Functionalized composite material, expiration collection device assembled based on functionalized composite material, detection method and application

Abstract

The invention relates to the technical field of amphetamine drug detection, and particularly discloses a functional composite material, an expiration collection device assembled based on the functional composite material, a detection method and application. Wherein the functional composite material is formed by superposing and combining functional polypropylene cotton and a functional polypropylene film, the functional polypropylene cotton is obtained by modifying a polypropylene material with polydopamine and tetraethoxysilane, and the functional composite material can be assembled into the portable expiration collection device and is used for expiration collection. The invention also provides a detection method which comprises the following steps: enriching amphetamine drugs in exhaled air under the adsorption action of the functionalized composite material, then eluting the functionalized composite material, concentrating, carrying out constant volume filtration, and finally carrying out detection analysis by using high performance liquid chromatography-tandem triple quadrupole mass spectrometry. The method can be used for accurately and quickly screening the drug addicts, and is also suitable for screening the drug addicts with low drug intake and low drug concentration in expiration to pg level after long-time metabolism.

Description

[0001] This application claims priority to the Chinese patent application with application number 202411636542.8 and filing date November 15, 2024. Technical Field

[0002] The present application relates to the technical field of amphetamine drug detection, and in particular to a functional composite material, a breath collection device assembled based on the functional composite material, a detection method and an application thereof. Background Art

[0003] Amphetamine drugs include amphetamine (AMP), methamphetamine (METH), 3,4-methylenedioxyaniline (MDA), 3,4-methylenedioxyphenylamphetamine (MDMA) and ephedrine (EPH). Among them, AMP, METH, MDA and MDMA are widely abused drugs worldwide and have become the focus of attention of countries around the world. Ephedrine (EPH) is the raw material for the preparation of methamphetamine (METH), and even long-term abuse can cause dependence and addiction. Based on the principle of pharmacokinetic, blood, urine and hair are usually used as common sample types for monitoring the illegal abuse of amphetamine drugs. However, the collection of these samples has many limitations in time and space dimensions, and the collection process requires professional knowledge support. In addition, it may infringe personal privacy or cause sample adulteration.

[0004] The exhaled aerosol collection method has significant advantages such as being non-invasive, simple, rapid, and not limited by time and space, making it a very potential source of samples for amphetamine drug detection. However, the content of amphetamine drugs in exhaled aerosol after human metabolism is extremely low compared to other sample types, which makes it difficult for existing analytical methods to directly and accurately measure it. Therefore, it is particularly necessary to improve the sensitivity and selectivity of the detection method by using sample pretreatment techniques such as amphetamine drug enrichment in exhaled aerosol.

[0005] Chinese patent CN102498398B discloses a portable system for collecting samples from a subject's exhaled aerosol, aiming to detect or determine drugs in the exhaled aerosol. The invention uses solid phase extraction columns and electret membranes to collect drugs in exhaled aerosols. The drugs involved basically cover amphetamines in existing cases, thereby meeting the needs for collecting and detecting amphetamines in exhaled air. However, it is worth noting that solid phase extraction columns, as disposable consumables, have a single price of tens or even hundreds of yuan, which is costly. The electret membrane not only loses its charge easily, but also lacks adsorption selectivity for amphetamines. It can be seen that it is of vital importance to explore an adsorbent material that is inexpensive and has good selective adsorption for amphetamines. Summary of the invention

[0006] In view of this, the purpose of the present application is to provide a functional composite material and a breath collection device and a detection method and application assembled based on the functional composite material, so as to solve the problem that the existing adsorption materials are expensive and difficult to use for low concentration detection.

[0007] In order to achieve the above technical purpose, the present application provides a functional composite material, characterized in that it is composed of a stacked combination of functionalized polypropylene cotton and a functionalized polypropylene film;

[0008] The preparation method of the functional composite material comprises the following specific steps:

[0009] Step S1, placing polypropylene cotton and / or polypropylene membrane in a first mixed solution containing Tris-HCl buffer, dopamine solution and sodium periodate solution, soaking for a first period of time, washing and drying to obtain polydopamine-modified polypropylene cotton and / or polypropylene membrane;

[0010] Step S2, adding tetraethoxysilane dropwise to a mixed solution of ethanol, water and ammonia water to form a second mixed solution, placing polydopamine-modified polypropylene cotton and / or polypropylene film in the second mixed solution, and soaking for a second period of time to obtain functionalized polypropylene cotton and / or polypropylene film;

[0011] Step S3, stacking and combining the functionalized polypropylene cotton and the functionalized polypropylene film to obtain a functionalized composite material.

[0012] Furthermore, the first mixed solution is composed of Tris-HCl buffer, dopamine solution, and sodium periodate solution in a volume ratio of (40~50): (4~6): (0.4~0.6); the second mixed solution is composed of anhydrous ethanol, ultrapure water, ammonia water, and tetraethoxysilane in a volume ratio of (40~60): (3~4): (0.2~1): (8~12).

[0013] Furthermore, the functional composite material is composed of a plurality of layers of functional polypropylene cotton and a layer of functional polypropylene film stacked together.

[0014] Furthermore, the functional composite material is composed of three layers of functional polypropylene cotton and one layer of functional polypropylene film.

[0015] The present application provides an application of a functional composite material for adsorbing amphetamine drugs.

[0016] The present application provides an exhaled breath collection device assembled based on functional composite materials, comprising an air intake pipe 1, an adsorption module 2,

[0017] The adsorption module 2 comprises an air inlet 211, a first shell 221, a first support portion 231, a functional composite material (24), a second support portion 232, a second shell 222, and an air outlet 212, which are arranged in sequence;

[0018] The air inlet 211 of the adsorption module 2 is detachably connected to one end of the air inlet pipe 1; the first shell 221 is detachably connected to the second shell 222; the adsorption module 2 also includes a first end cover 251 and a second end cover 252, which are used to seal the air inlet 211 and the air outlet 212 so that the adsorption module 2 is in a closed state;

[0019] The functionalized composite material 24 is disposed between the first supporting portion 231 and the second supporting portion 232 .

[0020] Furthermore, the cavity volume of the adsorption module 2 is 4~20cm 3 .

[0021] Furthermore, a plurality of peripheral protrusions are horizontally arranged along the outer wall of the first shell 221; a plurality of grooves surrounding the inner wall and a plurality of parallel peripheral notches vertically connecting the grooves are longitudinally arranged along the inner wall of the second shell 222; the first shell 221 and the second shell 222 are embedded and rotated along the grooves through a plurality of peripheral protrusions, so that a plurality of peripheral protrusions and peripheral notches at the same level are interlocked to achieve buckling, and the cavity volume of the adsorption module 2 is adjusted by controlling the embedding amplitude of the plurality of peripheral protrusions along the grooves.

[0022] Furthermore, a contact surface of the first shell 221 and / or the second shell 222 is provided with an annular groove for accommodating the sealing ring 26 .

[0023] The present application provides a detection method based on an exhaled breath collection device, which uses an exhaled breath collection device to collect exhaled breath. The detection method is as follows:

[0024] Step S1, breath collection: the subject rinses his mouth with water for 0.1 to 1 minute, then exhales into the breath collection device for 4 to 6 minutes, and after exhalation, the adsorption module is sealed with an end cap;

[0025] Step S2, sample pretreatment: taking out the functionalized composite material in the adsorption module and immersing it in an organic solvent for ultrasonication, taking the liquid portion after the ultrasonication, blowing and concentrating it with liquid nitrogen, then adding an organic solvent for oscillation to redissolve it to obtain a reconstituted solution, and filtering the reconstituted solution through a 0.22 μm filter membrane to obtain an extract;

[0026] Step S3, sample detection: HPLC-MS / MS is used to detect the content of amphetamine drugs in the extract.

[0027] Furthermore, before performing the breath collection operation, the content of amphetamine drugs in the breath of different test subjects is predicted, and functional composite materials with different adsorption properties are selected based on the prediction results. The cavity volume of the adsorption module is adjusted according to the size of the functional composite materials with different adsorption properties, so as to achieve the purpose of saving functional composite materials.

[0028] In summary, the present application provides a functional composite material and an exhaled breath collection device and a detection method and application assembled based on the functional composite material. Among them, the functional composite material is a functionalized polypropylene cotton obtained by modifying the polypropylene material with polydopamine and tetraethoxysilane and a functionalized polypropylene film, which has a good selective adsorption capacity for amphetamine drugs. Compared with the prior art, the functionalized composite material has the advantages of simple preparation and low price. At the same time, the functionalized composite material can be assembled into a portable exhaled breath collection device for exhaled breath collection. The present application also provides a detection method based on an exhaled breath collection device. During the exhaled breath collection process, the functionalized composite material is enriched with amphetamine drugs in the exhaled breath by adsorption, and then the functionalized composite material is eluted and concentrated, and then filtered at a constant volume, and finally the content of amphetamine drugs is detected and analyzed using a high performance liquid chromatography-tandem triple quadrupole mass spectrometry. The above method can realize accurate and rapid detection of amphetamine drugs in exhaled breath, and then efficiently complete the screening of drug addicts. Compared with the existing technology, the detection method proposed in this application can effectively solve the problem of low-concentration detection. It is especially suitable for drug addicts who have a small drug intake and a long period of metabolism, with the drug concentration in their breath as low as pg level, thereby reducing missed detections due to detection limitations. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0030] Figure 1 is the attenuated total reflection infrared image of the functionalized composite material prepared in Example 3;

[0031] Figure 2 is a schematic structural diagram of an exhaled breath collection device assembled based on a functional composite material provided in Example 5;

[0032] Figure 3 This is a physical picture of the components and the whole of the breath collection device assembled based on the functional composite material provided in Example 5;

[0033] Figure 4The adsorption of amphetamine drugs by the functionalized polypropylene materials provided in Examples 7 to 8 and Comparative Examples 1 to 4 under the conditions of simulated exhalation at different flow rates;

[0034] Figure numerals: 1, air inlet pipe; 2, adsorption module; 211, air inlet; 212, air outlet; 221, first shell; 222, second shell; 231, first support part; 232, second support part; 24, functional composite material; 251, first end cover; 252, second end cover; 26, sealing ring. DETAILED DESCRIPTION

[0035] The technical solutions of the embodiments of the present application will be described clearly and completely below in conjunction with the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the specification of the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection requested by the present application.

[0036] In the description of the present application, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicating the orientation or positional relationship, are based on the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the present application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present application. In addition, the terms "first", "second", and "third" are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance.

[0037] Unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in this application can be understood according to specific circumstances.

[0038] The sources of all raw materials in the present invention are not particularly limited and can be purchased from the market or prepared according to conventional methods known to those skilled in the art.

[0039] The embodiment of the present invention provides a functional composite material, which is composed of a functionalized polypropylene cotton and a functionalized polypropylene film stacked together;

[0040] The preparation method of the functional composite material comprises the following specific steps:

[0041] Step S1, placing polypropylene cotton and / or polypropylene membrane in a first mixed solution containing Tris-HCl buffer, dopamine solution and sodium periodate solution, soaking for a first period of time, washing and drying to obtain polydopamine-modified polypropylene cotton and / or polypropylene membrane;

[0042] Step S2, adding tetraethoxysilane dropwise to a mixed solution of ethanol, water and ammonia water to form a second mixed solution, placing polydopamine-modified polypropylene cotton and / or polypropylene film in the second mixed solution, and soaking for a second period of time to obtain functionalized polypropylene cotton and / or polypropylene film;

[0043] Step S3, stacking and combining the functionalized polypropylene cotton and the functionalized polypropylene film to obtain a functionalized composite material.

[0044] Specifically, the thickness of the polypropylene cotton is 2.53 mm, the thickness of the polypropylene film is 0.36 mm, and the polypropylene cotton and the polypropylene film are cut into cylinders with a diameter of 1.5-8 cm before the experiment; the concentration of Tris-HCl buffer is 0.05 M, and the pH is 8.5; the concentration of the dopamine solution is 20 mg / mL; the concentration of the sodium periodate solution is 0.002 M; in step S3, the stirring rate is 300-400 r / min; the first time length is 12-36 h; and the second time length is 12-36 h.

[0045] In some embodiments, the first mixed solution is composed of Tris-HCl buffer, dopamine solution, and sodium periodate solution in a volume ratio of (40-50): (4-6): (0.4-0.6); the second mixed solution is composed of anhydrous ethanol, ultrapure water, ammonia water, and tetraethoxysilane in a volume ratio of (40-60): (3-4): (0.2-1): (8-12).

[0046] Preferably, the volume ratio of Tris-HCl buffer, dopamine solution and sodium periodate solution is 45:5:0.5; the volume ratio of anhydrous ethanol, water, ammonia water and tetraethoxysilane is 50:3.6:0.5:10; and the polypropylene cotton and polypropylene film are cut into cylinders with a diameter of 4.5 cm.

[0047] In some embodiments, the functionalized composite material is composed of a plurality of layers of functionalized polypropylene cotton and a layer of functionalized polypropylene film.

[0048] More preferably, the functional composite material is composed of three layers of functional polypropylene cotton and one layer of functional polypropylene film stacked together.

[0049] The embodiment of the present invention provides an application of a functional composite material for adsorbing amphetamine drugs, specifically, for selectively adsorbing amphetamine drugs in gas and solution.

[0050] See also Figure 2 The embodiment of the present application provides a breath collection device assembled based on a functional composite material, including an air intake pipe 1 and an adsorption module 2.

[0051] The adsorption module 2 includes an air inlet 211, a first shell 221, a first support portion 231, a functional composite material 24, a second support portion 232, a second shell 222, and an air outlet 212, which are arranged in sequence;

[0052] The air inlet 211 of the adsorption module 2 is detachably connected to one end of the air inlet pipe 1; the first shell 221 is detachably connected to the second shell 222; the adsorption module 2 also includes a first end cover 251 and a second end cover 252, which are used to seal the air inlet 211 and the air outlet 212 to put the adsorption module 2 in a closed state; the functionalized composite material 24 is arranged between the first support portion 231 and the second support portion 232.

[0053] Specifically, the mouthpiece is in the shape of a flat duckbill.

[0054] It should be noted that Figure 3 The actual picture of the components and the whole of the breath collection device. The breath collection device assembled with the functional composite material provided in the embodiment of the present invention has the characteristics of convenient and fast collection, and will not cause invasive damage to the person being tested during the collection process, which greatly improves the comfort and acceptance of the person being tested. At the same time, the convenient and fast collection characteristics ensure the efficiency of the detection process.

[0055] Specifically, the first support portion 231 and the second support portion 232 are both formed by cross-arranged ribs being fixedly connected, and the second support portion 232 is provided with a circular baffle for changing the flow path of exhalation.

[0056] It should be noted that a circular baffle is provided in the cavity. The presence of the circular baffle changes the airflow path and flow field distribution in the cavity, making the movement trajectory of the exhaled aerosol in the cavity more complicated and prolonging the residence time of the exhaled aerosol, which can significantly increase the contact probability between the exhaled aerosol and the material, thereby effectively improving the adsorption performance of the material.

[0057] In some embodiments, the cavity volume of the adsorption module 2 is 4-20 cm 3 .

[0058] In some embodiments, a plurality of peripheral protrusions are horizontally arranged along the outer wall of the first shell 221; a plurality of grooves surrounding the inner wall and a plurality of parallel peripheral notches vertically connecting the grooves are longitudinally arranged along the inner wall of the second shell 222; the first shell 221 and the second shell 222 are embedded and rotated along the grooves through a plurality of peripheral protrusions, so that a plurality of peripheral protrusions and peripheral notches at the same level are interlocked to achieve buckling, and the cavity volume of the adsorption module 2 is adjusted by controlling the embedding amplitude of the plurality of peripheral protrusions along the grooves.

[0059] It should be noted that the breath collection device has strong internal compatibility and can adjust the cavity volume of the adsorption module according to the functional composite materials of different thicknesses.

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

[0061] The present application provides a detection method based on an exhaled breath collection device, which uses an exhaled breath collection device to collect exhaled breath. The detection method is as follows:

[0062] Step S1, breath collection: the subject rinses his mouth with water for 0.1 to 1 minute, then exhales into the breath collection device for 4 to 6 minutes, and after exhalation, the adsorption module is sealed with an end cap;

[0063] Step S2, sample pretreatment: taking out the functionalized composite material in the adsorption module and immersing it in an organic solvent for ultrasonication, taking the liquid portion after the ultrasonication, blowing and concentrating it with liquid nitrogen, then adding an organic solvent for oscillation to redissolve it to obtain a reconstituted solution, and filtering the reconstituted solution through a 0.22 μm filter membrane to obtain an extract;

[0064] Step S3, sample detection: high performance liquid chromatography tandem triple quadrupole mass spectrometry (HPLC-MS / MS) is used to detect the content of amphetamine drugs in the extract.

[0065] In some embodiments, before performing the breath collection operation, the content of amphetamine drugs in the breath of different test subjects is predicted, and functionalized composite materials with different adsorption properties are selected based on the prediction results. The cavity volume of the adsorption module is adjusted according to the size of the functionalized composite materials with different adsorption properties to achieve the purpose of saving functionalized composite materials.

[0066] Specifically, the parent of amphetamine drugs is an amphetamine structure, including one or more of AMP, METH, MDA, MDMA, EPH, p-hydroxymethamphetamine, p-methoxymethamphetamine, 4-methylthioamphetamine, 3,4-methylenedioxyethylamphetamine, 3-methoxy-4,5-methylenedioxymethamphetamine and dimethoxyethylamphetamine; wherein, amphetamine drug information and mass spectrometry analysis parameters are shown in Tables 1-2.

[0067] Table 1. Basic information of amphetamine drugs

[0068]

[0069] Table 2. Mass spectrometry analysis parameters of amphetamines

[0070]

[0071] The applicant further provides the following reference specific embodiments to describe the present invention. It should be noted that these embodiments are merely illustrative and do not limit the present invention in any way.

[0072] Example 1

[0073] This embodiment provides a method for preparing a functional composite material, and the specific steps are as follows:

[0074] Step S1, cutting polypropylene cotton with a thickness of 2.53 mm and polypropylene film with a thickness of 0.36 mm into cylinders with a diameter of 1.5 cm, and then placing them in 200 mL of anhydrous ethanol and ultrapure water for ultrasonic cleaning for 10 minutes. After the cleaning is completed, the polypropylene cotton and the polypropylene film are immersed in 200 mL of anhydrous ethanol to obtain spare polypropylene cotton and / or polypropylene film;

[0075] Step S2, add 40 mL of Tris-HCl buffer (0.05 M, pH 8.5), 4 mL of dopamine solution (20 mg / mL), and 0.4 mL of sodium periodate solution (0.002 M) into the culture dish, stir evenly, put the polypropylene cotton and polypropylene film prepared after the treatment in step S1 into the culture dish and soak them for 12 hours, take them out after soaking, wash them with ultrapure water, and dry them to obtain a polydopamine modified material;

[0076] Step S3, adding 40 mL of anhydrous ethanol, 3 mL of ultrapure water and 0.2 mL of ammonia water into a beaker, stirring continuously at 300 r / min under room temperature, and adding 8 mL of tetraethoxysilane dropwise, placing the polydopamine modified material into the beaker and soaking it for 12 hours, taking it out after soaking, washing it with ultrapure water, and drying it to obtain functionalized polypropylene cotton and functionalized polypropylene film;

[0077] Step S4, stacking and combining the functionalized polypropylene cotton and the functionalized polypropylene film to obtain a functionalized composite material.

[0078] Example 2

[0079] This embodiment provides a method for preparing a functional composite material, and the specific steps are as follows:

[0080] Step S1, cutting polypropylene cotton with a thickness of 2.53 mm and polypropylene film with a thickness of 0.36 mm into cylinders with a diameter of 8 cm, and placing them in 400 mL of anhydrous ethanol and 400 mL of ultrapure water for ultrasonic cleaning for 40 min respectively. After the cleaning is completed, the polypropylene material is immersed in 400 mL of anhydrous ethanol to obtain spare polypropylene cotton and / or polypropylene film;

[0081] Step S2, add 50 mL of Tris-HCl buffer (0.05 M, pH 8.5), 6 mL of dopamine solution (20 mg / mL), and 0.6 mL of sodium periodate solution (0.002 M) into the culture dish, stir evenly, put the polypropylene cotton and polypropylene film prepared after the treatment in step S1 into the culture dish and soak for 36 hours, take out after soaking, wash with ultrapure water, and dry to obtain a polydopamine modified material;

[0082] Step S3, add 60 mL of anhydrous ethanol, 4 mL of ultrapure water and 1 mL of ammonia water into a beaker, continue stirring at 400 r / min under room temperature, and add 12 mL of tetraethoxysilane dropwise, put the polydopamine modified material into the beaker and soak it for 36 hours, take it out after soaking, wash it with ultrapure water, and dry it to obtain functionalized polypropylene cotton and functionalized polypropylene film;

[0083] Step S4, stacking and combining the functionalized polypropylene cotton and the functionalized polypropylene film to obtain a functionalized composite material.

[0084] Example 3

[0085] This embodiment provides a method for preparing a functional composite material, and the specific steps are as follows:

[0086] Step S1, cutting polypropylene cotton with a thickness of 2.53 mm and polypropylene film with a thickness of 0.36 mm into cylinders with a diameter of 4.5 cm, and placing them in 300 mL of anhydrous ethanol and 300 mL of ultrapure water for ultrasonic cleaning for 30 minutes respectively. After the cleaning is completed, the polypropylene material is immersed in 300 mL of anhydrous ethanol to obtain standby polypropylene cotton and / or polypropylene film;

[0087] Step S2, add 45 mL of Tris-HCl buffer (0.05 M, pH 8.5), 5 mL of dopamine solution (20 mg / mL), and 0.5 mL of sodium periodate solution (0.002 M) into the culture dish, stir evenly, put the reserved polypropylene material treated in step S1 into the culture dish and soak it for 24 hours, take it out after soaking, wash it with ultrapure water, and dry it to obtain a polydopamine modified material;

[0088] Step S3, adding 50 mL of anhydrous ethanol, 3.6 mL of ultrapure water and 0.5 mL of ammonia water into a beaker, stirring continuously at 350 r / min under room temperature, and adding 10 mL of tetraethoxysilane dropwise, placing the polydopamine modified material into the beaker and soaking it for 24 hours, taking it out after soaking, washing it with ultrapure water, and drying it to obtain functionalized polypropylene cotton and functionalized polypropylene film;

[0089] Step S4, stacking and combining the functionalized polypropylene cotton and the functionalized polypropylene film to obtain a functionalized composite material.

[0090] Characterization: The functionalized composite material prepared in Example 3 was characterized by attenuated total reflection infrared, see Figure 1 .from Figure 1 It can be seen that compared with the initial polypropylene material (polypropylene cotton or polypropylene film), the functionalized composite material A broad band appears in the wide frequency range, which is attributed to the stretching vibration of hydroxyl group and NH; another broad absorption band appears at , attributed to the C=C resonance vibration in the dopamine aromatic ring, the bending vibration of catechol and NH; in addition, An absorption peak appears at , which is attributed to the stretching vibration of the Si-O bond; at the same time, the characteristic absorption peak in the infrared spectrum matches the expected functional group and chemical bond vibration of the modified material, indicating that new functional groups and chemical bonds are introduced on the surface or inside of the polypropylene material, and the modification of the polypropylene material is successful.

[0091] Example 4

[0092] An exhaled breath collection device assembled based on functional composite materials, comprising an air intake pipe 1, an adsorption module 2,

[0093] The adsorption module 2 includes an air inlet 211, a first shell 221, a first support portion 231, a functional composite material 24, a second support portion 232, a second shell 222, and an air outlet 212, which are arranged in sequence;

[0094] The air inlet 211 of the adsorption module 2 is detachably connected to one end of the air inlet pipe 1, and the other end of the air inlet pipe 1 is in a flat duckbill shape; a plurality of peripheral protrusions are horizontally arranged along the outer wall of the first shell 221; a plurality of grooves surrounding the inner wall are longitudinally arranged along the inner wall of the second shell 222, and a plurality of parallel peripheral notches vertically connected to the grooves; the first shell 221 and the second shell 222 are embedded and rotated along the grooves through the plurality of peripheral protrusions, so that the plurality of peripheral protrusions and peripheral notches at the same level are mutually embedded to achieve buckling, and the volume of the cavity of the adsorption module 2 is adjusted by controlling the embedding amplitude of the plurality of peripheral protrusions along the grooves; ; The contact surface of the first shell 221 or the second shell 222 is provided with an annular groove for accommodating a sealing ring 26 made of nitrile rubber; the first support portion 231 and the second support portion 232 are both fixedly connected by cross-arranged ribs, and the second support portion 232 is provided with a circular baffle for changing the flow path of exhaled air; the adsorption module 2 also includes a first end cover 251 and a second end cover 252, which are used to seal the air inlet 211 and the air outlet 212 after the exhaled air collection is completed to put the adsorption module 2 in a closed state; the functionalized composite material 24 is arranged between the first support portion 231 and the second support portion 232.

[0095] Example 5

[0096] The present application provides a detection method based on a breath collection device, comprising the following steps:

[0097] Step S1, breath collection: connect the breath collection device prepared in Example 4 to the breath simulation generating device, prepare positive breath of amphetamine drugs at flow rates of 8.0 and 20.0 L / min, use the collection device to collect simulated breath for 5 minutes, and record the mass of the breath collection device before and after sampling; wherein, the functionalized composite material in the breath collection device is composed of the functionalized polypropylene cotton and the functionalized polypropylene film prepared in Examples 1 to 3 stacked and combined;

[0098] Step S2, sample pretreatment: after sampling, open the breath collection device, take out the functionalized composite material, use 5 mL of methanol to ultrasonically extract the liquid part to obtain an organic solution containing amphetamine drugs, blow the organic solution with nitrogen until it is almost dry, add 1 mL of methanol and oscillate at 3000 r / min for 0.5 min to obtain a re-solution, and filter the re-solution with a 0.22 μm disposable filter membrane to obtain an extract.

[0099] Step S3, sample testing:

[0100] Step S3-1: Prepare standard products and prepare standard curve: Use methanol (chromatographic grade) as solvent to prepare EPH standard solution containing 2000 pg / filter isotope internal standard, and set the concentration gradient of 40, 100, 200, 1000, 2000, 4000, 10000, 20000 pg / filter of standard products in sequence according to the EPH standard solution, and use HPLC-MS / MS for detection and analysis. Draw the standard working curve according to its response intensity and concentration (pg / filter), where Y is the ratio of the peak area of ​​the EPH target to the peak area of ​​the EPH isotope internal standard, and X is the concentration. The equation of the obtained standard working curve is: Y=0.17449X+0.02686;

[0101] Step S3-2: Detection and calculation of the concentration of amphetamine drugs in the extract: The extract is detected using HPLC-MS / MS, and the concentration of amphetamine drugs in the extract is calculated based on the detection intensity and the standard curve equation.

[0102] The test conditions are as follows:

[0103] Liquid phase conditions: SHIMADZU UFLCXR liquid chromatograph, chromatographic column is Kinetex Biphenyl column (100mm×3.0mm, 2.6μm), mobile phase A is ammonium acetate aqueous solution (0.015M) containing 0.1% by volume of formic acid, mobile phase B is acetonitrile containing 0.1% by volume of formic acid, flow rate is 0.4mL / min, column temperature is 40℃, injection volume is 8μL;

[0104] Mass spectrometry conditions: AB SCIEX API 4500 triple quadrupole mass spectrometer, ion source: electrospray ionization source ESI; scanning mode: positive ion mode, detection mode: multiple reaction detection MRM; ion source temperature: 550 °C; curtain gas (CUR), nebulizing gas (GS1), and heating gas (GS2) were 30 psi, 40 psi, and 55 psi, respectively.

[0105] According to the above detection method, the breath collection device based on the functional composite material prepared in Examples 1 to 3 was subjected to a spike recovery experiment. The detection results are shown in Table 3 and Figure 4 As shown in Table 3, within the range of 40.0~20000.0pg / filter, EPH shows a good linear relationship, its linear correlation coefficient R² reaches 0.9975, and the detection limit is 5.2pg / filter. Therefore, the above method can detect EPH in exhaled air; at the same time, the recovery rate of EPH in exhaled air by the functionalized composite material prepared in Example 3 is at the highest level, up to 90.48%, indicating that the functionalized composite material prepared in Example 3 has the best adsorption performance for EPH in exhaled air and can more effectively capture amphetamine drugs in exhaled air.

[0106] Table 3. Detection limit, linear range and spike recovery of EPH

[0107]

[0108] Example 6

[0109] The difference from Example 5 is that the functional composite material is composed of two layers of functional polypropylene cotton placed in front and one layer of functional polypropylene film placed in the back.

[0110] Example 7

[0111] The difference from Example 5 is that the functional composite material is composed of three layers of functional polypropylene cotton placed in front and one layer of functional polypropylene film placed in the back.

[0112] Comparative Example 1

[0113] The difference from Example 5 is that the functionalized composite material is a layer of functionalized polypropylene film.

[0114] Comparative Example 2

[0115] The difference from Example 5 is that the functionalized composite material is a three-layer functionalized polypropylene film.

[0116] Comparative Example 3

[0117] The difference from Example 5 is that the functionalized composite material is 4 layers of functionalized polypropylene films.

[0118] Comparative Example 4

[0119] The difference from Example 5 is that the functionalized composite material is one layer of functionalized polypropylene cotton.

[0120] Comparative Example 5

[0121] The difference from Example 5 is that the functionalized composite material is three layers of functionalized polypropylene cotton.

[0122] Comparative Example 6

[0123] The difference from Example 5 is that the functionalized composite material is 4 layers of functionalized polypropylene cotton.

[0124] For the test results of Examples 6-7 and Comparative Examples 1-6, see Figure 4 .like Figure 4 As shown in a, as the number of functionalized polypropylene membrane layers increases from one to three, the adsorption rate shows an upward trend, reaching 56.36±1.68%~62.57±1.24% when there are three layers (see Figure 4 a); As the number of functionalized polypropylene cotton layers increases from one to three, the adsorption rate shows an upward trend, reaching 66.30±1.18%~74.53±1.41% when there are three layers (refer to Figure 4 b) The above data show that the adsorption performance of the material can be significantly improved by stacking functionalized polypropylene cotton / membrane layers within a certain range.

[0125] However, the adsorption rate of the four-layer functionalized polypropylene film provided in Comparative Example 3 is only 56.49±1.71%~62.82±2.26%, and the adsorption rate of the four-layer functionalized polypropylene cotton provided in Comparative Example 6 is 66.62±1.20%~75.29±1.45%. The above data show that the adsorption amount cannot be significantly increased by continuously stacking layers of functionalized polypropylene cotton or functionalized polypropylene membrane. On the contrary, it will enhance the exhalation resistance, which is not conducive to the enrichment of amphetamine drugs in exhaled breath collection; therefore, the adsorption effect cannot be simply improved by increasing the number of layers of functionalized polypropylene cotton / membrane. Based on the above conclusions, the experimenters combined the physical properties of functionalized polypropylene cotton and functionalized polypropylene membrane to study the hybrid combination of multiple layers of functionalized polypropylene cotton plus a layer of functionalized polypropylene membrane, including two layers of functionalized polypropylene cotton plus a layer of functionalized polypropylene membrane and three layers of functionalized polypropylene cotton plus a layer of functionalized polypropylene membrane. The test results can be found in Figure 4c and 4d, Examples 6-7 show that the adsorption rates of two layers of functionalized polypropylene cotton plus one layer of functionalized polypropylene film and three layers of functionalized polypropylene cotton plus one layer of functionalized polypropylene film are 72.34±1.20%~83.59±1.27% and 82.56±1.42%~94.24±1.68%, respectively. The results show that there is a synergistic effect after the combination of functionalized polypropylene cotton and functionalized polypropylene film, and the adsorption amount of the hybrid combination is much higher than the adsorption amount of functionalized polypropylene cotton or functionalized polypropylene film alone; at the same time, three layers of functionalized polypropylene cotton plus one layer of functionalized polypropylene film is a functional composite material with the best adsorption performance, which can achieve efficient adsorption of amphetamine drugs in simulated exhaled breath and is more suitable for capturing amphetamine drugs in exhaled breath.

[0126] Example 8

[0127] An application of a detection method based on a breath collection device, the specific steps are as follows:

[0128] Step S1, breath collection: the subject rinses his mouth with water for 0.5 min, then exhales into the collection device for 5 min. After the exhalation is completed, the adsorption module is sealed with an end cover to obtain a breath sample; wherein the functionalized composite material in the breath collection device is prepared by Example 7.

[0129] Step S2, sample pretreatment: open the breath collection device, take out the functionalized composite material, use 5 mL of methanol to ultrasonically extract the liquid part to obtain an organic solution containing amphetamine drugs, blow the organic solution with nitrogen until it is almost dry, add 1 mL of methanol and oscillate at 3000 r / min for 0.5 min to obtain a re-solution, and filter the re-solution with a 0.22 μm disposable filter membrane to obtain an extract.

[0130] Step S3-1: Prepare standard products and prepare standard curve: Use methanol (chromatographic grade) as solvent to prepare EPH standard solution containing 2000 pg / filter isotope internal standard, and set the concentration gradient of 40, 100, 200, 1000, 2000, 4000, 10000, 20000 pg / filter of standard products in sequence according to the EPH standard solution, and use HPLC-MS / MS for detection and analysis. Draw the standard working curve according to its response intensity and concentration (pg / filter), where Y is the ratio of the peak area of ​​the EPH target to the peak area of ​​the EPH isotope internal standard, and X is the concentration. The equation of the obtained standard working curve is: Y=0.17449X+0.02686;

[0131] Step S3-2: Detection and calculation of the concentration of amphetamine drugs in the extract: The extract was detected using HPLC-MS / MS, and the concentration of amphetamine drugs in the extract was calculated based on the detection intensity and the standard curve equation. The detection results of EPH in the sample are shown in Table 4.

[0132] Table 4. Detection results of EPH in breath samples

[0133]

[0134] It can be seen from Table 4 that by collecting breath samples using a collection device based on functionalized composite materials and conducting detection using LC-MS / MS technology, EPH can be detected from actual breath samples, and the detected EPH concentration range is between 421.5±29.1 and 1576.8±49.6 pg / filter. This result further shows that the above detection method is feasible for the detection of amphetamine drugs in actual breath, and provides a strong basis for the application of such drugs in the field of actual breath detection.

[0135] In summary, the solution of the present invention has the following beneficial effects:

[0136] (I) The present invention provides a functional composite material, which is composed of polypropylene cotton and polypropylene membrane functionally modified by tetraethoxysilane and polydopamine and combined and optimized to obtain the ability to adsorb amphetamine drugs in exhaled breath. Compared with the existing technology, the functional composite material has the advantages of simple preparation and low price; at the same time, the functional composite material of the present invention uses a soft membrane-based material as a matrix material, has the property of being rollable, and can change the area and shape at will, which makes up for the problem that the existing solid phase extraction materials are rigid and cannot be deformed and the operation is relatively complicated.

[0137] (II) The present invention also provides a portable breath collection device assembled based on functional composite materials. The device does not cause invasive damage to the person being tested and can collect samples quickly and easily. At the same time, the volume of its cavity is adjustable and can accommodate adsorption materials of different thicknesses, with strong material compatibility. In addition, a circular baffle is provided in the cavity, which can effectively increase the contact probability between the exhaled aerosol and the material, thereby improving the collection and enrichment performance of the breath device.

[0138] (III) The present invention provides a portable detection method for a breath collection device assembled based on functional composite materials. The method has simple operation steps, short analysis time, and accurate results. It can achieve accurate and rapid detection of amphetamine drugs in breath, and thus efficiently complete the screening of drug users. Compared with the prior art, the detection method proposed in this application effectively solves the problem of low-concentration detection, and is particularly suitable for drug users who have a low drug intake and have undergone long-term metabolism, with a drug concentration in their breath as low as pg level, reducing missed detections due to detection limitations.

[0139] The above are only preferred embodiments of the present application and are not intended to limit the present invention. Although the present application has been described in detail with reference to the examples, those skilled in the art can still modify the technical solutions recorded in the aforementioned examples or make equivalent substitutions for some of the technical features therein. However, any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.

Claims

1. A functional composite material, characterized in that: It is composed of functionalized polypropylene cotton and functionalized polypropylene film. The preparation method of the functional composite material comprises the following specific steps: Step S1, placing polypropylene cotton and / or polypropylene membrane in a first mixed solution containing Tris-HCl buffer, dopamine solution and sodium periodate solution, soaking for a first period of time, washing and drying to obtain polydopamine-modified polypropylene cotton and / or polypropylene membrane; Step S2, adding tetraethoxysilane dropwise to a mixed solution of ethanol, water and ammonia water to form a second mixed solution, placing polydopamine-modified polypropylene cotton and / or polypropylene film in the second mixed solution, and soaking for a second period of time to obtain functionalized polypropylene cotton and / or polypropylene film; Step S3, stacking and combining the functionalized polypropylene cotton and the functionalized polypropylene film to obtain a functionalized composite material.

2. The functionalized composite material according to claim 1, characterized in that: The first mixed solution is composed of Tris-HCl buffer, dopamine solution, and sodium periodate solution in a volume ratio of (40-50): (4-6): (0.4-0.6); the second mixed solution is composed of anhydrous ethanol, ultrapure water, ammonia water, and tetraethoxysilane in a volume ratio of (40-60): (3-4): (0.2-1): (8-12).

3. The functionalized composite material according to claim 1, characterized in that: The functional composite material is formed by stacking and combining multiple layers of functional polypropylene cotton and a layer of functional polypropylene film.

4. The functionalized composite material according to claim 3, characterized in that: The functional composite material is composed of three layers of functional polypropylene cotton and one layer of functional polypropylene film.

5. An application of the functionalized composite material according to any one of claims 1 to 4, characterized in that: Used to adsorb amphetamine drugs.

6. A breath collection device assembled based on functional composite materials, characterized in that: It comprises an air intake pipe (1), an adsorption module (2), The adsorption module (2) comprises an air inlet (211), a first shell (221), a first support portion (231), the functional composite material (24) according to any one of claims 1 to 4, a second support portion (232), a second shell (222), and an air outlet (212), which are arranged in sequence; The air inlet (211) of the adsorption module (2) is detachably connected to one end of the air inlet pipe (1); the first shell (221) is detachably connected to the second shell (222); the adsorption module (2) further comprises a first end cover (251) and a second end cover (252) for sealing the air inlet (211) and the air outlet (212) so that the adsorption module (2) is in a sealed state; The functionalized composite material (24) is arranged between the first supporting portion (231) and the second supporting portion (232).

7. The breath collection device assembled based on functional composite materials according to claim 6, characterized in that: The cavity volume of the adsorption module (2) is 4 to 20 cm 3 .

8. The breath collection device assembled based on functional composite materials according to claim 7, characterized in that: A plurality of peripheral protrusions are horizontally arranged along the outer wall of the first shell (221); A plurality of grooves surrounding the inner wall are longitudinally arranged along the inner wall of the second shell (222), as well as a plurality of parallel peripheral notches vertically connected to the grooves; The first shell (221) and the second shell (222) are embedded and rotated along the groove via a plurality of peripheral protrusions, so that a plurality of peripheral protrusions and peripheral notches at the same level are interlocked with each other to achieve buckling, and the volume of the cavity of the adsorption module (2) is adjusted by controlling the embedding amplitude of the plurality of peripheral protrusions along the groove.

9. The breath collection device assembled based on functional composite materials according to claim 6, characterized in that: The contact surface of the first shell (221) or / and the second shell (222) is provided with an annular groove for accommodating a sealing ring (26).

10. A detection method based on a breath collection device, characterized in that: The breath collection device according to any one of claims 7 to 9 is used to collect breath, and the detection method is as follows: Step S1, breath collection: the subject rinses his mouth with water for 0.1 to 1 minute, then exhales into the breath collection device for 4 to 6 minutes, and after exhalation, the adsorption module is sealed with an end cap; Step S2, sample pretreatment: taking out the functionalized composite material in the adsorption module and immersing it in an organic solvent for ultrasonication, taking the liquid portion after the ultrasonication, blowing and concentrating it with liquid nitrogen, then adding an organic solvent for oscillation to redissolve it to obtain a reconstituted solution, and filtering the reconstituted solution through a 0.22 μm filter membrane to obtain an extract; Step S3, sample detection: HPLC-MS / MS is used to detect the content of amphetamine drugs in the extract.

11. The detection method based on the breath collection device according to claim 10, characterized in that: Before the breath collection operation, the content of amphetamine drugs in the breath of different test subjects is predicted, and functional composite materials with different adsorption properties are selected according to the prediction results. The cavity volume of the adsorption module is adjusted according to the size of the functional composite materials with different adsorption properties to achieve the purpose of saving functional composite materials.

Images