CN111679013A - Method for analyzing trace drugs and related substances in high-water-content test material - Google Patents
Method for analyzing trace drugs and related substances in high-water-content test material Download PDFInfo
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- CN111679013A CN111679013A CN202010689857.4A CN202010689857A CN111679013A CN 111679013 A CN111679013 A CN 111679013A CN 202010689857 A CN202010689857 A CN 202010689857A CN 111679013 A CN111679013 A CN 111679013A
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- 238000012360 testing method Methods 0.000 title claims abstract description 19
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- 238000000605 extraction Methods 0.000 claims description 10
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000523 sample Substances 0.000 claims description 8
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- 231100000053 low toxicity Toxicity 0.000 claims description 3
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- 239000003208 petroleum Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
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- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 claims description 2
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- 239000010802 sludge Substances 0.000 claims description 2
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- YQEZLKZALYSWHR-UHFFFAOYSA-N Ketamine Chemical compound C=1C=CC=C(Cl)C=1C1(NC)CCCCC1=O YQEZLKZALYSWHR-UHFFFAOYSA-N 0.000 description 5
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- 238000004451 qualitative analysis Methods 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- SHXWCVYOXRDMCX-UHFFFAOYSA-N 3,4-methylenedioxymethamphetamine Chemical compound CNC(C)CC1=CC=C2OCOC2=C1 SHXWCVYOXRDMCX-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- ZPUCINDJVBIVPJ-LJISPDSOSA-N cocaine Chemical compound O([C@H]1C[C@@H]2CC[C@@H](N2C)[C@H]1C(=O)OC)C(=O)C1=CC=CC=C1 ZPUCINDJVBIVPJ-LJISPDSOSA-N 0.000 description 2
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- 241000700605 Viruses Species 0.000 description 1
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- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- -1 biological excrement Substances 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
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- 229960001252 methamphetamine Drugs 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- OEHAYUOVELTAPG-UHFFFAOYSA-N methoxyphenamine Chemical compound CNC(C)CC1=CC=CC=C1OC OEHAYUOVELTAPG-UHFFFAOYSA-N 0.000 description 1
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- 230000001629 suppression Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N30/08—Preparation using an enricher
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
A method for analyzing trace drugs and related substances in a high-water-content test material comprises the following steps: (1) concentrating and enriching; (2) solvent extraction; (3) and (6) analyzing by an instrument. The analysis method adopted by the invention can not be influenced by the factors such as the clarification degree of the material to be detected, insoluble particles, dissolved sticky matters, the volume of a water sample and the like, only one-step freeze drying operation is carried out to remove a large amount of water in the material to be detected with high water content, the whole process is carried out at the temperature below 0 ℃, the loss of trace target matters with low boiling points and easy volatilization is prevented, the analysis method has simple flow, no need of manual guard, no waste discharge in the whole process, no environmental pollution problem exists, the freeze drying treatment time is completely determined by the temperature difference of an environment cold trap, the temperature difference of a material tray and the power of a vacuum pump, the efficiency of freeze drying the sample with high water content can be improved by increasing the temperature difference and improving the power of the vacuum pump.
Description
Technical Field
The invention relates to the technical field of detection and analysis, in particular to an analysis method for trace drugs and related substances in a high-water-content detection material.
Background
With the development of information technology, the concealment of the virus suppression and drug absorption phenomena is gradually strengthened, and the possibility of finding the clues is gradually reduced. The method is characterized in that discharged sewage is extracted in a sensitive place and a sensitive node in a concealed manner, content changes of drugs and metabolites thereof, easily-made chemicals and a drug-making intermediate (hereinafter, collectively referred to as a target object) in the discharged sewage are monitored, a scientific basis is provided for judging whether drug absorption and drug making phenomena exist in the area, and a good technical support is provided for public security drug administration and drug judicial identification.
However, the content of the target substance in the high-water content detection material is extremely low, the high-sensitivity liquid chromatography tandem mass spectrometry cannot be used for direct determination, and the concentration is integrated into the key factor of the application and popularization. At present, the traditional enrichment method is a solid-phase extraction method, but the traditional enrichment method has strict requirements on the clarification degree of a high-water-content detection material source, one-step or several-step treatment operation is needed before extraction, target substances are possibly lost, the enrichment time is long, certain trace components are volatile when the extraction is carried out at room temperature, and a solid-phase extraction cartridge is easy to dry, so that good technical support cannot be provided for public security drug control and drug judicial identification conveniently.
Public security criminal investigation, judicial appraisal and environmental protection often contact various materials of examining of higher water content, such as municipal sewage, blowdown sediment, even human excrement, secretion, blood etc. examine the material branch and belong to different detection areas, examine the material processing method differently, compatibility is poor each other, the analytic process is not unified, the standard is different, so lead to the analytical result difficult intercommunication, interoperable between different fields. Therefore, the method has strong practical application significance for exploring a universally applicable analysis method aiming at the material to be detected with higher water content.
Disclosure of Invention
In order to solve the problems, the invention provides a general, simple and nondestructive enrichment and concentration method for a target object so as to meet the concentration requirement of the target object for sample injection analysis of an instrument.
The technical scheme adopted by the invention is as follows:
a method for analyzing trace drugs and related substances in a high-water-content test material comprises the following steps:
(1) concentration and enrichment: the method comprises the steps of freezing a high-water-content material to be detected into a solid state in a refrigerator in advance by using an open container by adopting a freeze-drying method, then transferring the material to the freeze-drying machine, vacuumizing to enable the environment of the material to be detected to be below a triple point of water, and directly subliming water in the material to be detected into a gas state from the solid state (ice) and pumping away the water by a vacuum pump. Liquid water is not generated in the whole process of the freeze drying method, the test material is not subjected to the processes of volume reduction and precipitate collapse caused by the change from solid ice to liquid water, and finally, the precipitate in the test material exists in a fluffy state.
(2) Solvent extraction: the solid material after freeze drying treatment is fluffy, and can be leached by organic solvent, cleaned, filtered and concentrated, and then redissolved by organic solvent to prepare sample solution.
(3) Analyzing by an instrument: and (4) qualitatively and quantitatively analyzing the corresponding target object by referring to relevant national standards or ministerial technical specifications.
The high water content detection material is a detection material with the water content of more than 30 percent, and comprises but is not limited to municipal sewage, sludge, biological excrement, blood, fruit juice, beverage, milk and the like.
The extraction organic solvent is a low-boiling-point, volatile and low-toxicity organic solvent.
The extraction organic solvent includes but is not limited to one or a mixture of several of the following substances: methanol, ethanol, acetone, ethyl acetate, acetonitrile, chloroform, dichloromethane, benzene homologues, petroleum ether and mixtures thereof.
The instrument analysis adopts a gas chromatography-mass spectrometry combined method and a liquid chromatography-mass spectrometry combined method.
The whole process of the freeze drying treatment of the material to be detected is always in a solid state below 0 ℃, the water component is always in a process of directly converting from a solid state to a gas state, and the loss of low-boiling-point volatile trace target substances can be prevented.
In the freeze drying process of the material to be detected, the temperature of the environment is provided by the temperature difference between the environment cold trap and the material tray, the temperature of the cold trap is usually-80 to-20 ℃, the temperature of the material tray is usually-10 to +10 ℃, and the freeze drying efficiency can be improved by increasing the temperature difference between the environment cold trap and the material tray.
Examine material in freeze-drying process, the pressure of environment is provided by the vacuum pump, improves the work efficiency of vacuum pump and can improve freeze-drying's efficiency.
The invention has the beneficial effects that: the freeze drying method adopted by the invention can not be influenced by factors such as the clarification degree of the material to be detected, insoluble particles, dissolved sticky matters, the volume of a water sample and the like, a large amount of water in the material to be detected with high water content can be removed only by one-step freeze drying operation, the whole process is carried out at the temperature of below 0 ℃, and the loss of low-boiling-point volatile trace target substances can be prevented; the method has simple flow, does not need manual guard, does not discharge waste in the whole process, does not have the problem of environmental pollution, has the freeze-drying treatment efficiency completely determined by the temperature difference of the environmental cold trap and the material tray and the working efficiency of the vacuum pump, can improve the efficiency of freeze-drying the high-water content material to be detected by increasing the temperature difference and improving the power of the vacuum pump, and has large subsequent research and development space and wide application prospect.
Drawings
FIG. 1 is a total ion flow diagram of the detection of municipal sewage after drug samples are added.
FIG. 2 is an ion diagram of ketamine extraction according to the invention.
FIG. 3 is an ion diagram of the extraction of norketamine according to the invention.
Detailed Description
The concentration and enrichment method of the target object in the high water content test material adopts a freeze drying method, the test material is always in a solid state below 0 ℃ in the whole process of treatment, the water component is always in a process of converting from a solid state to a gas state, and no liquid water exists in the whole process.
A method for analyzing trace drugs and related substances in a high-water-content test material comprises the following steps:
(1) concentration and enrichment: the method comprises the steps of freezing a high-water-content material to be detected into a solid state (ice) in a refrigerator in advance by using an open container, transferring the solid state (ice) into a freeze dryer, vacuumizing to enable the material to be detected to be below the triple point of water, namely, the temperature is less than 0.01 ℃, the pressure is less than 611.73Pa, so that the water in the high-water-content material to be detected is directly sublimated into a gas state from the solid ice and is pumped away by a vacuum pump;
(2) solvent extraction: the solid material after freeze drying treatment is fluffy, and is extracted by using low-boiling point, volatile and low-toxicity extraction organic solvent, wherein the extraction organic solvent comprises but is not limited to one or a mixture of several substances: eluting materials with methanol, ethanol, acetone, ethyl acetate, acetonitrile, chloroform, dichloromethane, benzene homologues, petroleum ether and their mixture by spray, filtering, concentrating, and analyzing with instrument to obtain standard concentration;
(3) analyzing by an instrument: and (3) qualitatively and quantitatively analyzing the corresponding target by using a gas chromatography-mass spectrometry combined method and a liquid chromatography-mass spectrometry combined method according to related national standards or technical specifications issued by the ministry.
The whole process of the freeze drying treatment of the material to be detected is always in a solid state below 0 ℃, the water component is always in a process of directly converting from a solid state to a gas state, and the loss of low-boiling-point volatile trace target substances can be prevented.
In the freeze drying process of the material to be detected, the temperature of the environment is provided by the temperature difference between the environment cold trap and the material tray, the temperature of the cold trap is usually-80 to-20 ℃, the temperature of the material tray is usually-10 to +10 ℃, and the freeze drying efficiency can be improved by increasing the temperature difference between the environment cold trap and the material tray.
Examine material in freeze-drying process, the pressure of environment is provided by the vacuum pump, improves the work efficiency of vacuum pump and can improve freeze-drying's efficiency.
Example 1
The invention selects the urban sewage added with 10 standard drugs as the verification of the invention.
A method for analyzing trace drugs and related substances in a high-water-content test material comprises the following steps:
(1) concentration and enrichment:
250mL of municipal sewage inspection material added with 10 standard drugs is placed into a tray and frozen into ice blocks in a refrigerator, the ice blocks are placed into a freeze dryer, the vacuum is kept at 10Pa, the temperature of a cold trap is-45 ℃, the temperature of the tray is 10 ℃, the vacuum pumping is carried out at the rate of 62L per minute, the water is completely removed after 24 hours of maintenance, and fluffy solid matters are remained in the tray;
(2) solvent extraction:
the solid material after freeze drying is rinsed by 10mL of methanol for multiple times, filtered and volatilized, and then redissolved by 1mL of methanol.
(3) Analyzing by an instrument:
and filtering the well-fixed volume sample injection solution by using a 0.22 micron filter membrane, and performing qualitative and quantitative analysis by using triple quadrupole liquid chromatography-mass spectrometry.
Adding the quality of a drug standard sample into 250mL of urban sewage: 1# -8 #: 16 ng; 9 #: 40 ng; 10 #: 4ng, 10 drugs are detected under the concentration by applying the method of the invention, and the detection data is shown in a table 1:
TABLE 1 data relating to the detection of 10 drugs in sewage by freeze-drying method
| Serial number | Name (R) | RT1 | Ion 1/A1 | RT2 | Ion 2/A2 | |
| 1 | AMP | 3.082 | 91.1/5317.13 | 3.074 | 119.1/1047.38 | 19.7 |
| 2 | MAMP | 3.725 | 91.0/11502.46 | 3.711 | 119.1/3141.22 | 27.3 |
| 3 | MDMA | 4.193 | 163.0/6474.08 | 4.193 | 105.1/2977.46 | 46.0 |
| 4 | Morphine (morphine) | 0.794 | 165.0/397.14 | 0.801 | 201.0/144.42 | 36.4 |
| 5 | Monoacetylmorphine | 4.280 | 165.1/790.74 | 4.280 | 211.0/117.51 | 14.9 |
| 6 | Ketamine (Ketamine) Ketamine | 5.782 | 125.0/4814.04 | 5.782 | 179.1/1412.33 | 29.3 |
| 7 | Norketamine | 5.741 | 125.0/1619.49 | 5.740 | 207.0/598.74 | 37.0 |
| 8 | Cocaine | 6.221 | 182.2/17298.7 | 6.221 | 150.2/1254.03 | 7.2 |
| 9 | Benzoyl Aikangning | 5.346 | 168.0/2582.66 | 5.339 | 105.0/1228.41 | 49.9 |
| 10 | Methoxyphenamine | 5.588 | 121.0/892.31 | 5.595 | 149.1/683.87 | 76.6 |
The total ion flow diagram in this example is shown in figure 1. The extraction ion figures for ketamine and norketamine are shown in figures 2 and 3.
Example 2
A method for analyzing trace drugs and related substances in a high-water-content test material comprises the following steps:
(1) concentration and enrichment:
250ml of sewage inspection material in a septic tank added with MDMA and MAMP standard drugs is placed in a tray and frozen into ice blocks in a refrigerator, the ice blocks are placed in a freeze dryer, the vacuum is kept at 10Pa, the temperature of a cold trap is-50 ℃, the temperature of the tray is 0 ℃, the vacuum pumping is carried out at the rate of 124L per minute, the water is removed after the vacuum is kept for 15 hours, and fluffy solid substances are remained in the tray;
(2) solvent extraction:
and leaching the solid material subjected to freeze drying treatment by using 10mL of acetonitrile for multiple times, filtering and volatilizing, and re-dissolving by using 1mL of acetonitrile.
(3) Analyzing by an instrument:
and filtering the well-fixed volume sample injection solution by using a 0.22 micron filter membrane, and performing qualitative and quantitative analysis by using triple quadrupole liquid chromatography-mass spectrometry.
Example 3
A method for analyzing trace drugs and related substances in a high-water-content test material comprises the following steps:
(1) concentration and enrichment:
250ml of milk testing material added with methamphetamine is placed into a tray and frozen into ice blocks in a refrigerator, the ice blocks are placed into a freeze dryer, the vacuum is kept at 10Pa, the temperature of a cold trap is-70 ℃, the temperature of a tray is-10 ℃, a vacuum pump is 62L per minute, the water is completely removed after the vacuum pumping is kept for 24 hours, and fluffy solid state residues are left in the tray;
(2) solvent extraction:
the solid material after freeze drying is rinsed with 10mL ethyl acetate for multiple times, filtered and volatilized, and then redissolved with 1mL ethyl acetate.
(3) Analyzing by an instrument:
and filtering the sample solution with a constant volume by using a 0.22 micron filter membrane, and performing qualitative and quantitative analysis by using gas chromatography-mass spectrometry according to national standards.
The embodiments of the present invention have been described in detail, but the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. All equivalent changes and modifications made within the scope of the present invention shall fall within the scope of the present invention.
Claims (9)
1. A method for analyzing trace drugs and related substances in a high-water-content test material is characterized by comprising the following steps:
(1) concentration and enrichment: the method comprises the steps of freezing a high-water-content material to be detected into a solid state in a refrigerator in advance by using an open container by adopting a freeze drying method, transferring the material to be detected into a freeze drying machine, vacuumizing the freeze drying machine, and enabling the material to be detected to be below the triple point of water, namely, the temperature is less than 0.01 ℃ and the pressure is less than 611.73Pa, so that the water in the material to be detected is directly sublimated into a gas state from solid ice and is pumped away by a vacuum pump, no liquid water is generated in the whole process, the material to be detected does not have the process of volume reduction and precipitate collapse caused by the fact that the solid ice is changed into;
(2) solvent extraction: the solid material after freeze drying treatment is fluffy, is extracted by using an extraction organic solvent, is washed, is filtered and concentrated, and is re-dissolved by using the organic solvent to prepare a sample solution;
(3) analyzing by an instrument: and (4) qualitatively and quantitatively analyzing the corresponding target object by referring to relevant national standards or ministerial technical specifications.
2. The method as claimed in claim 1, wherein the high water content test material is a sample with a water content of more than 30%, and typical samples include municipal sewage, sludge, biological waste, blood, fruit juice, beverages, and milk.
3. The method of claim 1, wherein the ultra-fine chemicals and related substances are chemicals, chemicals susceptible to chemical reaction, metabolites of chemicals and chemical intermediates of chemical reaction.
4. The method as claimed in claim 1, wherein the organic solvent is a low-boiling, volatile, low-toxicity organic solvent.
5. The method for analyzing the trace amount of drugs and related substances in the high water content test material according to claim 4, wherein the organic solvent is one or more of methanol, ethanol, acetone, ethyl acetate, acetonitrile, chloroform, dichloromethane, benzene homologues and petroleum ether.
6. The method of claim 1, wherein the mass spectrometry is performed by gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry.
7. The method according to claim 1, wherein the temperature and pressure of the sample during the freeze drying process are below the triple point of water, i.e. the temperature is less than 0.01 ℃, the pressure is less than 611.73Pa, the water in the sample is always in the process of converting from solid to gas, and no liquid water is present during the whole process, thereby preventing the loss of trace volatile target substances with low boiling points.
8. The method for analyzing trace amount of drugs and their related substances in a test material with high water content according to claim 1, wherein during the freeze drying process of the test material, the temperature of the environment is provided by the temperature difference between the cold trap of the environment and the material tray, usually the temperature of the cold trap is-80 to-20 ℃, the temperature of the tray is-10 to +10 ℃, and the temperature difference between the two is increased to improve the efficiency of freeze drying.
9. The method for analyzing trace amounts of drugs and their related substances in a test material with high water content according to claim 1, wherein the pressure of the environment is provided by a vacuum pump during the freeze-drying process, and the efficiency of the freeze-drying process can be improved by increasing the working efficiency of the vacuum pump.
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| CN113219102A (en) * | 2021-05-25 | 2021-08-06 | 南开大学 | Method for measuring content of toxic substances and metabolites thereof in sewage |
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