Expiratory gas collecting device assembled based on cellulose sponge material and application of expiratory gas collecting device in amphetamine drug detection

Abstract

The invention belongs to the technical field of amphetamine drug detection, and discloses an exhaled air collecting device assembled based on a cellulose sponge material and application of the exhaled air collecting device in amphetamine drug detection. The cellulose sponge is prepared after being simply soaked in a sodium hydroxide solution, and the cellulose sponge can be used for exhaled air collection after being assembled with a simple and portable exhaled air collection device into a whole. The invention further provides a detection method, the cellulose sponge material enriches low-concentration amphetamine drugs through adsorption in the exhaled air collection process, a sample is eluted, concentrated, redissolved and filtered, and then the content of the amphetamine drugs is detected through high performance liquid chromatography-triple quadrupole mass spectrometry. The method can be used for simply, conveniently and accurately detecting the amphetamine drugs in the exhaled air and analyzing the content of the amphetamine drugs, so that the screening work can be quickly and efficiently completed.

Description

Technical Field

[0001] This application relates to the technical field of amphetamine drug detection, and particularly relates to an exhaled breath collection device assembled based on a cellulose sponge material and its application in amphetamine drug detection. Background Art

[0002] Amphetamine drugs include various types such as methamphetamine (METH), amphetamine (AMP), ephedrine (EPH), 3,4-methylenedioxyamphetamine (MDA), and 3,4-methylenedioxyphenylamphetamine (MDMA). Their abuse has attracted wide attention worldwide. Common biological specimens for amphetamine drugs include blood, urine, and hair. The collection of these biological specimens is either restricted by time and space or requires professional knowledge support. In addition, there are risks of invading personal privacy and sample adulteration. Exhaled breath has the potential to be used as a biological specimen for amphetamine drug detection due to the advantages of simple collection, non-invasive nature, and easy acceptance. However, compared with other biological specimens, the content of amphetamine drugs in exhaled breath is low, which poses challenges to its pretreatment and detection techniques. Therefore, in order to increase the content of amphetamine drugs in exhaled breath so that they can be detected by existing detection techniques, it is necessary to enrich the content of such drugs in exhaled breath through techniques such as adsorption and separation.

[0003] Chinese Patent CN119346080A discloses a functionalized composite material, an exhaled breath collection device assembled based on the functionalized composite material, a detection method, and an application, aiming to achieve the detection of low-concentration amphetamine drugs in exhaled breath. This invention uses the functionalized composite material to collect drugs in exhaled breath, elute and concentrate them, and then uses high-performance liquid chromatography tandem triple quadrupole mass spectrometry for detection to accurately and quickly screen drug addicts through amphetamine drugs in exhaled breath. However, the preparation process of this functionalized composite material is cumbersome and requires a large number of reagents and consumables, which is time-consuming, laborious, and costly. Therefore, it is of great significance to find an adsorption material with a simple preparation process, time-saving and labor-saving, low price, and capable of efficiently enriching amphetamine drugs in exhaled breath.

[0004] Sponge materials have a three-dimensional porous network structure with criss-crossing vertical and horizontal directions, a large specific surface area, and a high porosity. Due to their simple preparation and convenient use, they have been widely used in fields such as oil-water separation, sewage and waste gas purification. However, there are currently no relevant reports on the use of sponges for exhaled breath collection. The present invention provides a simple and easily available sponge material for enriching low-concentration amphetamine drugs in exhaled breath while collecting exhaled breath for accurate detection. Summary of the Invention

[0005] In order to overcome the shortcomings and deficiencies existing in the prior art, the first object of the present invention is to provide a cellulose sponge material and a simple preparation method thereof.

[0006] Another object of the present invention is to provide an exhaled gas collection device assembled based on the above cellulose sponge material.

[0007] Yet another object of the present invention is to provide an application of an exhaled gas collection device assembled based on the above cellulose sponge material in the detection of amphetamine drugs and to provide a convenient detection method.

[0008] The object of the present invention is achieved by the following technical solutions:

[0009] A cellulose sponge material, the preparation method thereof comprising the following steps:

[0010] Put the cellulose sponge into absolute ethanol and ultrasonically clean for a first duration, then put it into ultrapure water and ultrasonically clean for a second duration. Immediately afterwards, put it into a sodium hydroxide solution and soak at room temperature for a third duration. After cleaning and drying, the cellulose sponge material is obtained.

[0011] Further, the first duration is 20 - 40 min; the ultrasonic power is 100 - 500 W.

[0012] Further, the second duration is 20 - 40 min; the ultrasonic power is 100 - 500 W.

[0013] Further, the third duration is 10 - 14 h; the concentration of the sodium hydroxide solution is 0.8 - 1.2 mol / L; the volume ratio of the cellulose sponge to the sodium hydroxide solution is 0.2 - 2.

[0014] The cellulose sponge material obtained by the above preparation method has porous and irregular pore structures, including small pores, medium pores and large pores. The aperture of the small pores is 138 - 160 μm, the aperture of the medium pores is 366 - 411 μm, and the aperture of the large pores is 610 - 646 μm.

[0015] An exhaled gas collection device assembled based on the above cellulose sponge material, comprising an intake pipe, an adsorption module and a gas flow meter;

[0016] The adsorption module includes an air inlet, a first housing, a first support portion, a sponge material, a second support portion, a second housing and an air outlet arranged in sequence;

[0017] One end of the intake pipe is detachably connected to the air inlet of the adsorption module; the first housing and the second housing of the adsorption module are detachably connected; one end of the gas flow meter is detachably connected to the air outlet of the adsorption module; in addition, the adsorption module further includes a first end cap and a second end cap for sealing the air inlet and the air outlet, so that the adsorption module is in an overall airtight state;

[0018] The sponge material is arranged between the first support portion and the second support portion.

[0019] Further, the cavity volume of the adsorption module is 50 to 200 cm 3 .

[0020] Further, 1 to 5 peripheral protrusions are horizontally arranged on the outer wall of the first housing; 8 to 16 grooves surrounding the inner wall are longitudinally arranged on the inner wall of the second housing, and 1 to 5 parallel peripheral notches are arranged at the vertically communicating positions of the grooves; the grooves are evenly divided into 3 to 5 levels, and the number of grooves in each level is 1 to 5; the first housing and the second housing are rotated by inserting 1 to 5 peripheral protrusions into the grooves along the peripheral notches, so that 1 to 5 peripheral protrusions and notches at the same level are fitted together, and the internal volume of the adsorption module 2 can be adjusted by controlling the amplitude of inserting 1 to 5 peripheral protrusions into the grooves along the peripheral notches.

[0021] Further, an annular groove for accommodating a sealing ring is provided on the contact surface of the first housing or / and the second housing.

[0022] The present application provides an application of an exhaled breath collection device assembled based on the above cellulose sponge material in the detection of amphetamine drugs, which is used to collect amphetamine drugs in exhaled breath and detect their content. The method includes the following steps:

[0023] The subject rinses the mouth with drinking water for 0.05 to 2 min and then exhales into the exhaled breath collection device for 2 to 8 min; after the collection is completed, the cellulose sponge material is taken out and soaked in an organic solvent for ultrasonic elution, then the eluate is transferred to a new centrifuge tube and concentrated by nitrogen blowing under water bath conditions, and then redissolved with an organic solvent. The re-dissolved solution is filtered through a 0.22 μm filter membrane into a sample vial to obtain an extract; the content of amphetamine drugs in the extract is detected by high performance liquid chromatography tandem triple quadrupole mass spectrometry.

[0024] Further, before the exhaled breath collection, according to the self-reported information of the subject, the presence and content of amphetamine drugs in the exhaled breath of different subject populations are predicted. According to the prediction results, a sponge material with a suitable size and matching adsorption performance is selected, and at the same time, the internal volume of the exhaled breath collection device is adjusted according to the size of the sponge material, so as to achieve the purpose of effective adsorption while saving the sponge material.

[0025] For the application of the exhaled breath collection based on the above cellulose sponge material assembly in the detection of amphetamine drugs, the content of amphetamine drugs in exhaled breath can be detected within the range of 30.0 to 20000.0 pg / filter, and the accuracy rate can reach 87.49 ± 1.12% to 98.93 ± 2.46%.

[0026] In summary, the present application provides an exhaled gas collection device assembled based on a cellulose sponge material and its application in the detection of amphetamine drugs. The cellulose sponge material prepared by the simple method provided by the present invention has good adsorption and enrichment ability for amphetamine drugs in exhaled gas. Compared with the prior art, the preparation process of the sponge material is simple, convenient, easy to use, and highly available. In addition, after being assembled into a simple and portable exhaled gas collection device, the sponge material can be used for exhaled gas collection. The present application also provides an exhaled gas collection device assembled based on a cellulose sponge material and its application in the detection of amphetamine drugs. The cellulose sponge material can enrich low-concentration amphetamine drugs through adsorption during the exhaled gas collection process. After the sample is eluted, concentrated, redissolved, and filtered, the content of amphetamine drugs is detected by high-performance liquid chromatography-tandem triple quadrupole mass spectrometry. By using the above method, the detection and content analysis of amphetamine drugs in exhaled gas can be achieved simply, conveniently, and accurately, so as to quickly and efficiently complete the screening work of drug addicts. Compared with the prior art, for the first time in the present application, the cellulose sponge is directly used for exhaled gas collection without modification and realizes the adsorption and enrichment of amphetamine drugs therein, expanding the application field of the sponge material and stimulating its application potential.

[0027] The solution of the present invention has the following beneficial effects:

[0028] 1. The present invention provides a cellulose sponge material prepared by a simple process, which is obtained by soaking cellulose sponge in sodium hydroxide. It has high porosity, rough surface, diverse pore distribution, rich hierarchical structure, and rich functional groups, and can efficiently adsorb amphetamine drugs in exhaled gas. Compared with the prior art, the sponge material has the advantages of simple preparation, easy use, high availability, and low price.

[0029] 2. The present invention also provides a simple and portable exhaled gas collection device assembled based on a cellulose sponge material. Using this device for exhaled gas collection is simple, fast, and non-invasive; at the same time, in order to adapt to different types and thicknesses of sponges, the internal volume of its cavity can be adjusted, making it have good compatibility with the sponge material.

[0030] 3. The present invention provides an exhaled gas collection device assembled based on a cellulose sponge material and its application in the detection of amphetamine drugs, and provides a detection method. This method is simple and fast, and the output detection data has good accuracy and high reliability, so as to quickly and efficiently complete the screening work of drug addicts. Compared with the prior art, the present invention first uses cellulose sponge in the field of amphetamine drug detection, expanding the application field of the sponge material and disclosing its new application scope. Description of the Drawings

[0031] To more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the accompanying drawings required for the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only some embodiments of the present application. For those of ordinary skill in the art, without creative efforts, other accompanying drawings can also be obtained based on these drawings.

[0032] Figure 1 It is the microscopic image of the sponge material prepared in Example 3 after being magnified 100× by an optical microscope, and the scale is 100μm.

[0033] Figure 2 It is the attenuated total reflection infrared spectrum of the sponge material prepared in Example 3.

[0034] Figure 3 It is the structural schematic diagram of the exhaled breath collection device assembled with the sponge material provided in Example 5.

[0035] Figure 4 It is the physical diagram of the components and the whole of the exhaled breath collection device assembled with the sponge material provided in Example 5.

[0036] Figure 5 It is the adsorption situation of amphetamine drugs by the sponge materials provided in Example 5 and Comparative Examples 1-7 under the conditions of simulating exhaled breaths with different flow rates.

[0037] Figure 6 It is the microscopic image of the sponge materials prepared in Comparative Examples 1-7 after being magnified 100× by an optical microscope, and the scale is 100μm.

[0038] Figure 7 It is the attenuated total reflection infrared spectrum of the sponge materials prepared in Comparative Examples 1-7.

[0039] Reference numerals: 1, intake pipe; 2, adsorption module; 3, gas flow meter; 211, air inlet; 212, air outlet; 221, first housing; 222, second housing; 231, first support part; 232, second support part; 24, sponge material; 251, first end cap; 252, second end cap; 26, sealing ring. Detailed implementation manners

[0040] The following will clearly and completely describe the technical solutions of the embodiments of the present application with reference to the accompanying drawings. Obviously, the described embodiments are some, rather than all, of the embodiments of the present application. Based on the embodiments in this specification of the present application, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope claimed by the present application.

[0041] Among them, there are no special restrictions on the sources of all raw materials of the present invention, and they can be purchased on the market or prepared according to conventional methods well-known to those skilled in the art.

[0042] The embodiment of the present invention provides a cellulose sponge material, and its preparation method includes the following steps:

[0043] Put the cellulose sponge into absolute ethanol for ultrasonic cleaning for the first duration, then put it into ultrapure water for ultrasonic cleaning for the second duration, and then immediately put it into a sodium hydroxide solution for soaking at room temperature for the third duration. After cleaning and drying, the cellulose sponge material is obtained.

[0044] In some embodiments, the thickness of the sponge material is 40 mm, and before the experiment, it is cut into a cylinder with a diameter of 2 - 6 cm; the volume of absolute ethanol is 200 - 400 mL; the volume of ultrapure water is 200 - 400 mL.

[0045] In some embodiments, the first duration is 20 - 40 min, and the ultrasonic power is 100 - 500 W; the second duration is 20 - 40 min, and the ultrasonic power is 100 - 500 W; the third duration is 10 - 14 h, the concentration of the sodium hydroxide solution is 0.8 - 1.2 mol / L; the volume ratio of the cellulose sponge to the sodium hydroxide solution is 0.2 - 2.

[0046] Preferably, the first duration is 30 min, and the ultrasonic power is 300 W; the second duration is 30 min, and the ultrasonic power is 300 W; the third duration is 12 h, the concentration of the sodium hydroxide solution is 1.0 mol / L; the volume ratio of the cellulose sponge to the sodium hydroxide solution is 0.83.

[0047] Refer to Figure 3 , the embodiment of this application provides an exhaled gas collection device assembled based on the above-mentioned cellulose sponge material, including an intake pipe 1, an adsorption module 2, and a gas flowmeter 3;

[0048] The adsorption module 2 includes an air inlet 211, a first housing 221, a first support portion 231, a sponge material 24, a second support portion 232, a second housing 222, and an air outlet 212 arranged in sequence;

[0049] One end of the intake pipe 1 is detachably connected to the air inlet 211 of the adsorption module 2; the first housing 221 and the second housing 222 of the adsorption module 2 are detachably connected; one end of the gas flowmeter 3 is detachably connected to the air outlet 212 of the adsorption module 2; in addition, the adsorption module 2 further includes a first end cap 251 and a second end cap 252, which are used to seal the air inlet 211 and the air outlet 212, so that the adsorption module 2 is in an overall airtight state;

[0050] The sponge material 24 is arranged between the first support portion 231 and the second support portion 232.

[0051] In some embodiments, the mouthpiece of the exhaled gas collection device is flat and duckbill-shaped.

[0052] The physical diagrams of the whole exhaled gas collection device and its components are shown in Figure 4 . The exhaled gas collection device assembled with sponge material provided by the embodiments of the present invention can not only realize simple, rapid and convenient collection of exhaled gas, but also cause no invasive injury or psychological shadow to the subject, and has high acceptance willingness and comfort level of personnel.

[0053] In some embodiments, both the first support portion 231 and the second support portion 232 are formed by connecting 8 ribs to each other, and the second support portion 232 is provided with a circular baffle for changing the exhaled gas flow path.

[0054] The presence of the circular baffle in the cavity changes the exhaled gas movement path and speed entering the cavity, increases the movement time of the exhaled gas in the cavity and improves the contact probability between the sponge material and the exhaled gas, thereby increasing the content of amphetamine drugs adsorbed on the sponge material.

[0055] In some embodiments, the cavity volume of the adsorption module 2 is 50-200 cm 3 .

[0056] Preferably, the cavity volume of the adsorption module 2 is 100 cm 3 .

[0057] In some embodiments, 1-5 peripheral protrusions are horizontally arranged on the outer wall of the first housing 221; 8-16 grooves surrounding the inner wall are longitudinally arranged on the inner wall of the second housing 222, and 1-5 parallel peripheral notches are arranged at the vertical connection of the grooves; the grooves are evenly divided into 3-5 levels, and the number of grooves in each level is 1-5; the first housing 221 and the second housing 222 are rotated by inserting 1-5 peripheral protrusions into the grooves along the peripheral notches, so that 1-5 peripheral protrusions and notches at the same level are fitted together, and the internal volume of the adsorption module 2 can be adjusted by controlling the amplitude of the 1-5 peripheral protrusions inserted into the grooves along the peripheral notches.

[0058] Preferably, 3 peripheral protrusions are horizontally arranged on the outer wall of the first housing 221; 12 grooves surrounding the inner wall are longitudinally arranged on the inner wall of the second housing 222, and 3 parallel peripheral notches are arranged at the vertical connection of the grooves; the grooves are evenly divided into 4 levels, and the number of grooves in each level is 3; the first housing 221 and the second housing 222 are rotated by inserting 3 peripheral protrusions into the grooves along the peripheral notches, so that 3 peripheral protrusions and notches at the same level are fitted together, and the internal volume of the adsorption module 2 can be adjusted by controlling the amplitude of the 3 peripheral protrusions inserted into the grooves along the peripheral notches.

[0059] The exhaled breath collection device of the present invention has good material compatibility, and the internal volume of its adsorption module can be adjusted according to the sponge thickness and type.

[0060] In some embodiments, an annular groove for accommodating the sealing ring 26 is provided on the contact surface of the first housing 221 and / or the second housing 222.

[0061] The present application provides an application of an exhaled breath collection device assembled based on the above cellulose sponge material in the detection of amphetamine drugs, which is used to collect amphetamine drugs in exhaled breath and detect their content. The specific steps are as follows:

[0062] The subject rinses their mouth with drinking water for 0.05 - 2 min and then exhales into the exhaled breath collection device for 2 - 8 min; after the collection is completed, the sponge material is taken out and soaked in an organic solvent for ultrasonic elution, then the eluate is transferred to a new centrifuge tube and concentrated by nitrogen blowing under water bath conditions, and then re-dissolved with an organic solvent. The re-dissolved solution is filtered through a 0.22 μm filter membrane into a sample vial to obtain an extract; the content of amphetamine drugs in the extract is detected by high performance liquid chromatography tandem triple quadrupole mass spectrometry.

[0063] In some embodiments, before collecting exhaled breath, according to the self-reported information of the subject, the presence and content of amphetamine drugs in the exhaled breath of different subject populations are predicted. According to the prediction results, a sponge material with a suitable size and matching adsorption performance is selected, and the internal volume of the exhaled breath collection device is adjusted according to the sponge material size, so as to achieve the purpose of effective adsorption while saving sponge materials.

[0064] Specifically, the parent body of amphetamine drugs is the amphetamine structure, including one or more of AMP, METH, MDA, MDMA, EPH, p-hydroxymethamphetamine, p-methoxymethamphetamine, 4-methylthiopropylamine, 3,4-methylenedioxyethylamphetamine, 3-methoxy-4,5-methylenedioxymethamphetamine, and dimethoxyethylamphetamine.

[0065] The present invention will be described below with reference to specific embodiments. It should be noted that these embodiments are merely descriptive and do not limit the present invention in any way.

[0066] Example 1

[0067] A cellulose sponge material, and its preparation method includes the following steps:

[0068] Cut a cellulose sponge with a thickness of 40 mm into a cylinder with a diameter of 2 cm, and then put it into 200 mL of absolute ethanol for ultrasonic cleaning for 20 min. Then put it into 200 mL of ultrapure water and ultrasonic clean for 20 min. Immediately put it into 200 mL of sodium hydroxide solution (0.8 mol / L) and soak at room temperature for 10 h. After cleaning and drying, a cellulose sponge material is obtained.

[0069] Example 2

[0070] A cellulose sponge material, and its preparation method includes the following steps:

[0071] Cut a cellulose sponge with a thickness of 40 mm into a cylinder with a diameter of 6 cm, and then put it into 400 mL of absolute ethanol for ultrasonic cleaning for 40 min. Then put it into 400 mL of ultrapure water and ultrasonic clean for 40 min. Immediately put it into 400 mL of sodium hydroxide solution (1.2 mol / L) and soak at room temperature for 14 h. After cleaning and drying, a cellulose sponge material is obtained.

[0072] Example 3

[0073] A cellulose sponge material, and its preparation method includes the following steps:

[0074] Cut a cellulose sponge with a thickness of 40 mm into a cylinder with a diameter of 4 cm, and then put it into 300 mL of absolute ethanol for ultrasonic cleaning for 30 min. Then put it into 300 mL of ultrapure water and ultrasonic clean for 30 min. Immediately put it into 300 mL of sodium hydroxide solution (1.0 mol / L) and soak at room temperature for 12 h. After cleaning and drying, a cellulose sponge material is obtained.

[0075] Characterization:

[0076] To analyze the surface morphology of the sponge material prepared in Example 3, it was characterized by an optical microscope, see Figure 1 . Under the 100× magnification of the optical microscope, the pores of the sponge material are of different sizes, the pore distribution is diverse, and the pore structure is irregular. The pore area and pore radius are 0.06 - 1.31 mm 2 and 138 - 646 μm respectively. It shows that the pore structure of the cellulose sponge material prepared by the method of the present invention is diversified, with both large pores with a radius reaching 610 - 646 μm, small pores with a radius of only 138 - 160 μm, and medium pores with a radius of 366 - 411 μm.

[0077] Perform attenuated total reflection infrared characterization on the sponge material prepared in Example 3, see Figure 2 . From Figure 2It can be seen that the spectral curve is relatively smooth, with a small number of absorption peaks and a high degree of concentration, indicating that the chemical composition of the cellulose sponge material is relatively simple. The characteristic adsorption peak of the sponge material in the range of 3380 - 3272 cm -1 can be attributed to the stretching vibration of -OH, and the characteristic absorption peak at 894 cm -1 corresponds to the stretching vibration of the asymmetric ring in the cellulose molecule. These data indicate that the sponge material is rich in hydroxyl groups and the main framework is cellulose molecules.

[0078] Example 4

[0079] An exhaled gas collection device assembled with the cellulose sponge material prepared based on the above embodiments, comprising an intake pipe 1, an adsorption module 2, and a gas flow meter 3;

[0080] The adsorption module 2 includes an air inlet 211, a first housing 221, a first support portion 231, a sponge material 24, a second support portion 232, a second housing 222, and an air outlet 212 arranged in sequence;

[0081] One end of the intake pipe 1 is detachably connected to the air inlet 211 of the adsorption module 2, and the other end is in a flat duckbill shape; one end of the gas flow meter 3 is detachably connected to the air outlet 212 of the adsorption module 2; there are 3 peripheral protrusions horizontally arranged on the outer wall of the first housing 221; there are 12 grooves surrounding the inner wall longitudinally arranged on the inner wall of the second housing 222, and there are 3 parallel peripheral notches at the vertical connection of the grooves; the grooves are evenly divided into 4 levels, and the number of grooves in each level is 3; the first housing 221 and the second housing 222 are rotated by inserting 3 peripheral protrusions along the peripheral notches into the grooves, so that the 3 peripheral protrusions and notches at the same level are fitted together, and the internal volume of the adsorption module 2 can be adjusted by controlling the amplitude of the 3 peripheral protrusions inserted into the grooves along the peripheral notches; there is an annular groove for accommodating a silicone rubber seal ring 26 on the contact surface of the first housing 221 or / and the second housing 222; both the first support portion 231 and the second support portion 232 are formed by connecting 8 ribs to each other, and the second support portion 232 is provided with a circular baffle for changing the exhaled gas flow path. The sponge material 24 is arranged between the first support portion 231 and the second support portion 232; the adsorption module 2 further includes a first end cap 251 and a second end cap 252, which are used to seal the air inlet 211 and the air outlet 212 after the exhaled gas collection is completed, so that the adsorption module 2 is in a closed state.

[0082] Example 5

[0083] An application of an exhaled gas collection device assembled with the above cellulose sponge material in the detection of amphetamine drugs, for collecting amphetamine drugs in exhaled gas and detecting their content, comprising the following steps:

[0084] Step S1: Use the exhaled breath collection device prepared in Example 4 to perform simulated exhaled breath collection at flow rates of 8 L / min and 20 L / min respectively, with a collection time of 5 min; among them, the sponge material in the exhaled breath collection device is the sponge material prepared in Examples 1 to 3; after the collection, take out the sponge material and soak it in 10 mL of methanol (5% formic acid) solution for ultrasonic elution, then transfer the eluate to a new centrifuge tube and concentrate it by nitrogen blowing under water bath conditions, and then dissolve it again with 200 μL of methanol by shaking at 3000 r / min for 0.5 min. The reconstituted solution is filtered through a 0.22 μm filter membrane into a sample vial to obtain an extract.

[0085] Step S2, Sample detection:

[0086] Step S2-1: Preparation of the standard curve. Prepare a standard solution of amphetamine drugs with an isotope internal standard content of 2000 pg / filter using chromatographically pure methanol as the solvent, with concentration gradients of 30, 50, 100, 200, 1000, 2000, 4000, 10000, and 20000 pg / filter in sequence. Use high-performance liquid chromatography tandem triple quadrupole mass spectrometry for detection and analysis, and draw a standard working curve based on its response intensity and concentration (pg / filter). X and Y are the drug concentration and the ratio of the drug peak area to the isotope internal standard peak area respectively. The detection limit is calculated by three times the signal-to-noise ratio. The detection limits and linear information of 5 amphetamine drugs are shown in Table 1. The amphetamine drugs have good linearity in the concentration range of 30.0 - 20000.0 pg / filter (R 2 ≥0.9988), and the detection limits are in the range of 1.6 - 8.4 pg / filter, indicating that this method is suitable for the detection of amphetamine drugs in exhaled breath.

[0087] Table 1 Detection limits and linear information of amphetamine drugs

[0088]

[0089] Step S2-2: Use high-performance liquid chromatography tandem triple quadrupole mass spectrometry to detect the extract, and calculate the concentration of amphetamine drugs in it according to the standard curve equation.

[0090] The detection conditions are as follows:

[0091] Liquid phase conditions: Kinetex Biphenyl (100 mm × 3.0 mm, 2.6 μm) chromatographic column from Phenomenex, USA, with mobile phases of 0.1% formic acid in water (A) and acetonitrile containing 0.1% formic acid (B); the flow rate is set at 0.4 mL / min, the column temperature is set at 40 °C; the injection volume is set at 5 μL;

[0092] Mass spectrometry conditions: AB SCIEX API 4500 triple quadrupole mass spectrometer from the United States, determined in multiple reaction monitoring (MRM) mode under the electrospray positive ion (ESI + ) mode. The ESI ion source temperature is 550 °C, the electrospray voltage is 3.2 KV, the curtain gas (CUR) pressure is 30 psi, the nebulizing gas (GS1) pressure is 40 psi, and the heating gas (GS2) pressure is 40 psi.

[0093] Based on the above detection method, the spike recoveries of the exhaled breath collection devices assembled with the sponge materials prepared in Examples 1 to 3 were investigated, and the results are shown in Table 2.

[0094] Table 2 Spike recoveries of amphetamine drugs

[0095]

[0096] As can be seen from Table 2, the spike recovery of the sponge material prepared in Example 3 is the highest, reaching 87.49 ± 1.12% - 98.93 ± 2.46%, indicating that it can efficiently adsorb amphetamine drugs in exhaled breath and is more conducive to the enrichment of such drugs in exhaled breath. Since the concentrations, volumes, and soaking times of the sodium hydroxide solutions used to prepare the sponge materials in Examples 1, 2, and 3 are different, the recovery capabilities of the prepared sponge materials for amphetamine drugs in exhaled breath are also different. Soaking the sponge material with sodium hydroxide solution can cause the sponge material to swell, increase its porosity, and improve its chemical activity. However, too high a sodium hydroxide concentration, too large a sodium hydroxide volume, and too long a soaking time will damage the structure of the sponge material, change the morphology of the material, and reduce its adsorption performance for the target substance. In contrast, too low a sodium hydroxide concentration, too small a volume, and too short a soaking time will result in low swelling degree of the sponge, limited porosity, and insufficient chemical activity, thus reducing the adsorption performance for the target substance. Therefore, it is necessary to optimize the concentration, volume, and soaking time of the sodium hydroxide solution to optimize the adsorption performance of the sponge material, thereby improving its spike recovery for amphetamine drugs.

[0097] Comparative Example 1

[0098] The difference from Example 5 is that the sponge material is prepared by treating polyvinyl alcohol sponge with sodium hydroxide, and the sodium hydroxide concentration, soaking time, and material-liquid ratio are the same as those in Example 3. The optical micrograph and attenuated total reflection infrared spectrum of the prepared material are shown in Figure 6 and Figure 7 in (a).

[0099] Comparative Example 2

[0100] The difference from Example 5 is that the sponge material is prepared by treating latex sponge with sodium hydroxide, and the sodium hydroxide concentration, soaking time, and material-liquid ratio are the same as those in Example 3. The optical micrograph and attenuated total reflection infrared spectrum of the obtained material are shown in Figure 6 and Figure 7 (a) in

[0101] Comparative Example 3

[0102] The difference from Example 5 is that the sponge material is prepared by treating melamine sponge with sodium hydroxide, and the sodium hydroxide concentration, soaking time, and material-liquid ratio are the same as those in Example 3. The optical micrograph and attenuated total reflection infrared spectrum of the obtained material are shown in Figure 6 and Figure 7 (a) in

[0103] Comparative Example 4

[0104] The difference from Example 5 is that the sponge material is prepared by treating polyurethane sponge with sodium hydroxide, and the sodium hydroxide concentration, soaking time, and material-liquid ratio are the same as those in Example 3. The optical micrograph and attenuated total reflection infrared spectrum of the obtained material are shown in Figure 6 and Figure 7 (b) in

[0105] Comparative Example 5

[0106] The difference from Example 5 is that the sponge material is prepared by treating polyethylene sponge with sodium hydroxide, and the sodium hydroxide concentration, soaking time, and material-liquid ratio are the same as those in Example 3. The optical micrograph and attenuated total reflection infrared spectrum of the obtained material are shown in Figure 6 and Figure 7 (b) in

[0107] Comparative Example 6

[0108] The difference from Example 5 is that the sponge material is prepared by treating vinyl acetate sponge with sodium hydroxide, and the sodium hydroxide concentration, soaking time, and material-liquid ratio are the same as those in Example 3. The optical micrograph and attenuated total reflection infrared spectrum of the obtained material are shown in Figure 6 and Figure 7 (b) in

[0109] Comparative Example 7

[0110] The difference from Example 5 is that the sponge material is prepared by treating silica gel sponge with sodium hydroxide, and the sodium hydroxide concentration, soaking time, and material-liquid ratio are the same as those in Example 3. The optical micrograph and attenuated total reflection infrared spectrum of the obtained material are shown in Figure 6 and Figure 7 (b) in

[0111] For the test results of the cellulose sponge material prepared in Example 3 and the other sponge materials in Comparative Examples 1-7, see Figure 5 . As Figure 5 . As shown in (a) of Figure 5 , when the exhalation flow rate is 8 L / min, the adsorption capacities of cellulose sponge, polyvinyl alcohol sponge and latex sponge for amphetamine drugs in exhaled air are higher than those of melamine sponge, polyurethane sponge, polyethylene sponge, vinyl acetate sponge and silica gel sponge. The overall adsorption rate of cellulose sponge for amphetamine drugs is the highest, reaching 87.49±1.12% - 98.93±2.46%. Followed by polyvinyl alcohol sponge and latex sponge, which are 48.43±0.32% - 68.86±1.93%. The adsorption rate of silica gel sponge is the lowest, only 3.99±0.24% - 5.44±0.54%. The adsorption rates at an exhalation flow rate of 20 L / min can be seen in Figure 5 . (b) of Figure 5 . The variation law of the adsorption rate of the sponge at 20 L / min is similar to that at 8 L / min. The adsorption rate of cellulose sponge is still the highest, reaching 81.56±2.10% - 92.90±2.83%. Compared with that at 8 L / min, the overall adsorption rate of the sponge at 20 L / min decreases. This is related to the shorter contact time between amphetamine drugs in exhaled air and the sponge at high flow rates, and the stronger impact force of exhaled air on the sponge, making it easier to penetrate the sponge. Overall, the adsorption performance of cellulose sponge is the best, and that of silica gel sponge is the worst. Generally speaking, cellulose sponge can achieve efficient adsorption of amphetamine drugs in simulated exhaled air and is more suitable for enriching amphetamine drugs in exhaled air.

[0112] Comparing Figure 1 , 2 , 6, and 7, it can be found that among the eight sponge materials, the pore size of the silica gel sponge is too large to effectively intercept amphetamine drugs in exhaled air. The pores of polyvinyl alcohol sponge, melamine sponge and vinyl acetate sponge are small, the pore distribution is uniform and there is a lack of hierarchical structure, resulting in relatively weak adsorption capacity for amphetamine drugs in exhaled air. Polyethylene sponge lacks functional groups and has limited adsorption capacity. The density of latex sponge and polyurethane sponge is relatively low and the content of functional groups is relatively low, making their adsorption capacity relatively low. Cellulose sponge has a large density, high porosity, rough surface, diverse pore distribution, rich hierarchical structure and rich functional groups, and these properties enable it to efficiently adsorb amphetamine drugs in exhaled air.

[0113] The mechanism of cellulose sponge for adsorbing amphetamine drugs in exhaled breath includes physical capture and intermolecular interaction. When the turbulent exhaled breath diffuses to the outer surface of the sponge, the aerosol molecules in the exhaled breath collide with the sponge and disperse into smaller aerosols. Part of the aerosols are adsorbed on the sponge surface in the form of a monolayer structure, and the other part diffuses further into the internal space through the rich pore structure of the sponge and is captured by the internal network structure of the sponge. The amphetamine drugs adsorbed in the aerosol interact with the sponge through four possible adsorption mechanisms. One of them is dipole-dipole hydrogen bond, including the interaction between the hydrogen atom (hydrogen bond donor) of the hydroxyl group contained in the cellulose sponge and the available nitrogen atom (hydrogen bond acceptor) in the amphetamine drug, the interaction between the hydrogen atom (hydrogen bond donor) of the amino group contained in the amphetamine drug molecule and the oxygen atom (hydrogen bond acceptor) on the sponge, and the interaction between the hydrogen atom (hydrogen bond donor) of the hydroxyl group contained in the EPH molecule and the oxygen atom (hydrogen bond acceptor) on the sponge. The second interaction can be attributed to π-type hydrogen bond, that is, the interaction formed between the hydrogen atom of the hydroxyl group on the sponge and the aromatic ring in the amphetamine drug. The third interaction is attributed to n-π stacking, which mainly occurs when the oxygen lone pair electrons (electron donor) on the sponge delocalize into the π orbit of the aromatic ring (electron acceptor) in the amphetamine drug. The fourth possible interaction is van der Waals force, which enhances the adsorption performance.

[0114] Example 8

[0115] The exhaled breath collection device assembled based on the cellulose sponge material of the present invention is used for the detection of amphetamine drugs in actual human exhaled breath samples, and the specific steps are as follows:

[0116] The subject rinsed their mouth with drinking water for 0.5 min and then exhaled into the exhaled breath collection device for 5 min; among them, the sponge material assembled in the exhaled breath collection device was prepared in Example 3; after the collection, the sponge material was taken out and soaked in 10 mL of methanol (5% formic acid) solution for ultrasonic elution, then the eluate was transferred to a new centrifuge tube and concentrated by nitrogen blowing under water bath conditions, and then redissolved with 200 μL of methanol by oscillating at 3000 r / min for 0.5 min. The reconstituted solution was filtered through a 0.22 μm filter membrane into an injection vial to obtain the extract.

[0117] Step S2-1: Preparation of the standard curve. A standard solution of amphetamine drugs with an isotope internal standard content of 2000 pg / filter was prepared using chromatographically pure methanol as the solvent, and the concentration gradients were 30, 50, 100, 200, 1000, 2000, 4000, 10000, and 20000 pg / filter in sequence. It was detected and analyzed by high performance liquid chromatography tandem triple quadrupole mass spectrometry, and the standard working curve was plotted according to its response intensity and concentration (pg / filter). X and Y were the drug concentration and the ratio of the drug peak area to the isotope internal standard peak area, respectively. The detection limit was calculated by three times the signal-to-noise ratio. The detection limits and linear information of 5 amphetamine drugs are shown in Table 1.

[0118] Step S2-2: The extract was detected by high performance liquid chromatography tandem triple quadrupole mass spectrometry, and the concentration of amphetamine drugs in it was calculated according to the standard curve equation. Since it is difficult to obtain positive samples of amphetamine drugs such as AMP, METH, MDA, and MDMA, EPH was used as a model drug for research. The detection results of EPH in exhaled samples are shown in Table 3.

[0119] Table 3 Detection results of EPH in exhaled samples

[0120]

[0121] As shown in Table 3, the exhalation analysis method formed by combining the exhalation collection device equipped with sponge material with high performance liquid chromatography tandem triple quadrupole mass spectrometry can successfully detect EPH from human exhalation, with the content ranging from 261.6±92.2% to 2219.9±84.2 pg / filter. These results indicate that the above exhalation analysis method based on the exhalation collection device assembled with the cellulose sponge material of the present invention can be used for the detection of amphetamine drugs in actual human exhalation samples.

[0122] The above are the preferred embodiments of this application and are not used to limit the present invention. Although this application has been described in detail with reference to the examples, for those skilled in the art, they can still modify the technical solutions recorded in the foregoing examples, or perform equivalent replacements for some of the technical features. However, any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of this application shall be included within the protection scope of this application.

Claims

1. Application of an exhaled gas collection device assembled based on a cellulose sponge material in the detection of amphetamine drugs, characterized in that, The preparation method of the cellulose sponge material is as follows: Put the cellulose sponge into absolute ethanol and ultrasonically clean for the first duration, then put it into ultrapure water and ultrasonically clean for the second duration. Immediately afterwards, soak it in a sodium hydroxide solution at room temperature for the third duration. After cleaning and drying, the cellulose sponge material is obtained.

2. The application according to claim 1, characterized in that The first duration is 20 - 40 min, and the ultrasonic power is 100 - 500 W; the second duration is 20 - 40 min, and the ultrasonic power is 100 - 500 W; the third duration is 10 - 14 h, the concentration of the sodium hydroxide solution is 0.8 - 1.2 mol / L, and the volume ratio of the cellulose sponge to the sodium hydroxide solution is 0.2 - 2.

3. The application according to claim 1, characterized in that, The cellulose sponge material has pores with an irregular pore structure, including small pores, medium pores, and large pores.

4. The application according to claim 1, characterized in that, The small pore diameter of the cellulose sponge material is 138 - 160 μm, the medium pore diameter is 366 - 411 μm, and the large pore diameter is 610 - 646 μm.

5. The application according to claim 1, characterized in that, An exhaled breath collection device assembled based on the cellulose sponge material includes an intake pipe (1), an adsorption module (2), and a gas flow meter (3); The adsorption module (2) includes an air inlet (211), a first housing (221), a first support portion (231), a sponge material (24), a second support portion (232), a second housing (222), and an air outlet (212) arranged in sequence; One end of the intake pipe (1) is detachably connected to the air inlet (211) of the adsorption module (2); the first housing (221) and the second housing (222) of the adsorption module (2) are detachably connected; one end of the gas flow meter (3) is detachably connected to the air outlet (212) of the adsorption module (2); in addition, the adsorption module (2) further includes a first end cap (251) and a second end cap (252) for sealing the air inlet (211) and the air outlet (212), so that the adsorption module (2) is in an overall airtight state; The sponge material (24) is arranged between the first support portion (231) and the second support portion (232).

6. The application according to claim 5, characterized in that, The cavity volume of the adsorption module (2) is 50 to 200 cm 3 .

7. The application according to claim 5, characterized in that 1 - 5 peripheral protrusions are horizontally arranged on the outer wall of the first housing (221); 8 - 16 grooves surrounding the inner wall are longitudinally arranged on the inner wall of the second housing (222), and 1 - 5 parallel peripheral notches are arranged at the vertical connection of the grooves; the grooves are evenly divided into 3 - 5 levels, and the number of grooves in each level is 1 - 5; the first housing (221) and the second housing (222) are rotated by embedding 1 - 5 peripheral protrusions along the peripheral notches into the grooves, so that 1 - 5 peripheral protrusions and notches at the same level are fitted together, and the internal volume of the adsorption module (2) can be adjusted by controlling the amplitude of embedding 1 - 5 peripheral protrusions along the peripheral notches into the grooves; An annular groove for accommodating a sealing ring (26) is provided on the contact surface of the first housing (221) or / and the second housing (222).

8. The application according to claim 1, wherein An exhaled breath collection device assembled based on the cellulose sponge material is used to collect amphetamine drugs in exhaled breath and detect their content, including the following steps: The subject rinses the mouth with drinking water for 0.05 - 2 min and then exhales into the exhaled air collection device for 2 - 8 min; after the collection is completed, the cellulose sponge material is taken out and soaked in an organic solvent for ultrasonic elution, then the eluate is transferred to a new centrifuge tube and concentrated by nitrogen blowing under water bath conditions, and then re-dissolved with an organic solvent. The re-dissolved solution is filtered through a 0.22 μm filter membrane into a sample vial to obtain an extract; the content of amphetamine drugs in the extract is detected by high performance liquid chromatography tandem triple quadrupole mass spectrometry.

9. The application according to claim 8, wherein Before exhaled air collection, the presence and content of amphetamine drugs in the exhaled air of different subject populations are predicted according to the self-reported information of the subjects, a sponge material with a suitable size and matching adsorption performance is selected according to the prediction result, and the internal volume of the exhaled air collection device is adjusted according to the size of the sponge material.

10. The application according to claim 8, characterized in that, The content of amphetamine drugs in the exhaled air can be detected within the range of 30.0 - 20000.0 pg / filter, and the accuracy rate can reach 87.49 ± 1.12% - 98.93 ± 2.46%.

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