CN109655569B - SPME-GC detection method for amphetamine substances in urine - Google Patents
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Abstract
The invention relates to an SPME-GC detection method of amphetamine substances in urine, which is characterized in that PAF-41 coating fibers are connected to a micro sample injection needle of 5 mu L to be used as SPME fibers; SPME pretreatment is carried out on a urine sample containing the phenylpropylamine substances by using PAF-41 coating fibers, and then gas chromatography separation, ion flame detector detection and external standard method quantification are carried out. The SPME fiber used in the invention is PAF-41 coating fiber, and PAF-41 is a novel porous aromatic skeleton material, has larger specific surface area, uniform pore size distribution and good adsorption performance on volatile organic compounds; the aromatic compound has high aromaticity, can easily form pi-pi interaction with target analytes amphetamine and methamphetamine, and is beneficial to extraction of the target analytes; the skeleton of the porous material contains N atoms, and the-NH in the p-phenylpropylamine and the methamphetamine can be greatly enhanced through the similar compatibility principle, the hydrogen bond and other actions2Thereby improving the extraction capability and leading the extract to have unique selective adsorption performance on the phenylpropylamine and the methamphetamine.
Description
Technical Field
The invention relates to an SPME-GC detection method for amphetamine substances in urine, belonging to the field of analytical chemistry.
Background
The amphetamine type narcotics are artificially synthesized organic amine stimulants, have strong stimulation effect and belong to prohibited narcotics. Abuse of amphetamine can be confirmed by testing drugs in biological samples such as blood, urine, saliva and hair. Since the concentration of drugs in vivo gradually decreases with time, it is necessary to establish a sensitive, accurate, simple and rapid detection method for detecting trace amounts of drugs in biological samples.
According to the research results at home and abroad, the detection method of the amphetamine drugs mainly comprises gas chromatography, high performance liquid chromatography, capillary electrophoresis, high performance liquid chromatography-mass spectrometry combined detection, but complex pretreatment including solvent extraction, concentration and the like is usually required before the detection, so that the operation is complex and the efficiency is low. The invention adopts the application of the porous polytriphenylamine/gel mixed coating to the solid phase extraction technology, establishes a simple and rapid pretreatment method, combines with gas chromatography detection, has high sensitivity and strong selectivity, and provides a more efficient and simple method for the detection of the amphetamine. The Solid-phase microextraction (SPME) technique is a sample pretreatment technique integrating sampling, extraction, concentration and sample introduction, and has been widely applied to environmental engineering, bioengineering, pharmaceutical engineering and food engineering. The SPME technology is applied to the detection of the amphetamine in the urine of the drug addict, so that the sensitivity and the efficiency are effectively improved.
The core of SPME technology is the extraction fiber (or extraction head), and the quality of the extraction fiber depends on the efficiency, selectivity and stability of the concentration of the analyte in the extraction coating. According to different extraction principles, the method can be divided into absorption coating and adsorption coating, wherein the latter has higher sensitivity and selectivity and is suitable for detecting trace substances. The functional component of the adsorption coating is a solid Porous material, and a Porous Organic framework material (POFs) is a novel solid Porous material with regular pore channels, and attracts people's attention due to the diversity and controllability of the structure. Therefore, the research of the appropriate POFs material for detecting the amphetamine substances in the urine is of great significance.
Disclosure of Invention
The invention aims to provide an SPME combined Gas Chromatography (GC) which is simple to operate, high in sensitivity and high in accuracy and is used for detecting amphetamine substances in the urine of a drug addict.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
an SPME-GC detection method for amphetamine substances in urine comprises the following steps:
(1) diluting amphetamine and methamphetamine with water to the required concentration to be used as standard working solutions;
(2) taking a standard working solution, sequentially testing the concentration from low to high, placing the standard working solution in a headspace bottle, adjusting the pH value of the solution to 14 by using NaOH, adding 1.5-3mg of NaCl, uniformly stirring, and sealing the headspace bottle;
(3) connecting the PAF-41 coating fiber to a micro sample injection needle of 5 mu L to be used as a solid phase micro extraction fiber;
(4) inserting the solid-phase micro-extraction fiber mentioned in the step (3) into a headspace bottle, pushing out a solid-phase micro-extraction fiber head, placing the solid-phase micro-extraction fiber head at the headspace position of a sample solution, and keeping the temperature for 20-60min at the condition of 40 ℃, wherein the stirring speed is 400-;
(5) the extraction fiber head is drawn back into the micro-sampler, then the micro-sampler is drawn out and is immediately inserted into the gas chromatography sample inlet, and the extraction head is pushed out again, wherein the temperature of the sample inlet is 200-250 ℃, and the interpretation time is 0.5-3 min;
(6) performing gas chromatography separation and ion flame detection (FID) detector detection, and performing linear regression analysis on the measured peak area (y) and the mass concentration (x) of the standard solution to obtain a standard curve equation of each target compound;
(7) taking 1mL of a urine sample containing amphetamine, diluting with water, determining the urine sample according to the test method of the standard working solution in the steps 1-6, determining the retention time, measuring the peak area value of a target object, substituting the peak area value into a standard curve equation, and obtaining the contents of amphetamine and methamphetamine in the sample.
Preferably: the concentration of the standard solution of the amphetamine and methamphetamine is 10,50,100 and 500 mu g/L.
Preferably: the volume of the standard working solution in the step 2 is 5-10 mL.
Preferably: in the step 7, 1mL of the urine sample is diluted to 5-10 mL.
Preferably: the chromatographic conditions are as follows: DB-5MS UI type capillary column (30m x 0.25mm i.d.. times.0.25 μm); he flow rate of carrier gas is 1.0mL/min, and collision gas is N2Flow 40mL/min, syngas (N)2:O279:21) flow rate of 40mL/min, hydrogen flow rate of 400 mL/min; detector temperature 250 ℃, no separation mode for 2 minutes; temperature rising procedure: the initial temperature of 70 ℃ is increased to 250 ℃ at a rate of 10 ℃/min for 10 min.
Preferably: the preparation method of the PAF-41 coating fiber comprises the following steps:
(1) inserting one end of the substrate fiber with the hydroxylated surface into the mixture into the auxiliary glue for 0.5-30 minutes, slowly taking out, inserting into the prepared PAF-41 powder, drying at 50-90 ℃ for 2-60 minutes, and repeating the above operations until the required coating thickness is reached;
(2) finally, aging for 1-5 hours at the temperature of 200-250 ℃ to obtain the SPME extraction fiber.
Preferably: the auxiliary adhesive is polydimethylsiloxane, a prepolymer of polyimide or an ethylene oxide adhesive.
Preferably: the thickness of the coating is 20-100 mu m.
Preferably: the preparation method of the PAF-41 comprises the following steps:
(1) under the protection of nitrogen, bis- (1, 5-cyclooctadiene) nickel and 2, 2-bipyridine are added into a reactor in an equimolar ratio, and then a mixture of 1: 10-1:100 of anhydrous 1, 5-cyclooctadiene and anhydrous N, N-dimethylacetamide, wherein the concentration of bis- (1, 5-cyclooctadiene) nickel is 0.01-0.5 mol.L-1Heating and stirring the mixture at 80-95 ℃ for 0.5-5 hours to activate the catalyst;
(2) in the same way, under the protection of nitrogen, tris (4-bromobenzene) amine is dissolved in anhydrous N, N-dimethylacetamide at the concentration of 0.01-0.1 mol.L-1Stirring for 0.5-5 hours at the temperature of 80-95 ℃;
(3) then, mixing the two solutions, and heating and stirring the whole reaction system at 80-95 ℃ for 72-120 hours;
(4) after the temperature of the reaction system is reduced to room temperature, adding concentrated hydrochloric acid until the color is changed into emerald green, and filtering to obtain a crude product;
(5) washing with distilled water until the solution is neutral, washing the crude product with ethanol and chloroform for 3-10 times to remove unreacted raw materials and catalyst, and vacuumizing at 80-200 deg.C to obtain PAF-41.
Preferably: the other preparation method of the PAF-41 comprises the following steps:
(1) under the protection of nitrogen, anhydrous Lewis acid catalyst is added into a reactor, and anhydrous CHCl is injected3(the concentration of the catalyst is 0.02-0.2 mol. L-1) Stirring for 3 hours at the temperature of 60-90 ℃;
(2) dissolving 1, 3, 5-triphenylamine in anhydrous CHCl3(concentration of 0.02-0.2 mol. L)-1) Then;
(3) injecting the solution in the step (2) into the system in the step (1), wherein the mol ratio of the catalyst to the 1, 3, 5-triphenylamine is 0.4-3: reacting for 1-5 days at the temperature of 5, 60-90 ℃;
(4) after the reaction is finished and the temperature is reduced to room temperature, filtering is carried out, and hydrochloric acid (1-5 mol. L) is respectively used-1) Washing the product with methanol and acetone, and sequentially performing Soxhlet extraction on the product with ethanol, tetrahydrofuran and chloroform for 1-3 days;
(5) finally, vacuumizing at 80-200 ℃ to obtain the PAF-41.
Preferably: the Lewis catalyst is AlCl3，FeCl3，CuCl2
Preferably: the preparation method of the surface hydroxylated substrate fiber comprises the following steps: one end of the base fiber was soaked in sodium hydroxide solution, then excess hydroxide ions were neutralized with hydrochloric acid solution, and finally, the fiber was washed with deionized water and dried in air.
Compared with the prior art, the invention has the following advantages:
(1) the SPME fiber used in the invention is PAF-41 coating fiber, PAF-41 is a novel porous aromatic skeleton material,compared with the commercialized and reported fiber coating, the structural characteristics of the fiber coating enable the fiber coating to have specific selective adsorption performance on the phenylpropylamine and the methamphetamine. This is because: firstly, the adsorbent has a large specific surface area, uniform pore size distribution and good adsorption performance on volatile organic compounds; secondly, the material has high aromaticity, and pi-pi interaction is easily formed between the material and target analytes amphetamine and methamphetamine, so that extraction of the target objects is facilitated; thirdly, the skeleton of the porous material has N atoms, and the absence of-NH in target analysis can be greatly enhanced through a similar compatibility principle, hydrogen bonds and the like2Thereby improving the extraction capacity.
(2) The method does not need pretreatment steps such as solvent extraction and the like, does not need derivatization steps, and is convenient, efficient and quick, and the treatment time is less than 60 min.
Drawings
FIG. 1 chromatogram in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without any inventive step, are within the scope of the present invention.
Example 1
A preparation method of PAF-41 coating fiber comprises the following steps:
(1) under the protection of nitrogen, bis- (1, 5-cyclooctadiene) nickel and 2, 2-bipyridine are added into a reactor in an equimolar ratio, and then anhydrous 1, 5-cyclooctadiene and anhydrous N, N-dimethylacetamide (in a volume ratio of 1: 50) are injected, wherein the concentration of the bis- (1, 5-cyclooctadiene) nickel is 0.16 mol.L-1. The mixture was stirred at 80 ℃ for 1 hour to activate the catalyst.
(2) Under the protection of nitrogen, tris (4-bromobenzene) amine was dissolved in anhydrous N, N-dimethylacetamide at a concentration of 0.014mol·L-1. Stirring at 80 ℃ for 1 hour.
(3) The step 2 solution was injected into the step 1 system and the reaction was stirred at 80 ℃ for 72 hours.
(4) After the reaction was completed and the temperature of the system was reduced to room temperature, concentrated hydrochloric acid (12 mol. L) was added-1) The crude product was filtered off until the color changed to emerald green.
(5) Washing with distilled water until the solution is neutral, and sequentially washing the crude product with ethanol and chloroform for 5 times to remove unreacted raw materials and catalyst. Finally, the PAF-41 is obtained after vacuum pumping is carried out for 12 hours under the condition of 80 ℃.
(6) Adding 300 mu L of methyltrimethoxysilane, 180mg of polydimethylsiloxane at the end of hydroxyl and 30mg of polymethylhydrosiloxane into a centrifuge tube, and carrying out vortex oscillation for 5 minutes. Then 150. mu.L of trifluoroacetic acid (95%) was added and vortexed again for 5 min.
(7) Soaking one end (3cm) of stainless steel fiber (diameter 0.1mm, length 6cm) to concentration of 0.5-2mol.L-1Then, the sodium hydroxide solution is added with the sodium hydroxide solution with the concentration of 0.5-2mol-1Neutralizing redundant hydroxide ions by using a hydrochloric acid solution, and finally, cleaning the fiber by using deionized water and drying in the air to obtain the stainless steel fiber with the hydroxylated surface;
(8) inserting the hydroxylated end of the stainless steel fiber with the hydroxylated surface into the mixture obtained in the step 6 for 5 minutes, slowly taking out, inserting into the PAF-41 powder obtained in the step 5, and drying at 60 ℃ for 2 minutes; this was repeated 3 times until the desired coating thickness of about 60 μm was reached.
(9) And (3) aging the fiber obtained in the step (8) at 240 ℃ for 2 hours to obtain the PAF-41 coating fiber.
Example 2
A preparation method of PAF-41 coating fiber comprises the following steps:
(1) under the protection of nitrogen, bis- (1, 5-cyclooctadiene) nickel and 2, 2-bipyridine are added into a reactor in an equimolar ratio, and then anhydrous 1, 5-cyclooctadiene and anhydrous N, N-dimethylacetamide (in a volume ratio of 1: 10) are injected, wherein the concentration of the bis- (1, 5-cyclooctadiene) nickel is 0.01 mol.L-1. The mixture was stirred at 90 ℃ for 0.5 hour to activate the catalyst.
(2) Under the protection of nitrogen, dissolving tris (4-bromobenzene) amine in anhydrous N, N-dimethylacetamide at a concentration of 0.01 mol.L-1And stirred at 90 ℃ for 0.5 hour.
(3) The step 2 solution was injected into the step 1 system and the reaction was stirred at 90 ℃ for 100 hours.
(4) After the reaction was completed and the temperature of the system was reduced to room temperature, concentrated hydrochloric acid (12 mol. L) was added-1) The crude product was filtered off until the color changed to emerald green.
(5) Washing with distilled water until the solution is neutral, sequentially washing the crude product with ethanol and chloroform for 3 times to remove unreacted raw materials and catalyst, and vacuumizing at 120 deg.C for 10 hr to obtain PAF-41.
(6) One end (1cm) of a quartz fiber (diameter 0.1mm, length 6cm) was immersed to a concentration of 1mol.L-1Then, the sodium hydroxide solution was used at a concentration of 1mol.L-1Neutralizing redundant hydroxide ions by using a hydrochloric acid solution, and finally, cleaning the fiber by using deionized water and drying in the air to obtain quartz fiber with hydroxylated surface;
(7) adding 300 mu L of methyltrimethoxysilane, 180mg of polydimethylsiloxane at the end of hydroxyl and 30mg of polymethylhydrosiloxane into a centrifuge tube, and carrying out vortex oscillation for 5 minutes. Then 150. mu.L of trifluoroacetic acid (95%) was added and vortexed again for 5 min.
(8) Inserting the hydroxylated end of the quartz fiber with the hydroxylated surface into the mixture obtained in the step 7 for 0.5 minute, slowly taking out, inserting into the PAF-41 powder obtained in the step 5, and drying at 50 ℃ for 2 minutes; this was repeated 2 times until the desired coating thickness of about 20 μm was reached.
(9) And (3) aging the fiber obtained in the step (8) at 200 ℃ for 5 hours to obtain the PAF-41 coating fiber.
Example 3
A preparation method of PAF-41 coating fiber comprises the following steps:
(1) under the protection of nitrogen, adding equimolar into a reactorBis- (1, 5-cyclooctadiene) nickel and 2, 2-bipyridine in a molar ratio, followed by injection of anhydrous 1, 5-cyclooctadiene and anhydrous N, N-dimethylacetamide (in a volume ratio of 1: 50), wherein the concentration of bis- (1, 5-cyclooctadiene) nickel is 0.5 mol.L-1. The mixture was stirred at 95 ℃ for 5 hours to activate the catalyst.
(2) Under the protection of nitrogen, dissolving tris (4-bromobenzene) amine in anhydrous N, N-dimethylacetamide at the concentration of 0.1 mol.L-1Stirring at 95 deg.C for 0.5 hr.
(3) The step 2 solution is injected into the step 1 system, and the reaction is stirred at 95 ℃ for 120 hours.
(4) After the reaction was completed and the temperature of the system was reduced to room temperature, concentrated hydrochloric acid (12 mol. L) was added-1) The crude product was filtered off until the color changed to emerald green.
(5) Washing with distilled water until the solution is neutral, sequentially washing the crude product with ethanol and chloroform for 10 times to remove unreacted raw materials and catalyst, and vacuumizing at 200 deg.C for 3 hr to obtain PAF-41.
(6) One end (2cm) of a glass capillary tube having a stainless steel inner core was immersed to a concentration of 2mol-1Then, the sodium hydroxide solution was used at a concentration of 2mol-1Neutralizing redundant hydroxide ions by using a hydrochloric acid solution, and finally, cleaning the fiber by using deionized water and drying in the air to obtain the stainless steel fiber with the hydroxylated surface;
(7) 5mmol of 4, 4-diaminodiphenyl ether was completely dissolved in 20mL of anhydrous N, N-dimethylformamide. Under the condition of ice-water bath, slowly adding 5mmol of pyromellitic dianhydride into the solution while stirring to obtain auxiliary glue, namely the pre-polymerization liquid of polyimide.
(8) Inserting the hydroxylated end of the stainless steel fiber with the hydroxylated surface into the auxiliary glue obtained in the step 7, slowly taking out the auxiliary glue, then inserting the auxiliary glue into the PAF-41 powder obtained in the step 5, and drying the auxiliary glue for 2min at 90 ℃; this was repeated several times until the desired coating thickness of about 80 μm was reached.
(9) Aging the fiber obtained in the step 8 at 250 ℃ for 1 hour to obtain the PAF-41 coating fiber.
Example 4
A preparation method of PAF-41 coating fiber comprises the following steps:
(1) anhydrous aluminum chloride (3.5mmol) was added to a 100mL round bottom flask under nitrogen, followed by injection of 40mL anhydrous CHCl3And stirred at 60 ℃ for 3 hours.
(2)1, 3, 5-triphenylamine (1.5mmol)) was dissolved in 20mL of anhydrous CHCl3。
(3) The step 2 solution was injected into the step 1 system and the reaction was stirred at 60 ℃ for 24 hours.
(4) After the reaction is finished and the temperature of the system is reduced to room temperature, the reaction product is filtered and washed 3 times by hydrochloric acid (1mol/L), methanol and acetone respectively. Then, the product was subjected to soxhlet extraction with ethanol, tetrahydrofuran and chloroform in this order for 2 days.
(5) Vacuum-pumping is carried out for 12 hours at the temperature of 80 ℃, and PAF-41 is obtained.
(6) And dissolving the polydimethylsiloxane in the toluene until the viscosity is moderate, thereby obtaining the auxiliary glue.
(7) Soaking one end (3cm) of a quartz capillary tube with a stainless steel inner core into a sodium hydroxide solution with the concentration of 2mol/L, neutralizing redundant hydroxide ions by using a hydrochloric acid solution with the concentration of 2mol/L, and finally, cleaning fibers by using deionized water and drying in the air to obtain the quartz capillary tube with the hydroxylated surface;
(8) and (3) inserting one end of the quartz capillary tube obtained in the step (7) with the hydroxylated surface into the auxiliary glue obtained in the step (6), slowly taking out the auxiliary glue, inserting the auxiliary glue into the PAF-41 powder obtained in the step (5), and drying the auxiliary glue for 2 minutes at 60 ℃. This was repeated 3 times until the desired coating thickness of about 60 μm was reached.
(9) Aging the fiber obtained in the step 8 at 240 ℃ for 1 hour to obtain the PAF-41 coating fiber.
Example 5
A preparation method of PAF-41 coating fiber comprises the following steps:
(1) under the protection of nitrogen, anhydrous FeCl3(4.5mmol) was added to a 100mL round bottom flask followed by 40mL anhydrous CHCl3And stirred at 60 ℃ for 3 hours.
(2)1, 3, 5-triphenylamine (1.5mmol)) was dissolved in 20mL of anhydrous CHCl3。
(3) The step 2 solution was injected into the step 1 system and the reaction was stirred at 60 ℃ for 24 hours.
(4) After the reaction was completed and the temperature of the system was lowered to room temperature, the mixture was filtered, and then hydrochloric acid (1 mol. L) was added thereto-1) And washing the product for 3 times by using methanol and acetone. Then, the product was subjected to soxhlet extraction with ethanol, tetrahydrofuran and chloroform in this order for 2 days.
(5) Vacuum-pumping is carried out for 12 hours at the temperature of 80 ℃, and PAF-41 is obtained.
(6) One end (3cm) of a quartz capillary tube having a stainless steel inner core was immersed to a concentration of 2mol-1Then, the sodium hydroxide solution was used at a concentration of 2mol-1Neutralizing redundant hydroxide ions by using a hydrochloric acid solution, and finally, cleaning the fiber by using deionized water and drying in the air to obtain a quartz capillary tube with a hydroxylated surface;
(7) adding 300 mu L of methyltrimethoxysilane, 180mg of polydimethylsiloxane at the end of hydroxyl and 30mg of polymethylhydrosiloxane into a centrifuge tube, and carrying out vortex oscillation for 5 minutes. Then 150. mu.L of trifluoroacetic acid (95%) was added and vortexed again for 5 min.
(8) Inserting one end of the quartz capillary tube obtained in the step 6, which is subjected to surface hydroxylation, into the mixture obtained in the step 7 for 5 minutes, then slowly taking out the quartz capillary tube, inserting the quartz capillary tube into the PAF-41 powder obtained in the step 5, and drying the powder at 60 ℃ for 2 minutes. This was repeated 3 times until the desired coating thickness of about 60 μm was reached.
(9) Aging the fiber obtained in the step 8 at 240 ℃ for 1 hour to obtain the PAF-41 coating fiber.
Example 6
A preparation method of PAF-41 coating fiber comprises the following steps:
(1) under the protection of nitrogen, anhydrous CuCl is added2(0.8mmol) was added to a 200mL round bottom flask followed by 40mL anhydrous CHCl3And stirred at 75 ℃ for 3 hours.
(2)1, 3, 5-threeAniline (10mmol)) was dissolved in 50mL anhydrous CHCl3。
(3) The step 2 solution was injected into the step 1 system and the reaction was stirred at 70 ℃ for 72 hours.
(4) After the reaction was completed and the temperature of the system was lowered to room temperature, the mixture was filtered, and then hydrochloric acid (3 mol. L) was added thereto-1) And washing the product for 3 times by using methanol and acetone. Then, the product is subjected to soxhlet extraction by using ethanol, tetrahydrofuran and chloroform in sequence, wherein the extraction time is 1 day.
(5) Vacuum-pumping is carried out for 12 hours at the temperature of 80 ℃, and PAF-41 is obtained.
(6) One end (1cm) of the glass fiber was immersed in 1.5mol.L of the solution-1Then, the sodium hydroxide solution was used at a concentration of 1.5mol.L-1Neutralizing redundant hydroxide ions by using a hydrochloric acid solution, and finally, cleaning the fiber by using deionized water and drying in the air to obtain the glass fiber with the hydroxylated surface;
(7) 4mmol of 4, 4-diaminodiphenyl ether was completely dissolved in 15mL of anhydrous N, N-dimethylformamide. Under the condition of ice-water bath, 4mmol of pyromellitic dianhydride was slowly added to the above solution while stirring to obtain an auxiliary gum, i.e., a pre-polymerization solution of polyimide.
(8) And (3) inserting one end of the glass fiber obtained in the step (6) with the surface hydroxylated into the auxiliary glue obtained in the step (7) for 0.5 minute, slowly taking out, inserting into the PAF-41 powder obtained in the step (5), and drying for 2 minutes at 50 ℃. This was repeated 2 times until the desired coating thickness of about 20 μm was reached.
(9) And (3) aging the fiber obtained in the step (8) at 200 ℃ for 5 hours to obtain the PAF-41 coating fiber.
Example 7
A preparation method of PAF-41 coating fiber comprises the following steps:
(1) anhydrous aluminum chloride (6mmol) was added to a 100mL round bottom flask under nitrogen, followed by 30mL anhydrous CHCl3And stirred at 90 ℃ for 3 hours and then transferred to a 1000ml round bottom flask.
(2)1, 3, 5-triphenylamine (10mmol)) was dissolved in 500mL of anhydrous CHCl3。
(3) The step 2 solution was injected into the step 1 system and the reaction was stirred at 60 ℃ for 24 hours.
(4) After the reaction was completed and the temperature of the system was lowered to room temperature, the mixture was filtered, and then hydrochloric acid (5 mol. L) was added thereto-1) And washing the product for 3 times by using methanol and acetone. Then, the product was subjected to soxhlet extraction with ethanol, tetrahydrofuran and chloroform in this order for 3 days.
(5) Vacuum-pumping is carried out for 12 hours at the temperature of 80 ℃, and PAF-41 is obtained.
(6) One end (1cm) of the quartz fiber is soaked to the concentration of 0.5 mol.L-1Then, the sodium hydroxide solution was added to the reaction solution at a concentration of 0.5 mol. L-1Neutralizing redundant hydroxide ions by using a hydrochloric acid solution, and finally, cleaning the fiber by using deionized water and drying in the air to obtain quartz fiber with hydroxylated surface;
(7) and (3) dissolving the polydimethylsiloxane into the toluene until the viscosity is moderate, so as to obtain the auxiliary glue.
(8) And (3) inserting one end of the quartz fiber obtained in the step (6) with the surface hydroxylated into the auxiliary glue obtained in the step (7) for 30 minutes, slowly taking out, inserting into the PAF-41 powder obtained in the step (5), and drying for 2 minutes at 90 ℃. This was repeated several times until the desired coating thickness of about 100 μm was reached.
(9) Aging the fiber obtained in the step 8 at 230 ℃ for 3 hours to obtain the PAF-41 coating fiber.
Example 8
An SPME-GC detection method for amphetamine substances in urine comprises the following steps:
(1) diluting amphetamine and methamphetamine solutions with concentrations of 1.0mg/mL to 10,50,100,500 μ g/L with water to serve as standard working solutions;
(2) taking 5mL of standard working solution, sequentially testing the concentration from low to high, placing the solution in a headspace bottle, adjusting the pH value of the solution to 14 by using NaOH, adding 1.5mg of NaCl, uniformly stirring, and sealing the headspace bottle;
(3) connecting the PAF-41 coating fiber prepared in the example 1 to a micro-sampling needle of 5 mu L to be used as a solid phase micro-extraction fiber;
(4) inserting the solid-phase microextraction fiber mentioned in (3) into a headspace bottle, pushing out a solid-phase microextraction fiber head, placing the solid-phase microextraction fiber head at a headspace position of a sample solution, and keeping the temperature for 30min at 40 ℃ with the stirring speed of 600 r/min;
(5) drawing the extraction fiber head back into the microinjector, then drawing out the microinjector, immediately inserting the microinjector into the gas chromatography sample inlet, and pushing out the extraction head again, wherein the temperature of the sample inlet is 240 ℃, and the interpretation time is 0.5 min;
(6) and (3) performing gas chromatography separation and ion flame detector (FID) detection, and performing linear regression analysis on the measured peak area (y) and the mass concentration (x) of the standard solution to obtain a standard curve equation of each target compound. The chromatographic conditions are as follows: DB-5MS UI type capillary column (30m x 0.25mm i.d.. times.0.25 μm). The flow rate of the carrier gas He is 1.0mL/min, and the collision gas N2Flow rate of 40mL/min2:O279:21) flow rate was 40mL/min and hydrogen flow rate was 400 mL/min. The detector temperature was 250 ℃ without separation mode for 2 minutes. Temperature rising procedure: the initial temperature of 70 ℃ is increased to 250 ℃ at a rate of 10 ℃/min for 10 min.
(7) Taking 1mL of a urine sample containing amphetamine, diluting the urine sample to 5mL by using water, determining the urine sample according to the test method of the standard working solution in the steps 1-6, determining the urine sample by using retention time, measuring a peak area value of a target object, substituting the peak area value into a standard curve equation, and obtaining the contents of amphetamine and methamphetamine in the sample.
The results are shown in tables 1 and 2, and the chromatograms are shown in FIG. 1.
Table 1 linear range, correlation coefficient, detection limit and repeatability of the method.
TABLE 2 actual sample determination and recovery
Example 9
An SPME-GC detection method for amphetamine substances in urine comprises the following steps:
(1) diluting amphetamine and methamphetamine solutions with concentrations of 1.0mg/mL to 10,50,100,500 μ g/L with water to serve as standard working solutions;
(2) taking 8mL of standard working solution, sequentially testing the concentration from low to high, placing the solution in a headspace bottle, adjusting the pH value of the solution to 14 by using NaOH, adding 2.4mg of NaCl, uniformly stirring, and sealing the headspace bottle;
(3) connecting the PAF-41 coating fiber prepared in the example 1 to a micro-sampling needle of 5 mu L to be used as a solid phase micro-extraction fiber;
(4) inserting the solid-phase microextraction fiber mentioned in the step (3) into a headspace bottle, pushing out a solid-phase microextraction fiber head, placing the solid-phase microextraction fiber head at a headspace position of a sample solution, and keeping the temperature for 20min at 40 ℃ with the stirring speed of 400 r/min;
(5) drawing the extraction fiber head back into the microinjector, then drawing out the microinjector, immediately inserting the microinjector into the gas chromatography sample inlet, and pushing out the extraction head again, wherein the temperature of the sample inlet is 220 ℃, and the interpretation time is 3 min;
(6) and (3) performing gas chromatography separation and ion flame detector (FID) detection, and performing linear regression analysis on the measured peak area (y) and the mass concentration (x) of the standard solution to obtain a standard curve equation of each target compound. The chromatographic conditions are as follows: DB-5MS UI type capillary column (30m x 0.25mm i.d.. times.0.25 μm). The flow rate of the carrier gas He is 1.0mL/min, and the collision gas N2Flow rate of 40mL/min2:O279:21) flow rate was 40mL/min and hydrogen flow rate was 400 mL/min. The detector temperature was 250 ℃ without separation mode for 2 minutes. Temperature rising procedure: the initial temperature of 70 ℃ is increased to 250 ℃ at a rate of 10 ℃/min for 10 min.
(7) Taking 1mL of a urine sample containing amphetamine, diluting the urine sample to 8mL by using water, determining the urine sample according to the test method of the standard working solution in the steps 1-6, determining the urine sample by using retention time, measuring a peak area value of a target object, substituting the peak area value into a standard curve equation, and obtaining the contents of amphetamine and methamphetamine in the sample.
Specific results are shown in tables 3 and 4.
Table 3 linear range, correlation coefficient, detection limit and repeatability of the method.
TABLE 4 actual sample determination and recovery
Example 10
An SPME-GC detection method for amphetamine substances in urine comprises the following steps:
(1) the amphetamine and methamphetamine solutions at concentrations of 1.0mg/mL were diluted with water to the desired concentrations as standard solutions ((10,50,100, 500. mu.g/L));
(2) taking 10mL of standard working solution, sequentially testing the concentration from low to high, placing the solution in a headspace bottle, adjusting the pH value of the solution to 14 by using NaOH, adding 3mg of NaCl, uniformly stirring, and sealing the headspace bottle;
(3) the PAF-41 coating fiber prepared in the example 4 is connected to a micro-sampling needle of 5 mu L to be used as a fiber of a solid phase micro-extraction device;
(4) inserting the solid-phase microextraction fiber mentioned in (3) into a headspace bottle, pushing out a solid-phase microextraction fiber head, placing the solid-phase microextraction fiber head at a headspace position of a sample solution, and keeping the temperature for 60min at 40 ℃ with the stirring speed of 500 r/min;
(5) drawing the extraction fiber head back into the microinjector, then drawing out the microinjector, immediately inserting the microinjector into the gas chromatography sample inlet, and pushing out the extraction head again, wherein the temperature of the sample inlet is 250 ℃, and the interpretation time is 1 min;
(6) and (3) performing gas chromatography separation and ion flame detector (FID) detection, and performing linear regression analysis on the measured peak area (y) and the mass concentration (x) of the standard solution to obtain a standard curve equation of each target compound. The chromatographic conditions are as follows: DB-5MS UI type capillary column (30m x 0.25mm i.d.. times.0.25 μm). The flow rate of the carrier gas He is 1.0mL/min,collision gas N2Flow rate of 40mL/min2:O279:21) flow rate was 40mL/min and hydrogen flow rate was 400 mL/min. The detector temperature was 250 ℃ without separation mode for 2 minutes. Temperature raising procedure: the initial temperature of 70 ℃ is increased to 250 ℃ at a rate of 10 ℃/min for 10 min.
(7) Taking 1mL of a urine sample containing amphetamine, diluting the urine sample to 10mL by using water, determining the urine sample according to the test method of the standard working solution in the steps 1-6, determining the urine sample by using retention time, measuring a peak area value of a target object, substituting the peak area value into a standard curve equation, and obtaining the contents of amphetamine and methamphetamine in the sample.
Specific results are shown in tables 5 and 6.
Table 5 linear range, correlation coefficient, detection limit and repeatability of the method.
TABLE 6 actual sample determination and recovery
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (6)
1. The SPME-GC detection method for the amphetamine substances in the urine is characterized by comprising the following steps of:
(1) diluting the amphetamine and methamphetamine solutions with water to the required concentration as standard working solutions;
(2) taking a standard working solution, sequentially testing the concentration from low to high, placing the standard working solution in an SPME headspace bottle, adjusting the pH value of the solution to 14 by using NaOH, adding 1.5-3mg of NaCl, uniformly stirring, and sealing the headspace bottle;
(3) connecting the PAF-41 coating fiber to a 5 mu L micro sample injection needle to be used as SPME fiber;
(4) inserting the SPME fiber mentioned in the step (3) into a headspace bottle, pushing out a fiber head, placing the fiber head at the headspace position of the sample solution, and keeping the temperature for 20-60min at the condition of 40 ℃ with the stirring speed of 400-;
(5) drawing the fiber head back into the micro sample injection needle, then drawing out, immediately inserting into the gas chromatography sample injection port, and pushing out the extraction head again, wherein the temperature of the sample injection port is 200-250 ℃, and the desorption time is 0.5-3 min;
(6) performing gas chromatography separation and ion flame detection (FID) detector detection, and performing linear regression analysis on the measured peak area y and the mass concentration x of the standard solution to obtain a standard curve equation of each target compound;
(7) taking a urine sample containing amphetamine, diluting with water, determining the urine sample according to the test method of the standard working solution in the steps (1) - (6), determining the urine sample by using retention time, determining a peak area value of a target object, substituting the peak area value into a standard curve equation, and obtaining the contents of amphetamine and methamphetamine in the sample;
the preparation method of the PAF-41 coating fiber comprises the following steps:
(1) inserting one end of the base fiber with the hydroxylated surface into the auxiliary glue, slowly taking out the base fiber, inserting the base fiber into the prepared PAF-41 powder, drying the base fiber at 50-90 ℃ for 2-60 minutes, and repeating the operation until the required coating thickness is reached;
(2) finally, aging for 1-5 hours at the temperature of 200-250 ℃ to obtain SPME extraction fiber;
(3) the auxiliary adhesive is polydimethylsiloxane, a prepolymer of polyimide or an ethylene oxide adhesive;
the preparation method of the PAF-41 comprises the following steps:
(1) under the protection of nitrogen, bis- (1, 5-cyclooctadiene) nickel and 2, 2-bipyridine are added into a reactor in an equimolar ratio, and then a mixture of 1: 10-1:100 of anhydrous 1, 5-cyclooctadiene and anhydrous N, N-dimethylacetamide, wherein the concentration of bis- (1, 5-cyclooctadiene) nickel is 0.01-0.5 mol/L, and the mixture is heated and stirred at 80-95 ℃ for 0.5-5 hours to activate the catalyst;
(2) similarly, under the protection of nitrogen, dissolving tris (4-bromobenzene) amine in anhydrous N, N-dimethylacetamide at the concentration of 0.01-0.1mol/L, and stirring at 80-95 ℃ for 0.5-5 hours;
(3) then, mixing the two solutions, and heating and stirring the whole reaction system at 80-95 ℃ for 72-120 hours;
(4) after the temperature of the reaction system is reduced to room temperature, adding concentrated hydrochloric acid until the color is changed into emerald green, and filtering to obtain a crude product;
(5) washing with distilled water until the solution is neutral, washing the crude product with ethanol and chloroform for 3-10 times to remove unreacted raw materials and catalyst, and vacuumizing at 80-200 deg.C to obtain PAF-41;
the chromatographic conditions are as follows: DB-5MS UI type capillary column 30m × 0.25mm i.d. × 0.25 μm; the flow rate of the carrier gas He is 1.0mL/min, and the collision gas N2Flow rate of 40mL/min. Synthesis gas N2:O2The flow rate of 21 is 40mL/min, and the flow rate of hydrogen is 400 mL/min; the temperature of the detector is 250 ℃, and the non-shunting mode lasts for 2 minutes; temperature rising procedure: raising the initial temperature of 70 ℃ to 250 ℃ at the speed of 10 ℃/min and keeping the temperature for 10 min; the thickness of the coating is 20-100 mu m.
2. The SPME-GC detection method for amphetamine-type substances in urine as claimed in claim 1, wherein the SPME-GC detection method comprises the following steps: the concentration of the standard working solution of the amphetamine and methamphetamine is 10,50,100 and 500 mu g/L.
3. The SPME-GC detection method for amphetamine-type substances in urine as claimed in claim 1, wherein the SPME-GC detection method comprises the following steps: and (3) the volume of the standard working solution in the step (2) is 5-10 mL.
4. The SPME-GC detection method for amphetamine-type substances in urine as claimed in claim 1, wherein the SPME-GC detection method comprises the following steps: in the step (7), the volume of the urine is 1mL, and the urine is diluted to 5-10 mL.
5. The SPME-GC detection method for amphetamine-type substances in urine as claimed in claim 1, wherein the SPME-GC detection method comprises the following steps: the preparation method of the PAF-41 comprises the following steps:
(1) under the protection of nitrogen, anhydrous Lewis acid catalyst is added into a reactor, and anhydrous CHCl is injected3The concentration is 0.02-0.2 mol/L, and the mixture is stirred for 3 hours at the temperature of 60-90 ℃;
(2) dissolving 1, 3, 5-triphenylamine in anhydrous CHCl3The concentration is 0.02-0.2 mol/L;
(3) injecting the solution in the step (2) into the system in the step (1), wherein the mol ratio of the catalyst to the 1, 3, 5-triphenylamine is 0.4-3:5, and the reaction lasts for 1-5 days at the temperature of 60-90 ℃;
(4) after the reaction is finished and the temperature is reduced to room temperature, filtering, washing the product by 1-5 mol/L hydrochloric acid, methanol and acetone respectively, and then performing soxhlet extraction on the product by ethanol, tetrahydrofuran and chloroform in sequence for 1-3 days;
(5) finally, vacuumizing at 80-200 ℃ to obtain the PAF-41.
6. The SPME-GC detection method for amphetamine-type substances in urine as claimed in claim 1, wherein the SPME-GC detection method comprises the following steps: the preparation method of the surface hydroxylated substrate fiber comprises the following steps: one end of the base fiber was soaked in sodium hydroxide solution, then excess hydroxide ions were neutralized with hydrochloric acid solution, and finally, the fiber was washed with deionized water and dried in air.
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