quantification. MBTH derivatives of acetaldehyde, acrolein, methacrolein and crotonaldehyde were also well separated on a Shim-pack XR-ODSII column and had good detection sensitivity. MRM chromatograms of the four MBTH-aldehyde derivatives were shown in FIGS. 2-5.
Since the derivatives of phenolic reagents with aldehydes have two C=N double bonds, they should theoretically have cis, trans or Z, E isomers. The MBTH-acetaldehyde derivative obtained under the condition of the invention is two MRM peaks, and the MBTH-acrolein derivative, the MBTH-methacrolein derivative and the MBTH crotonaldehyde derivative are all one MRM peak. the total area of the MRM is selected for calculation during quantitative analysis. In this experiment, it was found that the pH value of the reaction medium had a great influence on the composition ratio of the isomers of the MBTH-aldehyde derivative, and other MBTH-aldehyde derivatives were single products except for the presence of two MRM peaks in the MBTH-acetaldehyde derivative at the acidity of the reaction solution of the invention.
2. Influence of Mobile Phase
The effects of different kinds of MBTH-aldehyde derivatives on the flow of MBTH aldehyde derivatives were studied. Four mobile phases, acetonitrile-water, acetonitrile 0.1% formic acid aqueous solution, methanol-water solution and methanol-0.1% formic acid aqueous solution, were used. For the above four kinds of MBTH-aldehyde derivatives, the four kinds of mobile phases can obtain better separation effect only by selecting proper gradient, but there is certain difference in sensitivity, no matter adding formic acid into methanol-water or acetonitrile-water, the sensitivity of the compound to be detected is reduced, compared with acetonitrile-water solution, the retention time of the four kinds of MBTH-aldehyde derivatives is increased, and the peak shape is widened.
3. Selection of Quantitative Ions by Mass Spectrometry and Mechanism of Decomposition
Four kinds of MBTH-aldehyde derivatives (in terms of aldehyde) were injected into the ion source at a rate of 7 L/min in a standard solution of 100 [g/L. The results showed that the sensitivity of the four kinds of MBTH-aldehyde derivatives in the positive ion mode was much higher than that in the negative ion mode. However, in the positive ion mode, the fragment ions of the four MBTH-aldehyde derivatives are substantially similar, both m/z164 and m/z136, i. e., the fragment ions of the cleavage of the parent nucleus of the phenol reagent (see FIG. 6 for the schematic diagram), and both m/z164 are the base peaks.
According to the invention, the quantitative ions of the MBTH-acetaldehyde derivative are m/z 206 to 164, the quantitative ions of the MBTH-acrolein derivative are m/z 218 to 164, the quantitative ions of the MBTH-methacrolein derivative are m/z 232 to 164, and the quantitative ions of the MBTH- crotonaldehyde derivative are mlz 232 to 164.
The above-described embodiments only describe the preferred mode of the invention, and do not limit the scope of the invention, without departing from the design spirit of the invention, those of ordinary skill in the art have made various contributions to the technical solutions of the invention. Varations and improvements should fall within the protection scope determined by the claims of the invention.
Claims (8)
1. The collection and determination of four aldehydes such as acrolein in the work place,
characterized by the following steps:
(1) Preparation of sample solution: use the absorption liquid to collect the air sample to be
tested, and filter it with an aqueous microporous membrane to obtain the filtrate;
(2) Liquid chromatographic separation: namely carrying out liquid chromatography separation
on the filtrate in the step (1) using an ultra-high performance liquid chromatograph, wherein the
used chromatographic column is A Shim-pack XR-ODS II column with the diameter of
100mm*2.mm and the diameter of 2.5pm; mobile phase A phase is water, phase B is methanol,
then gradient elution is performed,, wherein the elution flow rate is 0.3mL/min, the sample injection
volume is 5.Ou L, and the column temperature is 40 ;
(3) Carrying out mass spectrum analysis on the eluent obtained in step (2);
The small-molecular aldehydes are acetaldehyde, acrolein, methacrolein and crotonaldehyde.
2. The collection and determination of four aldehydes such as acrolein in the workplace
according to claim 1, wherein the absorption solution in step (1) is a mixed solution of a phenol
reagent and concentrated hydrochloric acid, wherein the concentration of the phenol reagent is 0.35
to 1.0 mg/L.
3. The collection and determination of four aldehydes such as acrolein in the workplace
according to claim 2, wherein the phenol reagent is 3-methyl-2-benzothiazolone hydrazone
hydrochloride.
4. The collection and determination of four aldehydes such as acrolein in the workplace
according to claim 1, wherein the pH of the absorption solution in step (1) is 0 to 7.
5. The collection and determination of four aldehydes such as acrolein in the workplace
according to claim 1, wherein the collecting method in step (1) is to use a large bubble absorption tube containing absorption solution, with a concentration of 0.3-1.2L /min flow rate to collect the air sample to be tested for 5 to 20 minutes
.
6. The collection and determination of four aldehydes such as acrolein in the workplace
according to claim ,wherein in step (2), the gradient elution procedure is 0-2 min, 35% B-90% B, 2.0-5.50 min, 90% B, 5.50-6.5 min, 90% B-35% B, 6.50-7.50 min, and 35% B.
7. The collection and measurement of four aldehydes such as acrolein in the workplace
according to claim 1, wherein in step (3), the mass spectrometry detection mode electrospray is a
positive ion mode.
8. The collection and measurement of four aldehydes such as acrolein in a workplace
according to claim 1, wherein in the step (3), the ion spray voltage detected by mass spectrometry is 4.0 k, the ion source temperature is 450°C., and acquisition method is MRM; atomizer pressure
is 50.0 psi, auxiliary gas pressure is 50.0 psi, curtain gas pressure is 35.0 psi, collision gas is 7.0 psi,
scanning time is 50 ms, collision chamber outlet voltage is-10.0 V, and collision chamber inlet voltage is-10.0 V.
Figure 1 -1/4-
-2/4- 03 Sep 2020 2020102127
Figure 2
Figure 3
-3/4- 03 Sep 2020 2020102127
Figure 4
Figure 5
-4/4- 03 Sep 2020 2020102127
CH3 H N C N N C S R1 m/z136 m/z164
Figure 6
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113466011A (en) * | 2021-07-26 | 2021-10-01 | 江苏省疾病预防控制中心(江苏省公共卫生研究院) | Preparation method of microporous filter membrane quality control sample and quality control sample |
| CN114166834A (en) * | 2021-12-08 | 2022-03-11 | 桂林医学院 | Method for analyzing photo-decomposition degree of medicine by tracing auxiliary agent |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113466011A (en) * | 2021-07-26 | 2021-10-01 | 江苏省疾病预防控制中心(江苏省公共卫生研究院) | Preparation method of microporous filter membrane quality control sample and quality control sample |
| CN114166834A (en) * | 2021-12-08 | 2022-03-11 | 桂林医学院 | Method for analyzing photo-decomposition degree of medicine by tracing auxiliary agent |
| CN114166834B (en) * | 2021-12-08 | 2024-04-02 | 桂林医学院 | Method for analyzing photodecomposition degree of medicine by tracing auxiliary agent |
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