CN111105980B - Flash thermal analysis-time-delay purging sample introduction method for drug mixture detection - Google Patents
Flash thermal analysis-time-delay purging sample introduction method for drug mixture detection Download PDFInfo
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- CN111105980B CN111105980B CN201811249038.7A CN201811249038A CN111105980B CN 111105980 B CN111105980 B CN 111105980B CN 201811249038 A CN201811249038 A CN 201811249038A CN 111105980 B CN111105980 B CN 111105980B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
- H01J49/0468—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample
- H01J49/049—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample with means for applying heat to desorb the sample; Evaporation
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/64—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode using wave or particle radiation to ionise a gas, e.g. in an ionisation chamber
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/0027—Methods for using particle spectrometers
- H01J49/0031—Step by step routines describing the use of the apparatus
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
- H01J49/0459—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for solid samples
Abstract
The invention discloses a flash thermal analysis-delay purge sampling method for rapidly and simultaneously detecting volatile and difficultly volatile drug mixtures. The drugs have various types and large differences in structure and molecular weight, and the drugs are not volatile, so that the sensitivity of a drug detection instrument adopting thermal desorption sampling can be reduced, and the detection and identification efficiency of the opium or the new psychoactive drug mixture can be influenced. The analysis method solves the problem of rapid and simultaneous detection of volatile-difficult-to-volatile drug mixtures, and the analysis method utilizes a halogen lamp to perform 'flash heating', so that the drug mixtures are rapidly heated, and the vapor pressure of mixed samples is improved, thereby improving the ionization efficiency at normal pressure, and improving the signal intensity of the difficult-to-volatile samples in the mixtures by more than one order of magnitude. Combine the device that time delay was swept, realized sweeping the difficult volatility and the volatile matter that volatilizees out when will flashing heat simultaneously and get into the ionization chamber, reduced the loss of sweeping heating process in succession the sample, realized the simultaneous detection of difficult volatility and the volatile drugs both.
Description
Technical Field
The invention relates to a mass spectrometer, which essentially adopts a halogen lamp to simultaneously heat a mixture of volatile drugs and drugs which are difficult to volatilize, and can greatly increase the saturated vapor pressure of the drugs which are difficult to volatilize in the drug mixture, thereby improving the ionization efficiency of the drugs and improving the signal intensity of samples which are difficult to volatilize by more than one order of magnitude. The device is swept in the time delay of installation, has realized sweeping the difficult volatile and volatile drugs that volatilize out when will flashing heat simultaneously and has got into the ionization chamber, has reduced the loss of sweeping of sample in the heating process in succession.
Background
The common mixture instrument analysis method mainly combines a certain pretreatment method with the separation technology of chromatography. Chromatographic techniques include primarily Gas Chromatography (GC) and Liquid Chromatography (LC), and often require tandem mass spectrometry for further identification in the backend in order to further identify the separated material.
Gas chromatography, as the name implies, is a method for separation and analysis by converting components into gaseous state through a specific chromatographic column, and is the most dominant method for component analysis of complex mixtures today, because it can achieve extremely high resolution and recovery rate through modification of the chromatographic column or derivatization of the analyte. However, the chromatographic column is limited by materials and detectors of instruments, etc., and generally the column temperature does not rise above 350 ℃. This greatly limits the separation and analysis of the gas chromatography for the non-volatile high boiling point substances, and for this reason, two main solutions have been developed, namely pre-column derivatization to convert the substances into low boiling point substances, or identification analysis by means of cracked fragments of the substances using a cracked gas chromatography (PyGC-MS) that can heat the substances to a high temperature of 500 to 600 ℃. The disadvantage of the derivatization method is that not all substances are suitable for derivatization, and that more severe derivatization methods require extensive pretreatment times and steps.
The cracking gas chromatography is very suitable for analyzing high molecular compounds with high boiling points and extremely difficult volatilization. However, the disadvantage is that the mass spectrum generated after the lysis is very complicated and difficult to identify, and the temperature programming process also consumes a lot of time. Liquid chromatography analysis is undoubtedly a good solution for some mixtures with high polarity and difficult volatilization, but we know that liquid chromatography, especially a liquid chromatography mass spectrometer has a large volume, and meanwhile, a large amount of elution solvent needs to be consumed, a certain retention time is needed, and rapid field analysis of the mixtures cannot be realized.
In recent years, with the development of various atmospheric pressure ionization sources, mass spectra which are qualitative "gold standards" of substances can be used alone to perform rapid component analysis of mixtures without complicated pretreatment. But how to quickly ionize matter efficiently by the ionization source becomes another problem.
The method has the advantages of high speed, simple structure, high efficiency and the like by analyzing the sample through the heated heat, and is a common method before the front-end normal-pressure ionization source ionizes the gaseous sample. This is because the sample molecules in a gaseous state have higher ionization efficiency than the sample molecules in a solid state in which the intermolecular interaction is extremely large and in a liquid state subjected to solvation, and are suitable for various chemical ionization sources which have been developed at present. However, it has the disadvantage that thermal analysis is affected by the volatility and matrix of the sample, and the presence of a sample that is difficult to volatilize can affect the order of the results of the assay of the mixture and also affect the quantification of the components of the mixture.
The traditional thermal desorption sample injection heating mode comprises the following steps: metal block heating, laser heating, curie point heating, and the like. The metal block heating is essentially a method for heating a sample by utilizing air heat conduction and heat radiation, although the realization is simpler, the temperature rising speed is slow, the heating time is longer, the release efficiency difference of a high-boiling point sample and a low-boiling point sample is larger, the defects of sample residue and high power consumption exist, and more requirements are provided for the material and device heat dissipation of an instrument due to continuous high-temperature heating.
The laser heating has high temperature rise speed, so that the sample can be released instantly, but the heating mode is limited by the high price of the instrument. The Curie point heating can heat the sample to the Curie point temperature in the twinkling of an eye, the heating rate is fast, the temperature accuracy is high, but the Curie point hot foil needs to be replaced when the heating temperature is changed, and the operation is troublesome.
Therefore, the invention designs the light flash thermal analysis-time-delay purging sample introduction device and the analysis method for quickly and simultaneously detecting the volatile/difficult-to-volatile drug mixture, and solves the difficult problems of quickly and simultaneously detecting the volatile/difficult-to-volatile drug mixture. In this apparatus, a halogen lamp is disposed directly above a quartz optical lens, and light is irradiated through the lens onto a piece of tetrafluoro paper on which a sample is dropped to heat the piece of tetrafluoro paper, and pulse heating or continuous heating can be performed. The flash heat of the halogen lamp can reach a high temperature of 200 ℃ in the vicinity of the focal point of the halogen lamp within about 2 s. The halogen lamp light flash heat has the advantages of high temperature rising speed, high concentration of analyzed samples, no residue of the samples, low power consumption and the like. The sample is heated by adopting the flash heat of the halogen lamp, so that the saturated vapor pressure of the solid sample can be increased, the ionization efficiency is improved, and the signal intensity of the sample is improved by more than one order of magnitude.
Simultaneously, the device is swept in the time delay of installation, has realized once only sweeping the volatile and difficult volatile drugs that volatilize out when will flash heat and has got into the ionization chamber, has reduced the loss that the heating process sample was swept in succession to the tradition.
Disclosure of Invention
The invention aims to provide a method for rapidly and simultaneously detecting volatile and difficultly volatile drug mixtures.
In order to achieve the purpose, the invention adopts the technical scheme that:
the system comprises a mass spectrometer, a radio frequency lamp, a tetrafluoro seal sleeve, a halogen lamp, a quartz optical lens, a peek cavity, sample injection tetrafluoro cloth, a metal heating block, an ionization cavity, a three-way valve and three gas paths, wherein a residue removal purging gas path, a sample injection purging gas path and an acetone carrier gas path are arranged; the halogen lamp and the quartz optical lens are coaxial, the halogen lamp is positioned right above the sample PTFE cloth, and the focus of the halogen lamp is positioned in the peek cavity and falls on the PTFE sample cloth.
The peek chamber is a hollow cylinder with an open upper end, and a quartz optical lens is arranged at the open end of the upper surface of the peek chamber, and the upper surface of the quartz optical lens faces the halogen lamp. The surface of the peek cavity is provided with two inlets and an outlet, one strip-shaped inlet is used for inserting the PTFE sample inlet cloth, the other round hole inlet is used for sample introduction and sweeping air inlet of an air path, and the round hole outlet is connected with the ionization cavity. The gas inlet of the sample injection purging gas circuit is coaxially opposite to the gas outlet connected with the ionization chamber, but the diameter of the gas outlet is slightly larger than that of the gas inlet.
The ionization cavity is a closed hollow cavity, a radio frequency lamp is arranged on the side wall surface of the ionization cavity, light emitted by the radio frequency lamp irradiates the ionization cavity, and an air inlet leading to the peek cavity, an air inlet leading to the residue removing and purging air passage and an air outlet leading to the rear-end detection instrument are arranged on the side wall surface of the ionization cavity.
The internal diameter of the peek cavity is 30mm, the height of the peek cavity is 10mm, the inlet connected with the sample injection purging gas circuit is a threaded hole of M3, and the diameter of the outlet connected with the ionization cavity is 4 mm. The top is provided with a quartz optical lens which is sealed by a silica gel pad, and the bottom can be inserted with a rectangular tetrafluoro sampling cloth with the thickness of 1 mm. And a metal heating block is arranged at the bottom of the Peek cavity and used for preheating the Peek cavity.
The three-way valve is a gas path switching device which can be automatically controlled through a time sequence and is used for switching continuous gas flow from residual removal purging to sample introduction purging.
Before inserting into the sample PTFE cloth, the gas circuit in the three-way valve is in the residue removing and purging gas circuit for removing the residual sample in the device. When the tetrafluoro cloth is inserted into the peek cavity from the slot, the halogen lamp controlled by the time sequence can be automatically started, the halogen lamp light enters the peek cavity through the quartz optical lens and irradiates the sample tetrafluoro cloth, and the sample on the sample tetrafluoro cloth is analyzed through the light flash thermal decomposition. Then, at the moment when the halogen lamp is extinguished, the three-way valve of the time sequence control is automatically switched to a sample injection purging gas circuit, and simultaneously, a sample is purged into the ionization cavity to be ionized, and finally, the sample is detected by a detection instrument at the tail end. And after the sample introduction is finished, the gas path is switched to the residual-removing purging gas path again.
The light source adopted by the flash analysis is a halogen lamp, the power is 75W, the halogen lamp is required to have a light focusing function, the flash time of the halogen lamp is adjustable by using a controller, and the flash time of the halogen lamp is 2s according to the volatilization difficulty condition of a sample; the temperature of the halogen light at a focusing spot with the diameter of 2mm can reach more than 250 ℃ after the halogen light is flashed for 2s, and the temperature can reach 500 ℃ after the halogen light is continuously heated to 7 s.
The quartz optical lens is a high-temperature-resistant high-light-transmittance quartz optical lens, and the light of the halogen lamp can be projected on the tetrafluoro sampling cloth through the lens. In order to ensure higher light transmittance, the thickness used is 1.8 mm; meanwhile, the distance between the lamp holder of the halogen lamp and the tetrafluoro sample cloth is adjusted according to the focal length of the halogen lamp, and then the distance between the halogen lamp and the tetrafluoro sample cloth is finely adjusted according to the size of the sample spot on the tetrafluoro sample cloth, so that the radius of the focal point on the tetrafluoro sample cloth is equal to the radius of the sample spot.
The gas outlet of the device is a round hole with the inner diameter of 3mm, the gas outlet of the device is positioned on the ionization cavity, the inside of the ionization cavity is also a hollow cylinder, the inner diameter is 8, the height is 10, the volume of the ionization cavity is 0.5mL, and the gas outlet of the device can be connected with a mass spectrum detection device at the rear end. The ionization chamber is connected with the inlet of the residue removing and purging gas circuit and can be used for purging residual samples in the ionization region when no sample is introduced, and simultaneously, acetone reagent ions are supplemented in the ionization region, and the acetone reagent ions have a great promotion effect on chemical ionization of auxiliary drugs.
The sample-injection teflon cloth is made of polytetrafluoroethylene, a sample is placed at a specific position of the sample-injection cloth through a 1 mu L sample-injection needle, or the sample is directly wiped by the teflon cloth and then inserted into the peek cavity, so that the position stained with the sample is close to the focal position of the halogen lamp, and the halogen lamp light can be projected to the position stained with the sample through the quartz optical lens.
The rapid simultaneous detection optical flash heating-time-delay purging sample introduction method for the drug mixture works according to a specific time sequence, and comprises the following specific steps:
(1) the ionization source of the radio frequency lamp (4) is opened, and the three-way valve is positioned in the residue removing and purging gas circuit at the moment;
(2) injecting sample into the tetrafluoro cloth: inserting the black sample-injection tetrafluoro cloth (7) stained with the sample into the heatable thermal desorption micro-area (5);
(3) turning on a halogen lamp: the halogen lamp (2) controlled by the time sequence can be automatically turned on for a period of time and then turned off, and at the moment, the steam phase of the sample subjected to flash thermal desorption can temporarily stay in the peek cavity;
(4) and (3) switching a three-way valve: when the halogen lamp is extinguished, the three-way valve of the time sequence control can immediately switch the gas path from the residue removing purging gas path (11) to the sample introduction purging gas path (12), so that the sample steam of the nonvolatile and volatile sample volatilized from the peek cavity is purged into the ionization cavity (9) at the same time;
(5) sampling by an analytical instrument: the analysis and detection instrument at the air outlet of the device guides the ions in the ionization cavity (9) into the instrument;
(6) analytical instrument signal: analyzing and recording the signal intensity of the sample detected by the instrument;
(7) removing residues: taking out the tetrafluoro sample cloth, and simultaneously switching the three-way valve to a residue removing and purging gas circuit;
the volume flow of the time-delay purging gas can be controlled by adjusting the flow of the acetone carrier gas at the front end of the three-way valve, the use of the flow of the acetone carrier gas of the time-delay purging gas is too large or too small, which is unfavorable, the too large easily causes that the sample is not ready to be detected and then to be purged, the too small easily causes that the transmission efficiency of the sample is too low, and the flow of the used acetone carrier gas is 500 mL/min.
The invention has the advantages that:
the device of the invention utilizes the halogen lamp to carry out flash heating and combines time-delay blowing and sample introduction, and has the following main advantages:
1) the temperature rise speed is high, and the concentration of the analyzed sample is high, so that the sample injection amount in unit time is increased, and the detection sensitivity is improved;
2) low sample residue and low power consumption.
3) The sample blowing loss is avoided when the temperature is continuously raised, the thermal analysis area is blown out, and the rapid simultaneous detection of volatile and nonvolatile drug mixtures is realized.
The invention can increase the saturated vapor pressure of the solid sample, thereby improving the ionization efficiency and improving the signal intensity of the sample by more than one order of magnitude compared with the signal intensity of the sample heated by common metal.
Drawings
FIG. 1 is a diagram of a halogen lamp flash desorption-time-delay purging sample injection device
FIG. 2 is a timing diagram of the operation of the halogen lamp flash desorption-time-delay purging sample injection device
FIG. 3 is a mass spectrum of a 1ng remifentanil ion trap obtained by 2s flash thermal desorption using halogen lamp light
FIG. 4 is a mass spectrum of 1ng narcotine ion trap obtained by 2s flash desorption using halogen lamp light
FIG. 5 shows the results of mass spectrometry detection of ion traps using halogen lamp flash desorption continuous purge with time for the ten drug combinations in Table 2
FIG. 6 shows the results of mass spectrometry of ion traps with time variation of the ten drugs in Table 2 using halogen lamp flash desorption-time delay purge
Detailed Description
Fig. 1 is a diagram of a flash thermal desorption-time-delay purging sample injection device, and fig. 2 is a working timing diagram of the device. The sample-injection tetrafluoro cloth is made of polytetrafluoroethylene, the thickness of the sample-injection tetrafluoro cloth is 1mm, and a sample dissolved in a solvent is spotted on the tetrafluoro sample-injection cloth through a sample-injection needle of 1 mu L or the surface of the sample is directly wiped through the tetrafluoro cloth. The position stained with the sample is close to the focal position of the halogen lamp, and the halogen lamp light can be projected to the position stained with the sample through the quartz optical lens.
The halogen lamp is positioned right above the quartz optical lens and the tetrafluoro sample cloth, a sample spot with the diameter of 2mm on the tetrafluoro sample cloth is heated, the diameter of a focusing spot is 2mm, the distance between the quartz optical lens and the halogen lamp is about 35mm (namely the focal length of the halogen beam heating lamp LCB-50), the halogen lamp heats the sample continuously, and the heating time is 2 s.
The method for rapidly and simultaneously detecting the flash heating and the delayed purging sample injection of the drug mixture works according to a specific time sequence, as shown in fig. 2, and comprises the following specific steps:
(1) the ionization source of the radio frequency lamp (4) is opened, and the three-way valve is positioned in the residue removing and purging gas circuit at the moment;
(2) injecting sample into the tetrafluoro cloth: inserting the black sample-injection tetrafluoro cloth (7) stained with the sample into the heatable thermal desorption micro-area (5);
(3) turning on a halogen lamp: the halogen lamp (2) controlled by the time sequence can be automatically turned on for a period of time and then turned off, and at the moment, the steam phase of the sample subjected to flash thermal desorption can temporarily stay in the peek cavity;
(4) and (3) switching a three-way valve: when the halogen lamp is extinguished, the three-way valve of the time sequence control can immediately switch the gas path from the residue removing purging gas path (11) to the sample introduction purging gas path (12), so that the sample steam of the nonvolatile and volatile sample volatilized from the peek cavity is purged into the ionization cavity (9) at the same time;
(5) sampling by an analytical instrument: the analysis and detection instrument at the air outlet of the device guides the ions in the ionization cavity (9) into the instrument;
(6) analytical instrument signal: analyzing and recording the signal intensity of the sample detected by the instrument;
(7) removing residues: taking out the tetrafluoro sample cloth, and simultaneously switching the three-way valve to a residue removing and purging gas circuit;
example 1
The above method was applied by spotting 1. mu.g/mL of narcotine on a tetrafluoro cloth through a 1. mu.L needle with an absolute mass of 1ng, and then inserting the tetrafluoro cloth into the apparatus shown in FIG. 1. Fig. 3 is an ion trap mass spectrum of 1ng remifentanil obtained by using halogen lamp flash desorption-time-lapse purge sample injection, wherein the flash time of the halogen lamp is 2s, and the intensity can reach about 400.
FIG. 4 is a mass spectrum of an ion trap of 1ng narcotine obtained by halogen lamp flash desorption-time delay purge injection by the same method, wherein the flash time of the halogen lamp is 2s, and the intensity can also reach about 400.
Example 2
The above method is applied, and 10 mixtures of drugs with different boiling points are prepared, wherein table 1 shows their absolute mass and molecular weight, and fig. 5 shows the detection results of the ten mixtures of drugs with different boiling points after the teflon cloth is inserted into the peek cavity, i.e. the time change in step (5) in the working timing chart 2, when the mixture is subjected to halogen lamp flash desorption-time-delay purge sample injection. It can be seen that ten drug mixtures can be detected at the same time from the 0 th s, and the ten drugs have higher intensity in 0-3 s, so that the aim of simultaneously detecting and identifying a plurality of drug mixtures which are difficult to volatilize and volatile is fulfilled.
TABLE 1 Ten drug mixtures
Comparative example
The difference from the embodiment 2 is that the traditional halogen light flash-continuous purging sample injection is used, that is, while the halogen light heats the sample, the volatilized sample is continuously blown into the ionization cavity by the sample injection purging gas circuit to be ionized, and then is detected by the ion trap mass spectrum connected in series at the tail end. It can be seen that methamphetamine, MDMA, ketamine, cocaine and tetrahydrocannabinol with low boiling points are detected firstly in 0-3 s, while the signals of the drugs difficult to volatilize appear sequentially after 3s, and the intensity can only reach about 200 at most. This demonstrates that the use of halogen lamp flash-time-delay purge injection is advantageous for the simultaneous detection of the mixture of hard and volatile drugs, which helps the law enforcement officers to quickly screen and identify the accurate drugs on site.
Claims (11)
1. A flash thermal analysis-delay purging sample introduction method for detecting a drug mixture is characterized by comprising the following steps:
the adopted device comprises a hollow and sealed peek cavity (6), a through hole is formed in the upper end of the peek cavity (6), a quartz optical lens (5) is arranged in the through hole, and the peripheral edge of the quartz optical lens (5) is hermetically connected with the inner wall surface of the through hole; through holes which are used as a sample injection scavenging gas inlet and a sample gas outlet are respectively formed in the left side wall surface and the right side wall surface of the peek cavity (6), and the sample injection scavenging gas inlet is connected with a first interface of the three-way valve through a sample injection scavenging gas path (12); an electrically heated metal heating block (8) is arranged at the bottom in the peek cavity (6), a gap for the inlet and outlet of the PTFE sample injection cloth (7) is formed in the side wall surface of the middle lower part of the peek cavity (6), and the PTFE sample injection cloth (7) can be inserted above the metal heating block (8) in the cavity through the gap; a halogen lamp (4) is arranged above the peek cavity, and a light outlet of the halogen lamp (4) faces the quartz optical lens (5);
the ionization cavity (9) is a closed hollow cavity, the upper wall surface of the ionization cavity is provided with a radio frequency lamp (2), light emitted by the radio frequency lamp (2) irradiates the cavity, the lower wall surface of the ionization cavity is provided with a residue removing purging gas inlet connected with a second interface of the three-way valve through a residue removing purging gas circuit, the left side wall surface and the right side wall surface of the ionization cavity are respectively provided with a gas outlet and a gas inlet, and the gas inlets are connected with a sample gas outlet of the peek cavity (6); the air outlet (14) is connected with a detection instrument; the third interface of the three-way valve is connected with a carrier gas source through a carrier gas path; the volume flow of the delayed purge gas is controlled by adjusting the flow of an acetone carrier gas (13) at the front end of the three-way valve, the delayed purge gas is unfavorable to use too large or too small of the flow of the acetone carrier gas, the too large of the flow easily causes that a sample is not detected and is purged away, the too small of the flow easily causes that the transmission efficiency of the sample is too low, and the flow of the used acetone carrier gas is 500 mL/min-800 mL/min.
2. The method of claim 1, wherein:
the halogen lamp (4) and the quartz optical lens (5) are coaxial, the halogen lamp (4) is positioned right above the sample-injection tetrafluoro sample-injection cloth (7), the focus of the halogen lamp (4) is positioned in the peek cavity (6) and falls on the tetrafluoro sample-injection cloth (7), and the detecting instrument (1) at the rear end is a mass spectrometer or a mobility spectrometer; the carrier gas (13) is acetone saturated air.
3. The method of claim 1, wherein:
the peek cavity (6) is a hollow cylinder with an opening at the upper end and a closed lower end, the opening end of the upper surface of the peek cavity is provided with a quartz optical lens (5), the upper surface of the quartz optical lens faces the halogen lamp (4), the bottom of the peek cavity (6) is provided with a metal heating block (8) with the highest constant temperature of 200 ℃, and the peek cavity is preheated; the surface of the peek cavity (6) is provided with two inlets and an outlet, one strip-shaped inlet is used for inserting the PTFE sample injection cloth, the other round hole inlet is used for injecting the sample injection and sweeping gas circuit (12) for air inlet, and the round hole outlet is connected with the ionization cavity (9); the gas inlet of the sample injection purging gas circuit (12) is coaxially opposite to the gas outlet connected with the ionization chamber, but the diameter of the gas outlet is slightly larger than that of the gas inlet.
4. A method according to claim 1 or 3, characterized in that:
the inner diameter of the peek cavity (6) is 25-30 mm, the height of the peek cavity is 8-10 mm, the inlet connected with the sample injection purging gas circuit (12) is a threaded hole of M2 or M3, and the diameter of the outlet connected with the ionization cavity (9) is 3.5-4 mm; a quartz optical lens (5) is arranged at the top and sealed by a silica gel pad, and a rectangular tetrafluoro sample feeding cloth (7) is inserted at the bottom; the bottom of the peek cavity (6) is provided with a metal heating block (8), and the metal heating block (8) is limited by the performance of the peek material and the reduction of power consumption, so that the metal heating block is heated at a constant temperature of 100-120 ℃ and used for preheating the peek cavity (6);
the sample injection PTFE sample injection cloth is made of PTFE and has the thickness of 1 mm-2 mm; the solid sample to be detected is dissolved in the solvent, and then the surface of the solid sample to be detected is spotted on the tetrafluoro through a sample injection needle or directly wiped through a tetrafluoro sample injection cloth, but the position stained with the sample is ensured to be positioned in the focal radius of the halogen lamp.
5. The method of claim 1, wherein:
the three-way valve is a gas path switching device automatically controlled by a time sequence and is used for switching continuous gas flow from residual-removing purging to sample-feeding purging;
before inserting the tetrafluoro sample inlet cloth, the gas circuit in the three-way valve is in a residue removing and purging gas circuit and is used for removing a residual sample in the device; when the tetrafluoro sample cloth is inserted into the peek cavity (6) from the slot, the lamp is automatically turned on, halogen lamp light enters the peek cavity (6) through the quartz optical lens (5) and irradiates the tetrafluoro sample cloth (7), and the sample on the tetrafluoro sample cloth (7) is analyzed through light flash pyrolysis; then, at the moment when the halogen lamp is extinguished, the three-way valve controlled by the time sequence is automatically switched to a sample introduction purging gas circuit (12), and simultaneously, sample steam is purged to enter the ionization cavity (9) to be ionized when the sample steam is the same, and finally, the sample steam is detected by a detection instrument at the tail end; after the sample introduction is finished, the gas path is switched to a residual removing and purging gas path again;
the light source adopted by the flash analysis is a halogen lamp (4), the power is not less than 75W, the halogen lamp is required to have a light focusing function, the flash time of the halogen lamp is adjustable by using a controller, and the flash time of the used halogen lamp is 2-4 s according to the volatilization difficulty condition of a sample; the temperature of the halogen light after 2s flash heating reaches more than 250 ℃ at a focusing spot with the diameter of 2mm, and the heating is continued until 7s finally reaches 500 ℃.
6. The method of claim 1, wherein:
the quartz optical lens (5) is a high-temperature-resistant high-light-transmittance quartz optical lens, and the light of the halogen lamp (4) is projected on the tetrafluoro sample cloth (7) through the lens; in order to ensure a high light transmittance, the thickness used should be less than 1.8 mm; meanwhile, the distance between the lamp holder of the halogen lamp (4) and the tetrafluoro sample cloth (7) is adjusted according to the focal length of the halogen lamp, then the distance between the halogen lamp (4) and the tetrafluoro sample cloth is finely adjusted according to the size of a sample spot on the tetrafluoro sample cloth (7), and therefore the radius of a focus on the tetrafluoro sample cloth is equal to the radius of the sample spot.
7. The method according to claim 1 or 2, characterized in that:
the air outlet is a round hole with the inner diameter of 2mm-3mm positioned on the ionization cavity (9), the inside of the ionization cavity is also a hollow cylinder, the inner diameter is 8-9 mm, the height is 10-12 mm, the volume of the ionization cavity is 0.5mL-0.7mL, and a tetrafluoro sealing sleeve (3) is arranged outside the radio frequency lamp (2);
the ionization cavity (9) is connected with an outlet of the residue removing and purging gas circuit and is used for purging residual samples in the ionization region when no sample is introduced, and simultaneously, acetone reagent ions are supplemented into the ionization region, and have a great promotion effect on chemical ionization of auxiliary drugs.
8. The method of claim 1, wherein:
the kit is used for rapidly and simultaneously detecting volatile and nonvolatile drug mixtures; the rapid simultaneous detection optical flash heating-time delay purging sample introduction method for the drug mixture works according to a specific time sequence, and comprises the following specific steps:
(1) the ionization source of the radio frequency lamp (2) is opened, and the three-way valve is positioned in the residue removing and purging gas circuit;
(2) sample introduction by using tetrafluoro sample introduction cloth: an electrically heated metal heating block (8) is arranged at the bottom in the peek cavity (6), a gap for the inlet and outlet of the PTFE sample injection cloth (7) is arranged on the side wall surface of the middle lower part of the peek cavity (6), and the black sample injection PTFE sample injection cloth (7) with a sample is inserted above the metal heating block (8) in the cavity;
(3) turning on a halogen lamp: the halogen lamp (4) controlled by the time sequence can be automatically turned on for a period of time and then turned off, and at the moment, the steam phase of the sample subjected to flash thermal desorption can temporarily stay in the peek cavity;
(4) and (3) switching a three-way valve: when the halogen lamp is extinguished, the three-way valve of the time sequence control can immediately switch the gas path from the residue removing purging gas path (11) to the sample introduction purging gas path (12), so that the steam of the sample which is difficult to volatilize and volatile and volatilizes and is volatilized from the peek cavity is purged into the ionization cavity (9) at the same time;
(5) sampling by an analytical instrument: the analysis and detection instrument at the air outlet of the device guides the ions in the ionization cavity (9) into the instrument;
(6) analysis of instrument signals: analyzing and recording the signal intensity of the sample detected by the instrument;
(7) removing residues: taking out the tetrafluoro sample cloth, and simultaneously switching the three-way valve to a residue removing and purging gas circuit;
(8) and (5) repeating the steps (2) to (7) to finally obtain instrument signals at different halogen lamp turn-on times and different gas flow rates.
9. The method of claim 8, wherein:
the volatile drugs and the difficult-to-volatilize drugs are mainly distinguished through boiling points, the boiling point of the volatile drugs is 200-400 ℃, and the boiling point of the difficult-to-volatilize drugs is 400-600 ℃.
10. The method of claim 9, wherein: the volatile drug is one or more than two of amphetamine, methamphetamine, ketamine, cocaine, tetrahydrocannabinol and MDMA;
the hard volatile drug comprises one or more of narcotine and sedative drugs.
11. The method of claim 10, wherein: the hard volatile drugs comprise fentanyl drugs.
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