CN107389831B - Method for rapidly detecting forbidden substance estrone in spray cosmetics - Google Patents

Abstract

The invention discloses a method for quickly detecting a forbidden substance estrone in a spray cosmetic, which comprises the following steps: step one, manufacturing an open type double-tee capillary spraying device; step two, the open type double-tee capillary spraying device is arranged at the position 3-4 cm away from the front end of a sample inlet of a mass spectrometer, parameters of the mass spectrometer are set, and an aerosol valve of the sample bottle is pressed to obtain a mass spectrum response signal; and step three, in order to improve the response value of the analyte, introducing a derivatization reagent through a syringe pump, blowing atomized liquid drops by atomized gas, and mixing the atomized liquid drops with the sample in the front end space of the capillary spray tube to improve the mass spectrum response signal of the substance to be detected. The method is simple and rapid, and is suitable for rapid detection of the forbidden substance estrone in the spray cosmetics for rapid field detection.

Description

A rapid detection method of estrone, a banned substance in spray cosmetics

technical field

The invention relates to a detection method for chemical substances, in particular to a rapid detection method for estrone, a prohibited substance in spray cosmetics.

Background technique

Spray products are widely used products in our lives. There are two main types of products: one is aerodynamic spray products powered by the gas in the bottle, also called aerosol products, and the other is spray products powered by external force (manual) pressing, commonly known as pressing spray products. . The products are rich in variety, such as pesticides for agriculture, forestry and household use, hair dyeing sprays for hair dyeing, spray cosmetics for personal care, traditional Chinese medicine sprays for traumatic injuries, etc. While these products provide convenience in life, they also have potential harm to the human body and the environment. Spray products can exert their effect mainly because the products contain specific chemical active ingredients. However, in order to increase its efficacy, unscrupulous merchants may illegally add some banned substances with the same efficacy. During use, these inferior products contain toxic and harmful substances that can enter the human body through skin contact, eye contact, inhalation, etc., causing dizziness, nausea, vomiting, allergies and other symptoms, which seriously endanger human health. my country's "Cosmetics Safety Technical Specifications" (2015 Edition) and the EU Cosmetics Regulations (EC 1223/2009) clearly stipulate that estrone is a prohibited substance in cosmetics.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to provide a method for estrone, a prohibited substance in spray cosmetics, which is convenient, efficient and suitable for rapid on-site detection.

A rapid detection method for estrone, a prohibited substance in spray cosmetics, comprises the following steps:

Step 1, making an open double three-way capillary spray device;

The open double three-way capillary spray device includes a first three-way pipe and a second three-way pipe connected in series, forming a sample channel in the horizontal direction, and a capillary spray tube is arranged on the sample channel, and the capillary spray tube is The rear end is connected to one end of the shunt pipe, and the front end is arranged in the sample channel, close to the right end of the second tee, forming a mixing space with the right end of the second tee, and the shunt is The other end is connected to the sample bottle and the waste liquid bottle respectively through pipelines, the first three-way pipe is connected to the gas supply device through pipelines, and the second three-way pipe is connected to the syringe pump through pipelines. A mass spectrometer is arranged on the right side of the second tee;

Step 2, the open double three-way capillary spray device is placed 3-4 cm at the front end of the sample inlet of the mass spectrometer, and the parameters of the mass spectrometer are set as: positive ion mode, capillary voltage 4kV; set the gas pressure of the gas supply device to 30psi; Press the aerosol valve of the sample bottle to obtain a mass spectrum response signal;

Step 3. Improve the response value of the analyte

The syringe pump introduces liquid with a propelling speed of 20 μL/min. The atomizing gas blows away the atomized droplets, and mixes with the sample in the space at the front end of the capillary spray tube to improve the mass spectral response signal of the substance to be tested.

The method for rapid detection of estrone, a prohibited substance in spray cosmetics, according to the present invention, wherein the spray sample is spray cosmetics.

The method for rapid detection of estrone, a banned substance in spray cosmetics according to the present invention, wherein the mass spectrum information of the substance to be detected is shown in Table 1.

Table 1 The mass spectrometry information of the substance to be tested

The method for rapid detection of estrone, a prohibited substance in spray cosmetics, according to the present invention, wherein the first three-way pipe and the second three-way pipe both include a horizontal pipe and a vertical pipe, and the first three-way pipe includes a horizontal pipe and a vertical pipe. The left end of the horizontal pipe is closed with a fixed sheet, and the right end is connected with the left end of the horizontal pipe of the second three-way pipe. A through hole is provided on the fixed sheet, and the rear end of the capillary spray pipe is removed from the through hole. Pass it out and connect with the shunt tube.

The method for rapid detection of estrone, a prohibited substance in spray cosmetics according to the present invention, wherein the vertical pipe of the first three-way pipe is connected to the gas supply device through a pipeline, and the vertical pipe of the second three-way pipe is connected to the gas supply device through a pipeline. A straight pipe is connected to the syringe pump through a pipeline.

The method for rapid detection of estrone, a prohibited substance in spray cosmetics, according to the present invention, wherein the interface between the first three-way tube and the second three-way tube is 1/8 inch or 1/16 inch; the capillary tube The inner diameter of the spray tube is 10 to 200 μm.

The method for rapid detection of estrone, a prohibited substance in spray cosmetics according to the present invention, wherein the front end of the capillary spray tube is arranged in the second three-way tube, and the right end of the horizontal tube of the second three-way tube is located between The distance between them is 1 to 3 cm.

The rapid detection method for estrone, a prohibited substance in spray cosmetics, according to the present invention, wherein, a flow regulating valve is arranged on the shunt pipe.

The method for rapid detection of estrone, a prohibited substance in spray cosmetics, according to the present invention, wherein the liquid introduced by the syringe pump is a methoxyamine derivatization reagent.

The difference between the rapid detection method of the prohibited substance estrone in the spray cosmetic of the present invention and the prior art is:

The rapid detection method for estrone in spray cosmetics of the present invention establishes a detection method for rapid screening of estrone in spray cosmetics by double three-way capillary spray tandem ion trap mass spectrometry, which is convenient and efficient, and is suitable for rapid on-site detection. detection.

The innovation and advantages of the rapid detection method for the banned substance estrone in the spray cosmetic of the present invention are:

1. For the first time, the present invention proposes a method of double-three-way capillary spray tandem mass spectrometry to rapidly detect estrone, a prohibited substance in spray cosmetics.

2. The present invention is applicable to the detection method for the detection of banned substances in spray products by double-three-way capillary spray tandem mass spectrometry, and the response value of estrone is improved by introducing derivatization reagents, and the detection limit of estrone is 50 μg/kg.

3. The present invention does not need to use an extraction solvent.

The rapid detection method of estrone, a prohibited substance in the spray cosmetic of the present invention, will be further described below in conjunction with the accompanying drawings.

Description of drawings

Fig. 1 is the structural representation of the open type double three-way capillary spray device in the present invention;

Fig. 2 is the estrone mass spectrum in the cosmetic spray product in the method of the present invention;

The Chinese and English contrasts of all English appearing in the accompanying drawings of the description of the present invention are as follows:

m/z: cytoplasmic to nuclear ratio; Relative abundance: relative abundance; Intensity: intensity; Estrone: estrone.

Detailed ways

The first three-way tube and the second three-way tube (Swagelok (Shanghai) Fluid System Technology Co., Ltd.); P-1000 microelectrode drawing instrument (Sutter Company, USA); capillary spray tube (Yongnian Ruifeng Chromatography Devices Co., Ltd.) Company); BrukeramaZon ion trap mass spectrometer (Bruker Dalton, USA).

A rapid detection method for estrone, a prohibited substance in spray cosmetics, comprises the following steps:

Step 1, making an open double three-way capillary spray device;

As shown in Figure 1, the open double three-way capillary spray device includes a first three-way tube 1 and a second three-way tube 2 connected in series, forming a sample channel in the horizontal direction, and a capillary spray tube 3 is arranged on the sample channel, The rear end of the capillary spray pipe 3 is connected with one end of the shunt pipe 4, and the front end is arranged in the sample channel, close to the right end of the second three-way pipe 2, and forms a mixing space with the right end of the second three-way pipe 2, and the shunt pipe 4 The other end is connected to the sample bottle 5 and the waste liquid bottle 6 through pipelines, the first three-way pipe 1 is connected to the gas supply device 7 through pipelines, and the second three-way pipe 2 is connected to the syringe pump 8 through pipelines. A mass spectrometer 9 is arranged on the right side of the second three-way pipe 8;

The following are the preferred technical solutions of the open double three-way capillary spray device:

The first three-way pipe 1 and the second three-way pipe 2 both include a horizontal pipe and a vertical pipe. The left end of the horizontal pipe of the first three-way pipe 1 is closed by a fixing sheet 10, and the right end is connected to the horizontal pipe of the second three-way pipe 2. The left end of the capillary spray tube 3 is connected to the left end, and a through hole is provided on the fixing plate 10 , and the rear end of the capillary spray tube 3 passes through the through hole and is connected to the shunt tube 4 .

The vertical pipe of the first three-way pipe 1 is connected to the gas supply device 7 through a pipeline, and the vertical pipe of the second three-way pipe 2 is connected to the syringe pump 8 through a pipeline.

The interface between the first three-way pipe 1 and the second three-way pipe 2 is 1/8 inch or 1/16 inch; the inner diameter of the capillary spray pipe 3 is 10-200 μm.

The front end of the capillary spray pipe 3 is arranged in the second three-way pipe 2 , and the distance from the right end of the horizontal pipe of the second three-way pipe 2 is 1-3 cm.

A flow regulating valve is provided on the branch pipe 4 .

Step 2, the open double three-way capillary spray device is placed at 3-4 cm at the front end of the sample inlet of the mass spectrometer 9, and the parameters of the mass spectrometer 9 are set as: positive ion mode, capillary voltage 4kV; set the gas pressure of the gas supply device 7 to 30psi ; Press the aerosol valve of the sample bottle 5 to obtain the mass spectrum response signal;

Step 3. Improve the response value of the analyte

The liquid is introduced into the syringe pump 8, and the advancing speed is 20 μL/min. The atomizing gas blows away the atomized droplets, and mixes with the sample in the front space of the capillary spray tube 3 to improve the mass spectral response signal of the substance to be tested.

The spray sample in sample bottle 5 is a spray cosmetic sample.

The mass spectrometry information of the tested substances is shown in Table 1.

Table 1 The mass spectrometry information of the substance to be tested

The liquid introduced by the syringe pump 8 is the methoxyamine derivatization reagent.

The chemical information of the substance to be tested is shown in Table 2:

Table 2 Chemical information of the substances to be tested

The mass spectrum is shown in Figure 2.

The analyte analysis conditions involved in the present invention are all in positive ion mode, and derivatization reagents are usually introduced to improve the response value of the analyte. This patent relates to such a method of increasing the response value.

One way of the double three-way capillary spray device introduces atomizing gas, and the other way introduces derivatization reagent methoxyamine. It was determined that the response value of estrone in spray cosmetics was obviously improved through derivatization reaction. After testing, the detection limit of estrone was determined to be 50 μg/kg with a signal-to-noise ratio of about 3 times.

Application of specific detection methods:

1. Rapid detection of estrone in spray cosmetics.

The first step: make an open double three-way capillary spray device;

The second step: preparation of positive samples, adding different concentrations of estrogen ketone standard solutions to the detected estrogen-free cosmetic lotion to prepare positive samples.

Double three-way capillary rapid detection method: connect the positive spray lotion sample to the open double three-way capillary spray device. The inner diameter of the capillary spray tube 3 is 20 μm, the distance from the injection port of the mass spectrometer 9 is 3 cm, and the air pressure is 30 psi. Mass spectrometry conditions were set as: positive ion mode, capillary voltage 4kV. Press the product aerosol valve to get a mass spectral response signal.

Step 3: Improve the response of the analyte

Syringe pump 8 introduces 100 mM methoxyamine derivatization reagent, the advancing speed is 20 μL/min, the atomizing gas blows the atomized methoxyamine droplets, and the derivatization reaction occurs in the front space of the capillary spray tube 3 to improve the mass spectrum of estrone In response to the signal, its mass spectrum after derivatization is shown in Figure 2.

Before derivatization, the parent ion of estrone was m/z 271.3, which was greatly disturbed by noise and had a low response value. Through the device of the invention, the methoxyamine derivatization reagent is introduced, the monitoring parent ion of estrone is selected as m/z 300.2, the corresponding product ion is m/z 252.8, and the response value is significantly improved by 24 times compared with under-derivatization.

The above specific applications are only examples, not limitations, and all parameter selections within the scope of the present invention have obtained similar results.

The above-mentioned embodiments merely describe the preferred embodiments of the present invention, and do not limit the scope of the present invention. Without departing from the design spirit of the present invention, those of ordinary skill in the art can make various modifications to the technical solutions of the present invention. Variations and improvements should fall within the protection scope determined by the claims of the present invention.

Claims (7)

1. the rapid detection method of banned substance estrone in a spray cosmetic is characterized in that: comprise the steps: Step 1, making an open double three-way capillary spray device; The open double three-way capillary spray device comprises a first three-way pipe (1) and a second three-way pipe (2) connected in series, a sample channel is formed in a horizontal direction, and a capillary spray tube is arranged on the sample channel (3), the rear end of the capillary spray pipe (3) is connected with one end of the shunt pipe (4), and the front end is arranged in the sample channel, close to the right end of the second three-way pipe (2), and is connected to the A mixing space is formed between the right ends of the second three-way pipe (2), and the other end of the shunt pipe (4) is respectively connected with the sample bottle (5) and the waste liquid bottle (6) through pipelines. The three-way pipe (1) is connected to the gas supply device (7) through a pipeline, the second three-way pipe (2) is connected to the syringe pump (8) through a pipeline, and the second three-way pipe (2) A mass spectrometer (9) is arranged on the right side of the ; Step 2, the open double three-way capillary spray device is placed 3-4 cm at the front end of the sample inlet of the mass spectrometer (9), and the parameters of the mass spectrometer (9) are set as: positive ion mode, capillary voltage 4kV; set gas supply The air pressure of the device (7) is 30 psi; press the aerosol valve of the sample bottle (5) to obtain a mass spectrum response signal; Step 3. Improve the response value of the analyte: The syringe pump (8) introduces liquid, the advancing speed is 20 μL/min, the atomizing gas blows away the atomized droplets, and mixes with the sample in the front space of the capillary spray tube (3) to improve the mass spectral response signal of the substance to be tested. ; The liquid introduced by the syringe pump (8) is a methoxyamine derivatization reagent. 2. the rapid detection method of forbidden substance estrone in spray cosmetics according to claim 1, is characterized in that: Table 1 The mass spectrometry information of the substance to be tested

The mass spectrometry information of the tested substances is shown in Table 1. 3. The rapid detection method of estrone, a prohibited substance in spray cosmetics according to claim 2, characterized in that: the first three-way pipe (1) and the second three-way pipe (2) both comprise horizontal pipes and vertical pipe, the left end of the horizontal pipe of the first three-way pipe (1) is closed by a fixing piece (10), and the right end is connected with the left end of the horizontal pipe of the second three-way pipe (2). The fixing plate (10) is provided with a through hole, and the rear end of the capillary spray pipe (3) passes through the through hole and is connected with the shunt pipe (4). 4. The rapid detection method of estrone, a prohibited substance in spray cosmetics according to claim 3, characterized in that: the vertical pipe of the first three-way pipe (1) is connected to the gas supply device (7) through a pipeline. ), the vertical pipe of the second three-way pipe (2) is connected to the syringe pump (8) through a pipeline. 5. the rapid detection method of banned substance estrone in spray cosmetics according to claim 4, is characterized in that: the interface of described first three-way pipe (1) and described second three-way pipe (2) is 1 /8 inch or 1/16 inch; the inner diameter of the capillary spray tube (3) is 10-200 μm. 6. The rapid detection method of estrone, a prohibited substance in spray cosmetics, according to claim 5, characterized in that: the front end of the capillary spray pipe (3) is arranged in the second three-way pipe (2), and the The distance between the right ends of the horizontal pipes of the second three-way pipe (2) is 1-3 cm. 7. The method for rapid detection of estrone, a prohibited substance in spray cosmetics, according to claim 6, characterized in that: a flow regulating valve is provided on the shunt pipe (4).

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