Chromatography-mass spectrometry / mass spectrometry rapid detection method for heliotropin in essential oil for cleaning

Abstract

The invention provides a chromatography-mass spectrometry / mass spectrometry rapid detection method for heliotropin in essential oil for cleaning. The chromatography-mass spectrometry / mass spectrometry rapid detection method for heliotropin in essential oil for cleaning comprises the following steps: S1, sample pretreatment: carrying out ultrasonic extraction on an essential oil sample by using a mixed solvent of normal hexane and ethyl acetate to obtain an extracting solution; purifying the extracting solution through a silica gel solid-phase extraction column, leaching with n-hexane, eluting with ethyl acetate, and collecting the eluent; and S2, gas chromatography-tandem mass spectrometry analysis: carrying out GC-MS / MS analysis on the eluent obtained in the step S1, with a chromatographic column being a weakly polar or non-polar capillary column and mass spectrometry adopting a multi-reaction monitoring mode, and carrying out qualitative and quantitative detection on heliotropin by an internal standard method. The chromatography-mass spectrometry / mass spectrometry rapid detection method for heliotropin in essential oil for cleaning provided by the invention has the advantages of simple and convenient treatment steps, good sensitivity, high accuracy and short analysis time.

Description

Technical Field

[0001] This invention relates to the field of analytical chemistry, and in particular to a rapid chromatographic-mass spectrometry / mass spectrometry method for the detection of jasmine aldehyde in essential oils used for cleaning. Background Technology

[0002] Jasmine aldehyde is a synthetic fragrance with the scent of jasmine flowers, widely used as a blending agent and fixative. However, because it can be used to synthesize new types of drugs, it is classified as a Category I precursor chemical and included in the "Export Control List of Dual-Use Items of the People's Republic of China." Its production, sale, import, and export are strictly controlled and require effective monitoring.

[0003] Currently, methods for detecting hesperidin include gas chromatography (GC), high-performance liquid chromatography (HPLC), and infrared spectroscopy. However, GC carries a risk of misjudgment in qualitative analysis of complex essential oil matrices, and quantitative analysis using area normalization is severely affected by matrix interference, resulting in poor reproducibility. HPLC requires sophisticated pretreatment and has limited effectiveness in separating trace components in complex matrices. Infrared spectroscopy cannot accurately quantify hesperidin.

[0004] Therefore, it is necessary to provide a new rapid chromatographic-mass spectrometry / mass spectrometry method for the detection of jasmine aldehyde in essential oils used for cleaning to solve the above-mentioned technical problems. Summary of the Invention

[0005] The technical problem solved by this invention is to provide a rapid chromatographic-mass spectrometry / mass spectrometry detection method for jasmine aldehyde in cleaning essential oils, which has simple processing steps, good sensitivity, high accuracy, and short analysis time.

[0006] To solve the above-mentioned technical problems, the present invention provides a rapid chromatographic-mass spectrometry / mass spectrometry detection method for jasmine aldehyde in essential oils for cleaning, comprising the following steps:

[0007] S1. Sample pretreatment: The essential oil sample was ultrasonically extracted with a mixed solvent of n-hexane and ethyl acetate to obtain an extract; the extract was purified by silica gel solid phase extraction column, first eluted with n-hexane, then eluted with ethyl acetate and the eluent was collected.

[0008] S2. Gas Chromatography-Tandem Mass Spectrometry Analysis: The eluent obtained in S1 was analyzed by GC-MS / MS. The chromatographic column was a weakly polar or non-polar capillary column, and the mass spectrometry was performed in multiple reaction monitoring mode. The internal standard method was used for qualitative and quantitative detection of hesperidin.

[0009] Preferably, in S1, the volume ratio of n-hexane to ethyl acetate is 5:1.

[0010] Preferably, in step S1, the silica solid-phase extraction column is an RIPP silica solid-phase extraction column.

[0011] Preferably, in step S1, the volume of hexane used for rinsing is 2 mL, and the volume of ethyl acetate used for elution is 2 mL.

[0012] Preferably, in step S2, the gas chromatography conditions are: injection port temperature 280℃; carrier gas is helium, flow rate 3mL / min; split injection, split ratio 5:1; and the programmed temperature conditions are: initial temperature 40℃ held for 2 min, then increased to 290℃ at a rate of 10℃ / min and held for 6 min.

[0013] Preferably, in step S2, the mass spectrometry conditions are: EI ion source, ionization energy 70 eV, ion source temperature 230℃, and quadrupole temperature 150℃.

[0014] Preferably, in step S2, the monitored ion pairs of the multi-reaction monitoring mode are: hesperidin, parent ion m / z 150, daughter ions m / z 122, m / z 65, m / z 39, wherein m / z 150 > 122 is a quantitative ion pair; the internal standard is benzaldehyde, and its monitored ion pairs are: parent ion m / z 106, daughter ions m / z 77, m / z 51.

[0015] Preferably, the internal standard used in the internal standard method is benzaldehyde.

[0016] Compared with related technologies, the rapid chromatographic-mass spectrometry / mass spectrometry detection method for jasmine aldehyde in cleaning essential oils provided by this invention has the following advantages:

[0017] This invention provides a rapid chromatographic-mass spectrometry / mass spectrometry method for the detection of hesperidin in essential oils used for cleaning. Hesperidin is extracted from the fragrance using ethyl acetate via ultrasonic extraction, purified and eluted using a silica gel solid-phase extraction column, and then determined by gas chromatography-tandem mass spectrometry (MRM) in MRM mode. Results show that this method has advantages such as simple processing steps, high sensitivity, high accuracy, and short analysis time. It can accurately determine trace amounts of hesperidin in essential oils and their raw materials, providing technical support for customs supervision of import and export goods, and for cracking down on smuggling activities, especially the illegal trade of precursor chemicals. Attached Figure Description

[0018] Figure 1 The total ion chromatogram of jasmine aldehyde in essential oil raw materials such as floral fragrances is provided by the chromatographic-mass spectrometry / mass spectrometry rapid detection method for jasmine aldehyde in essential oils for cleaning purposes provided by the present invention. Detailed Implementation

[0019] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0020] Example:

[0021] A rapid chromatographic-mass spectrometric / mass spectrometric detection method for jasmine aldehyde in essential oils for cleaning, comprising the following steps:

[0022] Standard working solution:

[0023] Accurately transfer the jasmine aldehyde standard solution using a pipette, and prepare a series of working solutions with internal standard (benzaldehyde) concentrations of 0.5 μg / mL and jasmine aldehyde mass concentrations of 0.1, 0.2, 0.5, 1, 2, and 5 μg / mL using hexane / ethyl acetate (V:V=5:1).

[0024] Sample pretreatment:

[0025] Weigh 1.0 g (accurate to 0.01 g) of homogenized sample into a screw-cap bottle, dilute to volume with 10 mL of n-hexane / ethyl acetate (V:V=5:1), and sonicate at constant temperature for 10 min. Add 500 μL of extract to a hexane-activated RIPP silica gel solid-phase extraction column, elute with 2 mL of n-hexane, discard the eluent after all the extract has passed through the column, elute with 2 mL of ethyl acetate and collect the eluent. Filter the eluent through a microporous organic filter membrane before testing.

[0026] Gas chromatography-tandem mass spectrometry analysis conditions:

[0027] Chromatographic conditions: DB-5MS UI capillary column (30m×0.25mm×0.25µm); column flow rate: 3mL·min⁻¹; liner: inert split liner; carrier gas: high-purity helium; split mode: split ratio 5:1; injection port temperature: 280℃; injection volume: 1.0μL; temperature program: initial temperature 40℃, hold for 2 min, increase to 290℃ at a rate of 10℃·min⁻¹, hold for 6 min.

[0028] Mass spectrometry conditions: EI ion source, ionization energy 70 eV, ion source temperature 230℃, quadrupole mass analyzer temperature 150℃; monitoring mode: multiple reaction monitoring (MRM); solvent delay: 2.5 min. Quantitative and qualitative ion parameters of hesperidin are shown in Table 1.

[0029] Table 1. Quantitative and qualitative ion pairs and other parameters of hesperidin and internal standard.

[0030]

[0031] Methodological evaluation:

[0032] Linearity, limit of quantitation, and limit of detection tests:

[0033] Standard curves for hesperidin with concentrations ranging from 0.10 to 5.0 μg / mL were prepared in blank essential oil matrices. The curves were then quantitatively analyzed under the optimized chromatographic and mass spectrometric conditions described above. A linear equation was plotted with the ratio of hesperidin concentration to benzaldehyde concentration on the x-axis and the ratio of hesperidin peak area to benzaldehyde peak area on the y-axis. The results showed good linearity of hesperidin within the concentration range of 0.10–5.0 μg / mL, with a correlation coefficient (r²) ≥ 0.9980. The limits of detection (LOD) and quantitation (LOQ) were determined using the signal-to-noise ratio (S / N) of hesperidin peak area ≥ 3 and ≥ 10, respectively. The LOD for hesperidin was found to be 0.05–0.06 μg / mL, and the LOQ was 0.12–0.20 μg / mL. The test results are shown in Table 2.

[0034] Accuracy and precision tests:

[0035] A certain amount of hesperidin standard solution was added to blank matrix essential oil samples ① essential oil fragrance products, ② essential oil cleaning agents, and ③ essential oil raw materials to prepare sample spiking solutions with added mass concentrations of 0.10, 2.00, and 5.00 μg / mL, respectively. Under the above GC-MS / MS conditions, the same concentration spiking solutions were tested in parallel 6 times. The recovery rate and relative standard deviation of hesperidin were calculated. Finally, the recovery rate of hesperidin was found to be 95.0%~105%, and the relative standard deviation (RSD) was less than 5.01%, which met the requirements for effective extraction of hesperidin from essential oils. The recovery rate and precision results are shown in Table 2.

[0036] Table 2 Recovery rate and relative standard deviation of hesperidin

[0037]

[0038] Practical applications:

[0039] This method was used to screen 200 batches of imported and exported essential oil and fragrance products, essential oil raw materials, and fragrance-based cleaning agents. A total of 30 batches were found to contain hesperidin, a detection rate of 15%. The test results showed that hesperidin was detected in 30 out of 200 fragrance samples, a detection rate of 15%. The samples containing hesperidin were mainly daily chemical fragrances and floral fragrances, which are essential oil raw materials. The lowest detected content of hesperidin was 0.002%, and the highest reached 0.60%. The test results for a certain floral fragrance sample are shown below. Figure 1 .

[0040] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A rapid chromatographic-mass spectrometry / mass spectrometry method for the detection of jasmine aldehyde in essential oils for cleaning, characterized in that, Includes the following steps: S1. Sample pretreatment: The essential oil sample was ultrasonically extracted with a mixed solvent of n-hexane and ethyl acetate to obtain an extract; the extract was purified by silica gel solid phase extraction column, first eluted with n-hexane, then eluted with ethyl acetate and the eluent was collected. S2. Gas Chromatography-Tandem Mass Spectrometry Analysis: The eluent obtained in S1 was analyzed by GC-MS / MS. The chromatographic column was a weakly polar or non-polar capillary column, and the mass spectrometry was performed in multiple reaction monitoring mode. The internal standard method was used for qualitative and quantitative detection of hesperidin.

2. The rapid chromatographic-mass spectrometry / mass spectrometry detection method for jasmine aldehyde in cleaning essential oils according to claim 1, characterized in that, In S1, the volume ratio of n-hexane to ethyl acetate is 5:

1.

3. The rapid chromatographic-mass spectrometry / mass spectrometry detection method for jasmine aldehyde in cleaning essential oils according to claim 1, characterized in that, In step S1, the silica solid-phase extraction column is an RIPP silica solid-phase extraction column.

4. The rapid chromatographic-mass spectrometry / mass spectrometry detection method for jasmine aldehyde in cleaning essential oils according to claim 1, characterized in that, In S1, the volume of n-hexane used for rinsing is 2 mL, and the volume of ethyl acetate used for elution is 2 mL.

5. The rapid chromatographic-mass spectrometry / mass spectrometry detection method for jasmine aldehyde in cleaning essential oils according to claim 1, characterized in that, In S2, the gas chromatography conditions are: injection port temperature 280℃; carrier gas is helium, flow rate 3 mL / min; split injection, split ratio 5:1; programmed temperature conditions are: initial temperature 40℃ held for 2 min, then increased to 290℃ at a rate of 10℃ / min and held for 6 min.

6. The rapid chromatographic-mass spectrometry / mass spectrometry detection method for jasmine aldehyde in cleaning essential oils according to claim 1, characterized in that, In S2, the mass spectrometry conditions are: EI ion source, ionization energy 70 eV, ion source temperature 230℃, quadrupole temperature 150℃.

7. The rapid chromatographic-mass spectrometry / mass spectrometry detection method for jasmine aldehyde in cleaning essential oils according to claim 1, characterized in that, In S2, the monitored ion pairs of the multi-reaction monitoring mode are: hesperidin, parent ion m / z 150, daughter ions m / z 122, m / z 65, m / z 39, where m / z 150>122 is the quantitative ion pair; the internal standard is benzaldehyde, and its monitored ion pairs are: parent ion m / z 106, daughter ions m / z 77, m / z 51.

8. The rapid chromatographic-mass spectrometry / mass spectrometry detection method for jasmine aldehyde in cleaning essential oils according to claim 1, characterized in that, The internal standard used in the internal standard method is benzaldehyde.

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