CN113419018B - Pretreatment method of incense sample and method for detecting various cannabinoids in incense smoke - Google Patents
Pretreatment method of incense sample and method for detecting various cannabinoids in incense smoke Download PDFInfo
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- CN113419018B CN113419018B CN202110853532.XA CN202110853532A CN113419018B CN 113419018 B CN113419018 B CN 113419018B CN 202110853532 A CN202110853532 A CN 202110853532A CN 113419018 B CN113419018 B CN 113419018B
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Abstract
The invention relates to a pretreatment method of a burning incense sample and a method for detecting various cannabinoids compounds in burning incense smoke, wherein the pretreatment method comprises the following steps: igniting the incense in a smoke collecting device, enriching and collecting smoke by using a solvent, firstly carrying out solvent phase-change purification, and then purifying by using an ethylenediamine-N-propyl silane magnetic nano adsorbing material loaded with ferroferric oxide. The method for detecting various cannabinoids in the burning incense smoke comprises the following steps: compared with the common solid phase extraction small column purification method in the literature, the detection method has the advantages that the purification effect is good, and the recovery rate is improved by 15-30%; the operation efficiency is high, the magnet can be used for adsorption separation, the pretreatment requirements of 10 cannabinoids can be met within less than 20min, the operation is simple and convenient, and the reagent consumption is low.
Description
Technical Field
The invention relates to a pretreatment method of a burning incense sample and a method for detecting various cannabinoids in burning incense smoke.
Background
Cannabinoids are mainly derived from the cannabis plant, of which Tetrahydrocannabinol (THC) has been shown to have a strong addictive effect and psychoactive properties, and are classified as "narcotics" or "drugs" in the united nations convention and in the laws of many countries. The substances have long action time, simple use, easy acquirement and continuously increased illegal abuse phenomena, and at present, cannabinoids become the largest family of new psychoactive substances.
According to the information released by the public security department, the main ways of smoking cannabis psychoactive substances include injecting and smoking smoke after ignition, and a class of incense drugs named as 'small branches' are sold in illegal markets. Lawbreakers add drugs into incense, not only use the aroma of the drugs as a cover, but also use the burning mode of the drugs for camouflage and smoking, thus increasing the difficulty of striking and supervision.
For the problem of illegal addition of cannabinoids drug substances in the incense, no appropriate and effective detection scheme exists in the current relevant standards or documents, and the relevant literature data also does not relate to a detection method for the incense and smoke thereof. In the related standard or literature data, the objects to be detected for the cannabinoids are biological detection materials such as urine, blood and hair or substrates such as food and nutriment, and the objects do not relate to the aroma burning smoke. Although the gas chromatography-mass spectrometry and the liquid chromatography-mass spectrometry used for detection can detect the components of the hemp, the adopted pretreatment methods cannot be directly used for detecting the gaseous aroma-burning smoke. And the purification methods of the related documents all use a solid phase extraction column mode, and have defects in purification adaptability and efficiency. Patent CN 109521126A "a method for determining the content of 16 polycyclic aromatic hydrocarbons in cigarette smoke by thermal desorption/gas chromatography-mass spectrometry", provides a detection method for determining cigarette smoke matrix. However, in the method, smoke is adsorbed by a Tenax-TA packing thermal desorption tube, and then the smoke is desorbed by a thermal desorption mode for detection, the cannabinoids are unstable in chemical structure under the thermal desorption condition and are easy to convert and degrade cannabinol and cannabinolic acid, and the method disclosed in the patent CN 109521126A is not suitable for detecting the cannabinoids in the smoke of the burning incense.
In view of the above, there is a need for an effective method for detecting various cannabinoids in cigarette smoke. The method has very important effects on detecting psychoactive substances such as cannabinoids and the like in the incense burning smoke, identifying drug components, evaluating drug content and further judging criminal behaviors, crimes and the like
Disclosure of Invention
The invention aims to provide a pretreatment method of a burning incense sample and an effective method for detecting various cannabinoids in burning incense smoke.
The purpose of the invention is realized by the following technical scheme:
a pretreatment method of a burning incense sample comprises the following steps: igniting the incense in a smoke collecting device, enriching and collecting smoke by using a solvent, firstly carrying out solvent phase-change purification, and then purifying by using an ethylenediamine-N-propyl silane magnetic nano adsorbing material loaded with ferroferric oxide.
A method for detecting a plurality of cannabinoids in a burning incense smoke gas comprises the following steps: igniting the incense in a smoke collecting device, enriching and collecting smoke by using a solvent, firstly carrying out solvent phase-change purification, then purifying by using an ethylenediamine-N-propyl silane magnetic nano adsorbing material loaded by ferroferric oxide, and then detecting by using a liquid phase (LC), a GC-MS, an LC-MS/MS and the like.
The method for detecting various cannabinoids compounds in the burning incense smoke comprises the following steps:
(1) preparing a ferroferric oxide-loaded ethylenediamine-N-propyl silane magnetic nano adsorption material;
(2) preparing a sample to be tested: igniting the incense to be detected in a smoke gas collecting device, enriching and collecting smoke gas by using a solvent, firstly performing solvent phase-change purification, and then purifying by using the ferroferric oxide loaded ethylenediamine-N-propyl silane magnetic nano adsorbing material prepared in the step (1) to obtain a sample to be detected;
(3) preparing a blank matrix solution: selecting a burning incense sample without cannabinoid, igniting the burning incense sample in a smoke collecting device according to the method in the step (2), enriching and collecting the burning incense sample by using a solvent, firstly performing solvent phase-change purification, and then purifying the burning incense sample by using the ferroferric oxide loaded ethylenediamine-N-propyl silane magnetic nano adsorbing material prepared in the step (1) to obtain a blank matrix solution:
(4) preparation of standard solutions: the blank matrix solution obtained in the step (3) is used for preparing 10 cannabinoid standard solutions into mixed standard solutions with the contents of 1.00 mu g/L, 2.00 mu g/L, 5.00 mu g/L, 10.00 mu g/L, 20.00 mu g/L, 50.00 mu g/L and 100.00 mu g/L.
(5) Establishing a standard curve: performing gas chromatography-mass spectrometry combined determination on the mixed standard solution obtained in the step (4) by using a gas chromatography-mass spectrometer, and drawing a standard curve by using the mass concentration of each component standard series solution as a horizontal coordinate (x) and the corresponding chromatographic peak area as a vertical coordinate (y) to obtain a corresponding linear equation;
(6) and (3) detection of a sample to be detected: carrying out gas chromatography-mass spectrometry combined determination on the sample to be detected obtained in the step (2) by using a gas chromatography-mass spectrometer; performing qualitative detection on the cannabinoid compounds in the sample to be detected according to the existence of chromatographic peaks of the sample to be detected and the cannabinoid standard substances appearing at the same retention time; and (5) according to the chromatographic peak area of the sample to be detected, and combining the linear equation obtained in the step (5), and quantitatively detecting the cannabinoid compounds in the sample to be detected.
Compared with the prior art, the invention has the advantages that:
1. compared with the common purification method of the solid phase extraction column in the literature, the method has good purification effect, and the recovery rate is improved by 15-30%; the operation efficiency is high, the magnet can be used for adsorption separation, the pretreatment requirements of 10 cannabinoids can be met within no more than 20min (the compound types can be expanded after further verification), the operation is simple and convenient, and the reagent consumption is low.
2. The pretreatment method can meet the requirements of various technical methods such as gas chromatography-mass spectrometry (GC-MS), gas chromatography-tandem mass spectrometry (GC-MS/MS), liquid chromatography-tandem mass spectrometry (LC-MS/MS) and the like on separation and detection of cannabinoids in the combustion aroma gas. The method is simple to operate, quick and effective, has reliable results, has good purification effect on the burning aroma smoke sample with complex matrix, and meets the requirements on accuracy and precision.
3. Anhydrous calcium chloride + GCB + magnetic PSA (i.e., PSA/Fe) used in the present invention3O4) The purification combination is more efficient compared with other purification modes. This is because calcium ions can form chelate precipitates with polyphenols, pigments, a part of alkaloids, etc. which may be present in the combustion flue gas, thereby effectively removing a considerable part of impurities. The effect of using GCB, PSA, graphene, GCB + PSA or GCB + graphene alone is not as good as the effect of the combination of the invention.
4. The method standard, the literature data and the detection method of the colloidal gold kit for the hemp can not be directly used for detecting the gaseous incense smoke. The pretreatment method for the incense burning smoke has good purification effect, can be combined with various technical methods for detection, and has practical verification that both the precision and the accuracy can meet the detection requirements on the cigarette burning gas.
5. The purification scheme of the magnetic nano adsorption material and the purification combination of the anhydrous calcium chloride, the GCB and the magnetic nano PSA are different from the purification modes of the matrix dispersion extraction and the solid phase extraction column which are commonly used in the prior literature data, and the magnetic nano adsorption material has the characteristics of simple and convenient operation, good purification effect and high purification efficiency, and has no relevant research report.
Drawings
FIG. 1 is a flow chart of the present invention for detecting cannabinoids in a smoky gas.
Fig. 2 is a schematic structural view of the incense smoke collecting device.
Figure 3 is a chromatogram of 10 cannabinoid standards.
FIG. 4 is a CBD standard curve of the present invention.
Fig. 5 is a THC standard curve diagram of the present invention.
Fig. 6 is a CBN calibration graph of the present invention.
Fig. 7 is a graph of the ADB-PINACA standard of the present invention.
Figure 8 is a standard graph of RCS-4 of the present invention.
FIG. 9 is a graph of the AB-CHMINACA standard of the present invention.
Fig. 10 is a standard graph of AM2201 of the present invention.
FIG. 11 is a JWH-210 standard graph of the present invention.
FIG. 12 is a graph of the MAM2201 standard of the present invention.
FIG. 13 is a CP-47979 standard curve diagram of the present invention.
FIG. 14 is a chromatogram for detection of 10 commercially available incense samples.
Description of reference numerals: the device comprises a combustion chamber 1, a flue gas collecting test tube 2, a gas flowmeter 3, a vacuum pump 4 and a pipeline 5.
Detailed Description
The invention is described in detail below with reference to the drawings and examples of the specification:
a pretreatment method of a burning incense sample comprises the following steps: igniting the incense in a smoke collecting device, enriching and collecting smoke by using a solvent, firstly carrying out solvent phase-change purification, and then purifying by using an ethylenediamine-N-propyl silane magnetic nano adsorbing material loaded with ferroferric oxide.
The ferroferric oxide-loaded ethylenediamine-N-propyl silane magnetic nano-adsorption material is prepared by the following method:
1.4g of ferroferric oxide Fe3O4Mixing the obtained product with 0.6g of ethylenediamine-N-propyl silane PSA in a 50mL centrifuge tube, adding 10mL of absolute ethyl alcohol, whirling for 30s, uniformly mixing, performing ultrasonic treatment for 1h, taking out, standing for 1h at room temperature, centrifuging for 1min at 4000r/min, discarding supernatant, placing the product at 80 ℃ for vacuum drying for 4h, taking out a screen with the aperture of 150 mu m, and obtaining the ferroferric oxide-loaded ethylenediamine-N-propyl silane magnetic nano-adsorption material.
The pretreatment method comprises the following steps:
a. sample pretreatment: weighing the incense by using a smoke collection device, igniting the incense, putting the incense into a combustion chamber, adding 20mL of methanol solution into a smoke collection test tube, starting a vacuum pump to enable the air extraction flow to be larger than 0.5L/min, extracting air for 5min after the incense is completely burnt out, and closing the vacuum pump; collecting all unburnt incense, incense ash and other combustion objects, weighing, and comparing with the weighing result before combustion to obtain the weight of the actual combustion incense;
b. purifying: taking down a flue gas collection test tube, adding 2-5 mL of saturated sodium chloride solution, uniformly mixing by swirling for 30s, centrifuging for 3min at 4000rpm, taking an organic phase solution into another test tube, adding 1-5 g of anhydrous calcium chloride, swirling for 30s, centrifuging for 3min at 4000rpm, taking a supernatant, and blowing nitrogen to be nearly dry at 40 ℃;
adding 2mL of ethyl acetate into a test tube blown to be nearly dry by nitrogen to dissolve, adding 50-100 mg of ferroferric oxide loaded ethylenediamine-N-propylsilane magnetic nano adsorption material and 100-200 mg of Graphitized Carbon Black (GCB), swirling for 30s, adsorbing solids to the bottom and the side wall of a centrifuge tube by a magnet, and centrifuging for 3min at 4000 rpm; 1mL of organic phase solution obtained by centrifugation is filtered through a 0.22 mu m filter membrane to obtain a pretreated sample, namely the pretreatment of the incense burning sample is finished. The sample obtained after the pretreatment can be used for subsequent detection, such as detection of various cannabinoids in the incense sample by using a conventional analysis method (such as LC, GC-MS, LC-MS/MS and the like).
A method for detecting various cannabinoids in a burning incense smoke gas comprises the following steps: igniting the incense in a smoke collecting device, enriching and collecting smoke by using a solvent, firstly carrying out solvent phase-change purification, then purifying by using an ethylenediamine-N-propyl silane magnetic nano adsorbing material loaded by ferroferric oxide, and then detecting by using a liquid phase (LC), a GC-MS, an LC-MS/MS and the like.
The method for detecting various cannabinoids in the burning incense smoke comprises the following steps:
(1) preparing a ferroferric oxide-loaded ethylenediamine-N-propyl silane magnetic nano adsorption material;
(2) preparing a sample to be tested: igniting the incense to be detected in a smoke gas collecting device, enriching and collecting smoke gas by using a solvent, firstly performing solvent phase-change purification, and then purifying by using the ferroferric oxide loaded ethylenediamine-N-propyl silane magnetic nano adsorbing material prepared in the step (1) to obtain a sample to be detected;
(3) preparing a blank matrix solution: selecting a burning incense sample without cannabinoid, igniting the burning incense sample in a smoke collecting device according to the method in the step (2), enriching and collecting the burning incense sample by using a solvent, firstly performing solvent phase-change purification, and then purifying the burning incense sample by using the ferroferric oxide loaded ethylenediamine-N-propyl silane magnetic nano adsorbing material prepared in the step (1) to obtain a blank matrix solution:
(4) preparation of standard solutions: the blank matrix solution obtained in the step (3) is used for preparing 10 cannabinoid standard solutions into mixed standard solutions with the contents of 1.00 mu g/L, 2.00 mu g/L, 5.00 mu g/L, 10.00 mu g/L, 20.00 mu g/L, 50.00 mu g/L and 100.00 mu g/L.
(5) Establishing a standard curve: performing gas chromatography-mass spectrometry combined determination on the mixed standard solution obtained in the step (4) by using a gas chromatography-mass spectrometer, and drawing a standard curve by using the mass concentration of each component standard series solution as a horizontal coordinate (x) and the corresponding chromatographic peak area as a vertical coordinate (y) to obtain a corresponding linear equation;
(6) and (3) detection of a sample to be detected: carrying out gas chromatography-mass spectrometry combined determination on the sample to be detected obtained in the step (2) by using a gas chromatography-mass spectrometer; performing qualitative detection on the cannabinoid compounds in the sample to be detected according to the existence of chromatographic peaks of the sample to be detected and the cannabinoid standard substances appearing at the same retention time; and (5) according to the chromatographic peak area of the sample to be detected, and combining the linear equation obtained in the step (5), and quantitatively detecting the cannabinoid compounds in the sample to be detected.
The specific method for preparing the ferroferric oxide-loaded ethylenediamine-N-propyl silane magnetic nano adsorption material in the step (1) comprises the following steps:
1.4g of ferroferric oxide Fe3O4Mixing the obtained product with 0.6g of ethylenediamine-N-propyl silane PSA in a 50mL centrifuge tube, adding 10mL of absolute ethyl alcohol, whirling for 30s, uniformly mixing, performing ultrasonic treatment for 1h, taking out, standing for 1h at room temperature, centrifuging for 1min at 4000r/min, discarding supernatant, placing the product at 80 ℃ for vacuum drying for 4h, taking out a screen with the aperture of 150 mu m, and obtaining the ferroferric oxide-loaded ethylenediamine-N-propyl silane magnetic nano-adsorption material.
The specific method for preparing the sample to be detected in the step (2) comprises the following steps:
a. sample pretreatment: weighing the incense to be detected by using a smoke collecting device, igniting the incense, putting the incense into a combustion chamber 1, adding 20mL of methanol solution into a smoke collecting test tube 2, starting a vacuum pump 4 to enable the air extraction flow to be larger than 0.5L/min, extracting air for 5min after the incense is completely burnt out, and closing the vacuum pump 4; collecting all unburned incense, incense ash and other combustion objects, weighing, and comparing with the weighing result before combustion to obtain the actual burning incense weight;
b. purification: taking down a flue gas collection test tube 2, adding 2-5 mL of saturated sodium chloride solution, uniformly mixing by swirling for 30s, centrifuging for 3min at 4000rpm, taking an organic phase solution into another test tube, adding 1-5 g of anhydrous calcium chloride, centrifuging for 3min at 30s by swirling for 4000rpm, taking a supernatant, and blowing nitrogen to be nearly dry at 40 ℃;
adding 2mL of ethyl acetate into a test tube blown to be nearly dry by nitrogen to dissolve, adding 50-100 mg of ferroferric oxide loaded ethylenediamine-N-propylsilane magnetic nano adsorption material and 100-200 mg of Graphitized Carbon Black (GCB), swirling for 30s, and adsorbing the solid to the bottom and the side wall of the centrifuge tube by a magnet or centrifuging for 3min at 4000 rpm; 1mL of organic phase solution obtained by centrifugation is filtered through a 0.22 mu m filter membrane to obtain a sample to be detected.
When the combined gas chromatography-mass spectrometry is carried out in the steps (5) and (6), the gas chromatography conditions are as follows: a chromatographic column: HP-5MS (30 m.times.0.25 mm.times.0.25 μm); temperature program of chromatographic column: keeping the temperature at 70 ℃ for 2min, then increasing the temperature to 270 ℃ at the heating rate of 25 ℃/min, then increasing the temperature to 300 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 7 min; the carrier gas is high-purity helium, and the flow rate is 1.0 mL/min; sample inlet temperature: 280 ℃; sample introduction amount: 1 μ L, no split injection.
The mass spectrum conditions are as follows:
an ion source: an EI source; ionization energy: 70 eV; ion source temperature: 230 ℃; interface temperature of gas chromatography and mass spectrometry: 280 ℃; temperature of the quadrupole rods: 150 ℃; solvent retardation: 5 min; the scanning mode is as follows: the selected ions scan the SIM.
The detection method of the present invention is described in detail below with reference to specific examples:
the first embodiment is as follows:
1 experimental part
1.1 detection of cannabinoids targets
1.2 instruments and reagents
An Agilent 7890A/5975C gas chromatography-mass spectrometry combination, Agilent Chemstation workstation;
an electronic balance; a centrifuge; incense burning smoke collecting device.
Ferroferric oxide (Fe)3O4) And (3) particle: 30 nm; ethylenediamine-N-Propylsilane (PSA); graphitized Carbon Black (GCB).
1.3 ferroferric oxide loaded ethylenediamine-N-propyl silane magnetic nano adsorption material (PSA/Fe)3O4) Mixing 1.4g of ferroferric oxide (Fe3O4) and 0.6g of ethylenediamine-N-Propylsilane (PSA) in a 50mL centrifuge tube, adding 10mL of absolute ethyl alcohol, vortexing for 30s, uniformly mixing, performing ultrasonic treatment for 1h, taking out, standing at room temperatureStanding for 1h, centrifuging at 4000r/min for 1min, discarding supernatant, vacuum drying the product at 80 deg.C for 4h, and sieving with 150 μm mesh.
1.4 incense burning flue gas collection
The incense burning smoke gas collecting device is used for collecting incense burning smoke gas, wherein the structure of the incense burning smoke gas collecting device is shown in figure 2.
As can be seen from FIG. 2, the incense burning smoke collecting device comprises a combustion chamber 1, a smoke collecting test tube 2, a gas flow meter 3 and a vacuum pump 4. The combustion chamber 1, the flue gas collecting test tube 2, the gas flowmeter 3 and the vacuum pump 4 are sequentially connected through a pipeline 5.
After the incense burning sample is ignited in the combustion chamber 1, the air suction amount is adjusted through the vacuum pump 4, methanol solution is put into the smoke collection test tube 2, and the generated smoke is enriched in the test tube and then is measured.
1.5 sample pretreatment
The smoke collection device shown in fig. 2 is used, the incense is weighed and then ignited, the incense is placed in the combustion chamber 1, 20mL of methanol solution is added into the smoke collection test tube 2, the vacuum pump 4 is started, the air extraction flow is larger than 0.5L/min, the incense is extracted for 5min after being completely burnt out, and the vacuum pump 4 is closed. Collecting all unburnt incense, incense ash and other combustion objects, weighing, and comparing with the weighing result before combustion to obtain the actual burning incense weight.
1.6 purification
Taking down a flue gas collection test tube 2, adding 2-5 mL of saturated sodium chloride solution, uniformly mixing by swirling for 30s, centrifuging for 3min at 4000rpm, taking an organic phase solution into another test tube, adding 1-5 g of anhydrous calcium chloride, centrifuging for 3min at 4000rpm by swirling for 30s, taking a supernatant, and blowing nitrogen to be nearly dry at 40 ℃.
Adding 2mL of ethyl acetate into the test tube which is blown to be nearly dry by nitrogen for dissolving, and then adding 50-100 mgPSA/Fe3O4100-200 mg GCB, vortexing for 30s, and adsorbing the solid substance to the bottom and the side wall of a centrifuge tube by using a magnet or centrifuging for 3min at 4000 rpm.
1mL of the organic phase solution was filtered through a 0.22 μm filter and assayed.
1.7 Standard solution preparation
1.7.1 preparation of blank matrix solution
Selecting a burning incense sample without cannabinoid, and pretreating according to 1.5-1.6 to obtain a burning incense smoke to-be-tested liquid, namely a blank matrix solution, for preparing a standard curve.
1.7.2 preparation of Standard Curve
Diluting the 10 cannabinoid standard solutions in 1.1 with methanol to 10mg/L single standard, preparing into 1mg/L mixed standard of 10 mixed cannabinoids with methanol, and storing at 0-4 deg.C for 3 months.
When in use, 1mg/L of mixed standard is prepared into mixed standard solutions with the content of 1.00 mu g/L, 2.00 mu g/L, 5.00 mu g/L, 10.00 mu g/L, 20.00 mu g/L, 50.00 mu g/L and 100.00 mu g/L by using the blank matrix solution described in 1.7.1.
1.8 apparatus conditions
1.8.1 gas chromatography conditions
A chromatographic column: HP-5MS (30 m.times.0.25 mm.times.0.25 μm); temperature program of chromatographic column: keeping the temperature at 70 ℃ for 2min, then increasing the temperature to 270 ℃ at the heating rate of 25 ℃/min, then increasing the temperature to 300 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 7 min; the carrier gas is high-purity helium, and the flow rate is 1.0 mL/min; sample inlet temperature: 280 ℃; sample introduction amount: 1 μ L, no split injection.
1.8.2 Mass Spectrometry conditions
An ion source: an EI source; ionization energy: 70 eV; ion source temperature: 230 ℃; interface temperature of gas chromatography and mass spectrometry: 280 ℃; temperature of the quadrupole rods: 150 ℃; solvent retardation: 5 min; the scanning mode comprises the following steps: a selective ion Scan (SIM); the characteristic selection ions of each substance are shown in table 1.
Mass Spectrometry parameters for the 110 cannabinoids Table
1.9 matrix Effect investigation
In gas chromatography analysis, because the existence of matrix components reduces the opportunity of the interaction between active sites in a chromatographic system and molecules of an object to be detected, the matrix enhancement effect is usually shown, and particularly, the matrix effect condition of complex impurities such as burning incense smoke and the like needs to be investigated.
Selecting burning incense without cannabinoid, detecting no cannabinoid residue, taking the sample as a blank sample, carrying out sample pretreatment according to 1.5 and 1.6 to obtain a burning incense smoke to-be-detected solution, preparing a matrix standard solution with the concentration of 20 mug/L, comparing the matrix standard solution with a standard solution with the same concentration and prepared by methanol, and calculating the matrix effect by using the following formula: matrix effect ME (%) ═ l (a)2-A1)|/A1X 100% where A1Response values for 10 cannabinoids in methanol solution, A2Response values for 10 cannabinoids in the incense smoke blank sample solution. The results are shown in Table 2.
TABLE 2 matrix Effect of 10 cannabinoids in cigarette Smoke
| Serial number | Name (R) | Substrate effect of burning incense Smoke (%) |
| 1 | CBD | 71.4 |
| 2 | THC | 58.6 |
| 3 | CBN | 73.2 |
| 4 | CP-47497 | 56.3 |
| 5 | ADB-PINACA | 58.5 |
| 6 | RCS-4 | 123.5 |
| 7 | AB-CHMINACA | 201.7 |
| 8 | AM2201 | 841.5 |
| 9 | JWH-210 | 86.7 |
| 10 | MAM2201 | 438.5 |
The matrix effect is strong when the matrix effect is more than 50%, and as can be seen from table 2, the matrix effect of cannabinoids in the burning cigarette smoke is more than 50%, so that a method for eliminating matrix interference is needed. The method for preparing the standard curve by using the blank burning incense smoke matrix can effectively remove matrix interference in burning incense and burning incense smoke through the verification of recovery rate and precision.
1.10 comparison of purification Effect
The invention relates to ethylenediamine-N-propyl silane magnetic nano adsorption material (PSA/Fe) loaded by various purification materials of anhydrous calcium chloride, GCB and ferroferric oxide3O4) The purification effect of (a) and the combined effect of different materials are discussed. The comparison result shows that the single material or the common GCB + PSA purification can not play a good purification effect, and the anhydrous calcium chloride + GCB + magnetic nano PSA/Fe provided by the invention3O4The effect of (2) is the best.
Since metal ions can chelate with polyphenols and other compounds and even form insoluble complexes, the purification is usually performed by adsorption with anhydrous magnesium sulfate. The invention uses GCB + magnetic nano PSA/Fe3O4After the purification mode, the purification effect of the anhydrous magnesium sulfate in the combination is not as good as that of anhydrous calcium chloride, so the anhydrous calcium chloride is adopted to be combined with GCB and magnetic nano PSA/Fe3O4A combined purification mode.
1.11 Linear relationship and detection limits of the method
Taking mixed standard solutions with the concentrations of 1.00 mu g/L, 2.00 mu g/L, 5.00 mu g/L, 10.00 mu g/L, 20.00 mu g/L, 50.00 mu g/L and 100.00 mu g/L respectively, performing on-machine detection by using the instrument condition of 1.8, drawing standard curves by using the mass concentration of each component standard series solution as an abscissa (x) and the corresponding chromatographic peak area as an ordinate (y) (the standard curves of CBD, THC, CBN, ADB-PINACA, RCS-4, AB-CHMINACA, AM2201, JWH-210, MAM2201 and CP-47979 are shown in figures 4-13). The concentration of each compound calculated as a 3-fold signal-to-noise ratio (S/N ═ 3) was defined as the detection Limit (LOD), and the concentration of each compound calculated as a 10-fold signal-to-noise ratio (S/N ═ 10) was defined as the quantification Limit (LOQ). The results show that: the linear relationship in the obtained range is good, the correlation coefficients are all larger than 0.995, the detection limit and the quantification limit meet the requirement of identifying illegally added cannabinoids, and the results are shown in table 3. The chromatogram of the 10 cannabinoids psychoactive substance standard is shown in figure 3.
Linear method, correlation coefficient, detection limit and quantification limit of the method of Table 3
1.12 detection of samples to be tested (10 commercially available incense samples were detected):
preprocessing 10 incense samples to be detected sold in the market according to 1.5 and 1.6 to obtain corresponding samples to be detected. Carrying out gas chromatography-mass spectrometry combined determination on the obtained sample to be detected by using a gas chromatography-mass spectrometer (the conditions of gas chromatography and mass spectrometry are as described in 1.8); performing qualitative detection on the cannabinoid compounds in the sample to be detected according to the existence of chromatographic peaks of the sample to be detected and the cannabinoid standard substances appearing at the same retention time; and (3) according to the chromatographic peak area of the sample to be detected, combining the linear equation obtained in the step 1.11, and carrying out quantitative detection on the cannabinoids in the sample to be detected.
The 10 commercially available incense samples were tested and no cannabis content was detected. The detection results are shown in table 4, and the chromatogram of the detected incense sample is shown in fig. 14.
TABLE 4 test results on commercial incense samples
The foregoing is only a preferred embodiment of the present invention, and it should be noted that a person skilled in the art may make several changes, improvements and modifications without departing from the spirit of the present invention, and these changes, improvements and modifications should be construed as the protection scope of the present invention.
Claims (2)
1. A pretreatment method of a burning incense sample is characterized by comprising the following steps: the pretreatment method comprises the following steps: igniting the incense in a smoke collecting device, enriching and collecting smoke by using a solvent, firstly performing solvent phase-change purification, and then purifying by using a ferroferric oxide loaded ethylenediamine-N-propylsilane magnetic nano adsorbing material;
the pretreatment method of the incense sample is pretreatment for detecting cannabinoids in incense smoke, wherein the cannabinoids are THC, CBN, CBD, JWH-210, CP47497, AM-2201, RCS-4, MAM-2201, AB-CHMINCA and ADB-PINACA;
the pretreatment method comprises the following steps:
a. sample pretreatment: weighing the incense by using a smoke collection device, igniting the incense, putting the incense into a combustion chamber, adding 20mL of methanol solution into a smoke collection test tube, starting a vacuum pump to enable the air extraction flow to be larger than 0.5L/min, extracting air for 5min after the incense is completely burnt out, and closing the vacuum pump; collecting all unburned incense, incense ash and other combustion objects, weighing, and comparing with the weighing result before combustion to obtain the actual burning incense weight;
b. purifying: taking down a flue gas collection test tube, adding 2-5 mL of saturated sodium chloride solution, uniformly mixing by swirling for 30s, centrifuging for 3min at 4000rpm, taking an organic phase solution into another test tube, adding 1-5 g of anhydrous calcium chloride, swirling for 30s, centrifuging for 3min at 4000rpm, taking a supernatant, and blowing nitrogen to be nearly dry at 40 ℃;
blowing nitrogen into a nearly dry test tube, adding 2mL of ethyl acetate for dissolving, adding 50-100 mg of ferroferric oxide-loaded ethylenediamine-N-propylsilane magnetic nano adsorption material and 100-200 mg of graphitized carbon black GCB, swirling for 30s, adsorbing solid substances to the bottom and the side wall of a centrifuge tube by using a magnet, and centrifuging for 3min at 4000 rpm; 1mL of organic phase solution obtained by centrifugation is taken to pass through a 0.22 mu m filter membrane to obtain a pretreated sample, namely the pretreatment of the incense burning sample is completed;
the ferroferric oxide-loaded ethylenediamine-N-propyl silane magnetic nano-adsorption material is prepared by the following method:
1.4g of ferroferric oxide Fe3O4Mixing the obtained product with 0.6g of ethylenediamine-N-propyl silane PSA in a 50mL centrifuge tube, adding 10mL of absolute ethyl alcohol, whirling for 30s, uniformly mixing, performing ultrasonic treatment for 1h, taking out, standing for 1h at room temperature, centrifuging for 1min at 4000r/min, discarding supernatant, placing the product at 80 ℃ for vacuum drying for 4h, taking out a screen with the aperture of 150 mu m, and obtaining the ferroferric oxide-loaded ethylenediamine-N-propyl silane magnetic nano-adsorption material.
2. A method for detecting various cannabinoids compounds in incense smoke is characterized by comprising the following steps: the detection method comprises the following steps: igniting the incense in a smoke collecting device, enriching and collecting smoke by using a solvent, firstly performing solvent phase-change purification, then purifying by using an ethylenediamine-N-propyl silane magnetic nano adsorbing material loaded with ferroferric oxide, and then detecting by using liquid phase LC, GC-MS and LC-MS/MS; the cannabinoids are THC, CBN, CBD, JWH-210, CP47497, AM-2201, RCS-4, MAM-2201, AB-CHMINACA and ADB-PINACA;
the method for detecting various cannabinoids compounds in the burning incense smoke comprises the following steps:
(1) preparing a ferroferric oxide loaded ethylenediamine-N-propyl silane magnetic nano adsorption material;
(2) preparing a sample to be tested: igniting the incense to be detected in a smoke gas collecting device, enriching and collecting smoke gas by using a solvent, firstly performing solvent phase-change purification, and then purifying by using the ferroferric oxide loaded ethylenediamine-N-propyl silane magnetic nano adsorbing material prepared in the step (1) to obtain a sample to be detected;
(3) preparing a blank matrix solution: selecting a burning incense sample without cannabinoid, igniting the burning incense sample in a smoke collecting device according to the method in the step (2), enriching and collecting the burning incense sample by using a solvent, firstly performing solvent phase-change purification, and then purifying the burning incense sample by using the ferroferric oxide loaded ethylenediamine-N-propyl silane magnetic nano adsorbing material prepared in the step (1) to obtain a blank matrix solution:
(4) preparation of standard solutions: preparing 10 cannabinoid standard solutions into mixed standard solutions with the content of 1.00 μ g/L, 2.00 μ g/L, 5.00 μ g/L, 10.00 μ g/L, 20.00 μ g/L, 50.00 μ g/L and 100.00 μ g/L by using the blank matrix solution obtained in the step (3);
(5) establishing a standard curve: performing gas chromatography-mass spectrometry combined measurement on the mixed standard solution obtained in the step (4) by using a gas chromatography-mass spectrometer, and drawing a standard curve by using the mass concentration of each component standard series solution as a horizontal coordinate x and the corresponding chromatographic peak area as a vertical coordinate y to obtain a corresponding linear equation;
(6) and (3) detection of a sample to be detected: carrying out gas chromatography-mass spectrometry combined determination on the sample to be detected obtained in the step (2) by using a gas chromatography-mass spectrometer; performing qualitative detection on the cannabinoid compounds in the sample to be detected according to the existence of chromatographic peaks of the sample to be detected and the cannabinoid standard substances appearing at the same retention time; according to the chromatographic peak area of the sample to be detected, carrying out quantitative detection on the cannabinoid compound in the sample to be detected by combining the linear equation obtained in the step (5);
the specific method for preparing the ferroferric oxide-loaded ethylenediamine-N-propyl silane magnetic nano adsorption material in the step (1) comprises the following steps: 1.4g of ferroferric oxide Fe3O4Mixing the obtained product with 0.6g of ethylenediamine-N-propyl silane PSA in a 50mL centrifuge tube, adding 10mL of absolute ethyl alcohol, whirling for 30s, uniformly mixing, performing ultrasonic treatment for 1h, taking out, standing for 1h at room temperature, centrifuging for 1min at 4000r/min, discarding supernatant, placing the product at 80 ℃ for vacuum drying for 4h, taking out a screen with the aperture of 150 mu m, and obtaining the ferroferric oxide-loaded ethylenediamine-N-propyl silane magnetic nano adsorption material;
the specific method for preparing the sample to be detected in the step (2) comprises the following steps:
a. sample pretreatment: weighing the incense to be detected by using a smoke collecting device, igniting the incense, putting the incense into a combustion chamber, adding 20mL of methanol solution into a smoke collecting test tube, starting a vacuum pump to enable the air extraction flow to be larger than 0.5L/min, extracting air for 5min after the incense is completely burnt out, and closing the vacuum pump; collecting all unburned incense, incense ash and other combustion objects, weighing, and comparing with the weighing result before combustion to obtain the actual burning incense weight;
b. purification: taking down a flue gas collection test tube, adding 2-5 mL of saturated sodium chloride solution, uniformly mixing by swirling for 30s, centrifuging for 3min at 4000rpm, taking an organic phase solution into another test tube, adding 1-5 g of anhydrous calcium chloride, swirling for 30s, centrifuging for 3min at 4000rpm, taking a supernatant, and blowing nitrogen to be nearly dry at 40 ℃;
blowing nitrogen into a nearly dry test tube, adding 2mL of ethyl acetate for dissolving, adding 50-100 mg of ferroferric oxide-loaded ethylenediamine-N-propylsilane magnetic nano adsorption material and 100-200 mg of graphitized carbon black GCB, swirling for 30s, adsorbing solid substances to the bottom and the side wall of a centrifuge tube by using a magnet, and centrifuging for 3min at 4000 rpm; taking 1mL of organic phase solution obtained by centrifugation, and filtering the solution through a 0.22-micron filter membrane to obtain a sample to be detected;
when the combined gas chromatography-mass spectrometry is carried out in the steps (5) and (6), the gas chromatography conditions are as follows: a chromatographic column: HP-5MS 30m × 0.25mm × 0.25 μm; temperature program of chromatographic column: keeping the temperature at 70 ℃ for 2min, then increasing the temperature to 270 ℃ at the heating rate of 25 ℃/min, then increasing the temperature to 300 ℃ at the heating rate of 5 ℃/min, and keeping the temperature for 7 min; the carrier gas is high-purity helium, and the flow rate is 1.0 mL/min; sample inlet temperature: 280 ℃; sample introduction amount: 1 mu L, no shunt sample introduction;
when the gas chromatography-mass spectrometry combined measurement is carried out in the steps (5) and (6), the mass spectrometry conditions are as follows:
an ion source: an EI source; ionization energy: 70 eV; ion source temperature: 230 ℃; interface temperature of gas chromatography and mass spectrometry: 280 ℃; temperature of the quadrupole rods: 150 ℃; solvent retardation: 5 min; the scanning mode is as follows: the selected ions scan the SIM.
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