CN111105981B - Flash thermal desorption-pulse sampling method for rapid and high-sensitivity detection of drugs on site - Google Patents

Flash thermal desorption-pulse sampling method for rapid and high-sensitivity detection of drugs on site Download PDF

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CN111105981B
CN111105981B CN201811249081.3A CN201811249081A CN111105981B CN 111105981 B CN111105981 B CN 111105981B CN 201811249081 A CN201811249081 A CN 201811249081A CN 111105981 B CN111105981 B CN 111105981B
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CN111105981A (en
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李海洋
侯可勇
王伟民
王爽
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • 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
    • 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

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Abstract

The invention discloses a method for realizing rapid and high-sensitivity detection of drugs on site by combining pulse purging and halogen light flash thermal analysis. The device in the method mainly comprises the following steps: the device comprises a photo-thermal halogen lamp, a high-temperature resistant quartz optical lens, a high-voltage pulse valve, a heatable thermal desorption micro-area and the like. The method has the main principle that the halogen lamp is used for rapidly heating the heatable thermal desorption micro-area to heat the drugs, and the drugs can be heated to more than 250 ℃ at the focus within 2s, so that the saturated vapor pressure of the drugs is greatly improved, and the diffusion in a sample space is effectively reduced by the constructed narrow micro-thermal desorption area; the combination of the pulse valve for instantaneous high-speed purging can more effectively transmit the sample steam from the heatable thermal desorption micro-area to the ionization area, thereby improving the utilization rate of the sample. The halogen lamp has high flash heat analysis heating speed and small sample residue, and compared with the traditional constant-temperature metal contact type heating, the power consumption is greatly reduced; the combination of the two can fully meet the requirement of the field portable analysis instrument.

Description

Flash thermal desorption-pulse sampling method for rapid and high-sensitivity detection of drugs on site
Technical Field
The invention relates to a mass spectrum plasma analysis detection instrument, in particular to a field detection instrument for drugs. The problems of insufficient temperature and slow heating rate during thermal analysis sample injection are solved by using halogen lamplight flash heat, so that the saturated vapor pressure of the drugs is greatly improved, and the diffusion in a sample space is effectively reduced by a constructed narrow micro thermal analysis area; the combination of the pulse valve for instantaneous high-speed purging can more effectively transmit the sample steam from the heatable thermal desorption micro-area to the ionization area, thereby improving the utilization rate of the sample. By using the flash thermal analysis-pulse sampling device, the signal intensity of the drugs is improved by more than one order of magnitude compared with the traditional continuous blowing accumulated intensity, and the drug detection sensitivity reaches 10 pg.
Background
The thermal analysis sample has the advantages of high speed, simple structure, high efficiency and the like, and is the most common pretreatment method before the atmospheric pressure ionization source ionizes the gaseous sample at present. This is because the sample molecules in a gaseous state have higher ionization efficiency than solvation in a solid state and a liquid state, which have a great intermolecular interaction, and are suitable for various atmospheric pressure chemical ionization sources developed at present, but it is greatly affected by the thermal desorption temperature and the temperature rise rate, and it is difficult for a volatile sample to be detected when the temperature is insufficient.
The drugs have various types, and the difference of molecular weight and polarity causes the difference of volatility, for example, the boiling point of fentanyl type new psychoactive drugs is generally over 500 ℃, and the boiling point of methamphetamine, K powder, heroin and the like is about 300 ℃. At present, the components of emerging psychotropic drugs and plant samples are very complex, the number of the emerging psychotropic drugs managed and controlled in China is as much as 170, and the sensitivity of instrument detection is lower when the traditional continuous purging and metal contact type temperature rising thermal analysis are used for the hard-to-volatilize and volatile drug mixed samples. The main reasons are: 1) some detection instruments with low sample duty cycle, such as mass spectrometry using DAPI discontinuous sample injection, will have a part of the sample carried out of the ionization region by the continuously purged gas and not be detected; 2) the low-volatility drugs have low vaporization efficiency and poorer detection sensitivity when the temperature rise speed is not high enough or the temperature is not high enough due to low saturated vapor pressure; 3) loss of gaseous drug sample during sample transport.
In current ion detection instruments such as mass spectrometry or mobility spectrometry, in order to avoid residual contamination of a thermal analysis sample, a thermal analysis region and an ionization region are not located together, so that the sample enters an ionization cavity from the thermal analysis region and needs the transportation of carrier gas, and a certain diffusion effect and a certain delay effect exist when the sample is continuously blown and passes through a channel with a large pipe diameter, so that the detection signal is reduced, the sample remains, and the peak broadening is aggravated. The pulse valve is a common device for ultrasonic molecular beam/laser gas experiment/cluster in reaction kinetics, is used for forming low-temperature and low-kinetic-energy molecular beams in high vacuum, can be loaded with high pressure to form instant large-flow purging under atmospheric pressure, and can more effectively transmit sample steam to an ionization region by instant high-speed purging.
Therefore, the invention designs a method for improving the on-site detection sensitivity of drugs by combining halogen lamp light flash heat and pulse purging, wherein a halogen lamp is arranged right above a quartz optical lens, and light penetrates through the lens and irradiates on black tetrafluoro paper on which a sample is dripped for heating. The hard and volatile drugs are heated up and volatilized rapidly, then the vapor phase of the mixture drugs can stay in the heatable thermal desorption micro-area for a short time, and the structure has the advantage of ensuring the flash heating efficiency of halogen lamp light and reducing the diffusion of the sample in the space. The pulse purging and sampling method has the advantages that the pulse valve has higher efficiency compared with the traditional continuous purging and sampling mode, the instantaneous high-speed purging of the pulse sampling can effectively transmit the sample steam to the ionization region, the sample detection loss caused by low signal-to-noise ratio of the instrument, low DAPI discontinuous sampling duty ratio and the like in the continuous purging and sampling mode is reduced, the sample utilization rate is improved, and the signal intensity of the sample is improved by one order of magnitude compared with the traditional continuous purging and accumulating intensity. The halogen lamp has high flash heat analysis heating speed, small sample residue and low power consumption; the pulse sampling sample has high utilization rate and less gas consumption, and the combination of the two fully meets the requirements of field portable analysis instruments.
Disclosure of Invention
The invention aims to provide an analysis method for rapidly and sensitively detecting drugs on site. In order to achieve the purpose, the invention adopts the technical scheme that:
the device comprises a halogen lamp, a radio frequency lamp, a quartz optical lens, a high temperature resistant fluorine O ring, a heatable thermal desorption micro-area, a heat preservation fixing shell, a pulse valve, an acetone carrier gas, black PTFE sample inlet cloth, a micro-area air inlet, a micro-area air outlet, a stepping motor fixing piece, a stepping motor, a stainless steel top head, a stepping motor shaft, a device air outlet, an ionization cavity and a radio frequency lamp fixing clamping sleeve.
The halogen lamp, the quartz optical lens and the heatable thermal desorption micro-zone are coaxial, and the halogen lamp focus is located within the heatable thermal desorption micro-zone. A slot of the heat preservation fixing shell can be inserted into the tetrafluoro sampling cloth to enter a heatable thermal desorption micro-area, and the other round hole is used for connecting the sweeping and air inlet of the pulse valve gas.
The heatable thermal desorption micro-area is a hollow cylinder with openings at the left end and the right end, the outer side of the hollow cylinder is fixedly provided with a heat-preservation fixed shell, a quartz optical lens is arranged at the left opening end of the hollow cylinder, and the peripheral edge of the quartz optical lens is hermetically connected with the end face of the left opening end. The left side of the quartz optical lens faces the halogen lamp, the open end of the right end of the cylinder is provided with a stainless steel top capable of moving left and right, the stainless steel top is connected with a stepping motor shaft of a stepping motor, the stepping motor controls the stainless steel top to move left and right, the stainless steel top moves left to enable the left side wall face of the stainless steel top to be in sealing butt joint with the end face of the right open end of the cylinder, and black tetrafluoro sample introduction is arranged between the stainless steel top and the right open end of the cylinder.
The micro-area air inlet is arranged on the side wall surface of the upper part of the cylinder and is connected with a sweeping air source through a pulse valve, the micro-area air outlet is arranged on the side wall surface of the lower part of the cylinder and leads to the ionization cavity, the micro-area air inlet and the micro-area air outlet are coaxially opposite, but the diameter of the air outlet is slightly larger than that of the air 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, an air inlet and an air outlet of the ionization cavity are arranged on the side wall surface of the ionization cavity, and the air outlet is connected with a detection instrument.
A high-temperature resistant fluorine O ring is arranged between the quartz optical lens and the left opening end of the cylinder; the purge gas is acetone carrier gas; the stepping motor is fixedly connected with the heatable thermal desorption micro-interval through a stepping motor fixing piece; the radio frequency lamp can pass through the fixed cutting ferrule of radio frequency lamp and is fixedly connected with the ionization cavity.
The light source used for the flash analysis is a halogen lamp, the power is 75W, the focal length is 35mm, the halogen lamp has a light focusing function, the flash time of the halogen lamp is adjustable by using a controller, the flash time of the halogen lamp is 2s according to the boiling point of common drugs, and the temperature of a focusing spot with the diameter of 2mm can reach more than 250 ℃ after the halogen lamp flashes for 2 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 black tetrafluoro sample cloth through the lens; in order to ensure higher light transmittance, the thickness of the heating thermal desorption micro-area is 1.8mm, and the top of the heating thermal desorption micro-area is sealed by a high-temperature-resistant fluorine O ring; meanwhile, the distance between the lamp holder of the halogen lamp and the black tetrafluoro sample cloth is 35mm, and then the distance between the halogen lamp and the tetrafluoro sample cloth is adjusted slightly according to the size of the sample spot on the tetrafluoro sample cloth, so that the radius of the focus on the tetrafluoro sample cloth is equal to the radius of the sample spot.
In order to ensure effective flash illumination, the hollow cylinder in the heatable thermal desorption micro-area has the radius of 8mm, the height of 6mm and the volume of about 0.3 mL; the gas inlet of the upper micro-area of the cylinder is communicated with the pulse valve, and the gas outlet of the lower micro-area of the cylinder is communicated with the ionization cavity where the radio frequency lamp is positioned; in order to ensure better pulse purging efficiency, the diameter of an inlet small hole is 2.5mm, the diameter of an outlet is set to be 3.5mm, and the diameters of an inlet micro-area air inlet and a micro-area air outlet can directly influence the transmission efficiency and the dead volume of pipeline transmission.
The bottom of the heatable thermal desorption micro-area is communicated with the outside atmosphere when the stainless steel top head is not lifted, but when the bottom of the heatable thermal desorption micro-area is lifted at the stainless steel top head, a closed cavity can be formed in the heatable thermal desorption micro-area, and the sample obtained by flash thermal desorption is guaranteed to be efficiently transmitted to the ionization cavity.
Meanwhile, for example, in order to reduce the residue of the sample and ensure the efficiency of the transmission, the heating element attached to the surface of the thermal desorption micro-area is preheated, and the constant temperature is 100 ℃.
The air outlet of the device is a round hole with the inner diameter of 3mm, which is positioned on the ionization cavity, the inside of the ionization cavity is also a hollow cylinder, the inner diameter is 8mm, the height is 10mm, and the volume of the ionization cavity is 0.5 mL. The high-pressure pulse valve (7) is an axial flow path, the on-off of an internal valve core is controlled by the movement of a magneton which can oscillate back and forth, and the working frequency and the opening time width of the pulse valve (7) can be controlled by using a pulse signal time sequence provided by the outside; when the stepping motor moves rightwards, the thermal desorption micro-area can be heated to be communicated with the external atmospheric pressure, and the pulse valve is in a fully open state and is used for removing residues in the device.
The dead volume of pipeline transmission mainly comprises the dead volume of a transmission pipeline from the pulse valve to the micro-area air inlet and the dead volume of a transmission pipeline from the micro-area air outlet to the ionization chamber. The tubing transport should be as short as possible, but the inner diameter of the tubing is not as small as possible, since too small a volume will reduce the transport efficiency of the gas, and too large a volume will dilute the sample, where the dead volume of the tubing transport is about 0.2 mL.
The flash thermal analysis-pulse sampling of the rapid high-sensitivity detection of the drug on site works according to a specific time sequence, and the specific steps are as follows:
(1) turning on an ionization source of the radio frequency lamp;
(2) injecting sample into the tetrafluoro cloth: inserting the black sample-injection tetrafluoro cloth stained with the sample into a heatable thermal desorption micro-area;
(3) sealing the heatable thermal desorption micro-area: the stepping motor can automatically start to move leftwards, and simultaneously drives the stainless steel top head to fix the tetrafluoro sample injection cloth, so as to realize the sealing of the heatable thermal desorption micro-area;
(4) turning on a halogen lamp: the halogen lamp 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 heatable thermal desorption micro-area;
(5) opening a pulse valve: at the moment that the halogen lamp is extinguished, the pulse valve which is also controlled by the time sequence can be automatically opened for a period of time, and then the sample vapor phase in the heatable thermal desorption micro-area is swept and enters the ionization cavity at the rear end;
(6) sampling by an analytical instrument: at the moment when the pulse valve is closed, an analysis and detection instrument at the air outlet of the device guides ions in the ionization cavity into the instrument;
(7) analysis of instrument signals: analyzing and recording the signal intensity of the sample detected by the instrument;
(8) removing residues: software controls the stepping motor to move rightwards, the thermal desorption micro-area can be heated after unsealing, simultaneously the tetrafluoro sample cloth is taken out, and at the moment, the pulse valve can be completely opened to remove residual samples in the device;
(9) and (5) repeating the steps (2) to (8) to finally obtain instrument signals with different front-end pressures of the pulse valve and different pulse opening times.
The volume flow of the pulse scavenging gas can be controlled by adjusting the gas pressure at the front end of the pulse valve; the pressure of the front end is 0.1MPa, the volume flow of the heatable thermal desorption micro-area at the valve opening moment is 1.5L/min, and the valve opening time of the selected pulse valve is 10 m.
The invention has the advantages that:
the invention relates to a halogen lamp flash heat analysis-pulse sampling device, which utilizes a halogen lamp to heat:
1. the flash heating of the halogen lamp light has high heating speed, the temperature of 2s of light heat near the focus reaches more than 250 ℃, volatile and non-volatile drugs can be simultaneously heated from room temperature to be thermally analyzed, the concentration of a sample analyzed in unit time is high, the saturated vapor pressure is greatly improved, and the detection sensitivity is further improved;
2. compared with the traditional constant-temperature metal contact type heating sample, the method has the advantages that the residue is low, and the power consumption is greatly reduced;
3. compared with the traditional continuous purging and sample feeding mode, the pulse valve has higher purging efficiency by combining the used pulse purging and sample feeding device;
drawings
FIG. 1 is a diagram of a flash thermal desorption-pulse sampling apparatus
FIG. 2 is a working sequence of flash thermal analysis-pulse sampling
FIG. 3 is a mass spectrum of methamphetamine obtained by flash thermal desorption-pulse sampling
FIG. 4 is a mass spectrum of fentanyl obtained by flash thermal analysis-pulse sampling
FIG. 5 is a mass spectrum of a solid substance of suspected opium provided by a wooden corner inspection station in Miscanthus, Yunnan province, using halogen light flash thermal desorption-pulse sampling to detect
FIG. 6 is a mass spectrum of methamphetamine obtained by flash thermal analysis with continuous injection
FIG. 7 is a mass spectrum of fentanyl obtained by flash thermal analysis and continuous sample injection
Detailed Description
As shown in fig. 1, a halogen lamp flash thermal desorption-pulse sample injection device comprises a halogen lamp, a radio frequency lamp, a quartz optical lens, a high temperature resistant fluorine O ring, a heatable thermal desorption micro-area, a heat preservation fixing shell, a pulse valve, an acetone carrier gas, black tetrafluoro sample injection cloth, a micro-area gas inlet, a micro-area gas outlet, a stepping motor fixing piece, a stepping motor, a stainless steel top, a stepping motor shaft, a device gas outlet, an ionization cavity and a radio frequency lamp fixing sleeve.
The flash thermal analysis-pulse sampling of the rapid high-sensitivity detection of the drug on site works according to a specific time sequence, and the specific steps are as follows:
(1) turning on an ionization source of the radio frequency lamp;
(2) injecting sample into the tetrafluoro cloth: inserting the black sample-injection tetrafluoro cloth stained with the sample into a heatable thermal desorption micro-area;
(3) sealing the heatable thermal desorption micro-area: the stepping motor can automatically start to move leftwards, and simultaneously drives the stainless steel top head to fix the tetrafluoro sample injection cloth, so as to realize the sealing of the heatable thermal desorption micro-area;
(4) turning on a halogen lamp: the halogen lamp 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 heatable thermal desorption micro-area;
(5) opening a pulse valve: at the moment that the halogen lamp is extinguished, the pulse valve which is also controlled by the time sequence can be automatically opened for a period of time, and then the sample vapor phase in the heatable thermal desorption micro-area is swept and enters the ionization cavity at the rear end;
(6) sampling by an analytical instrument: at the moment when the pulse valve is closed, an analysis and detection instrument at the air outlet of the device guides ions in the ionization cavity into the instrument;
(7) analysis of instrument signals: analyzing and recording the signal intensity of the sample detected by the instrument;
(8) removing residues: software controls the stepping motor to move rightwards, the thermal desorption micro-area can be heated after unsealing, simultaneously the tetrafluoro sample cloth is taken out, and at the moment, the pulse valve can be completely opened to remove residual samples in the device;
(9) and (5) repeating the steps (2) to (8) to finally obtain instrument signals with different front-end pressures of the pulse valve and different pulse opening times.
Example 1
The method is applied, a 0.1 mu g/mL methamphetamine methanol standard solution is sucked by a 1 mu L sample injection needle and then is dripped on the tetrafluoro sample injection cloth, meanwhile, the flash focus of a halogen lamp is ensured to fall on a sample, and after a solvent is volatilized, the absolute amount of the sample on the tetrafluoro cloth is 0.1 ng. The boiling point of methamphetamine is about 200 deg.C, and figure 3 shows 0.1ng of methamphetamineAn amine halogen lamp flash thermal analysis pulse sample injection mass spectrogram, 91 is fragment ion [ M-C ] of methamphetamine3H9N]+150 is the peak of the proton addition of the molecular ion of methamphetamine, and 117 is the peak of the proton addition of acetone dimer.
Example 2
The method is applied, the boiling point of fentanyl is about 500 ℃, and the fentanyl belongs to drugs which are difficult to volatilize. 0.1 mu g/mL fentanyl methanol standard solution is sucked by a sample injection needle of 1 mu L and then is dripped on a tetrafluoro sample injection cloth, meanwhile, the flash heat focus of a halogen lamp is ensured to fall on a sample, and after a solvent is volatilized, the absolute amount of the sample on the tetrafluoro cloth is 0.1 ng. FIG. 4 is a 0.1ng fentanyl halogen lamp flash thermal desorption pulse injection mass spectrum. 337 is the peak of the molecular ion of fentanyl plus the proton, 117 is the peak of the adducted proton of acetone dimer.
Example 3
The method is applied, and figure 5 shows a sample of suspected opium detected by using halogen lamp light flash thermal analysis-pulse valve sample injection, and the sample is provided by a Konkan inspection station in Miscanthus, Yunnan province. Drying the pasty solid, grinding into powder, dissolving the obtained solution by 10mL of methanol through ultrasound, absorbing the solution by a 1-microliter sample injection needle, dripping the solution on black tetrafluoro sample injection cloth, and inserting the black tetrafluoro sample injection cloth into a flash thermal desorption pulse sample injection device. 6 components of narcotine, morphine, papaverine, codeine, heroin and thebaine were successfully detected simultaneously, and Table 1 is an indication of the main mass spectrum peaks in FIG. 5, thus confirming that the solid is opium.
TABLE 1 assignment of the main mass spectral peaks in FIG. 5
Figure BDA0001841220290000061
Comparative example
The difference from the embodiment 1 is that the traditional halogen light flash-continuous purging sample injection is used, namely, 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 at the tail end in series. Fig. 6 shows the result of superimposing the detection spectra of 0.1ng methamphetamine by halogen lamp-continuous purging injection, and it can be seen that the intensity of the ion peak of the methamphetamine molecule in the figure reaches up to 300, which is 4 to 5 times worse than the result in the embodiment example 1.
FIG. 7 shows the result of the superposition of the detection spectra of 0.1ng fentanyl by halogen lamp-continuous purge injection, and it can be seen that the peak of fentanyl molecular ion in the figure is basically not seen, which is 1 order of magnitude worse than the result in the embodiment example 2.

Claims (10)

1. A flash thermal analysis-pulse sampling method for rapid high-sensitivity detection of drugs on site is characterized in that:
mainly comprises a halogen lamp (1), a radio frequency lamp (2), a quartz optical lens (3), a heatable thermal resolution micro-area (5), a heat preservation fixing shell (6), a pulse valve (7), black tetrafluoro sample inlet cloth (9), a micro-area air inlet (10), a micro-area air outlet (11), a stainless steel top (12), a stepping motor shaft (13), a device air outlet (14), an ionization cavity (15) and a stepping motor (18);
the halogen lamp (1), the quartz optical lens (3) and the heatable thermal desorption micro-area (5) are coaxial, and the focus of the halogen lamp (1) is positioned in the heatable thermal desorption micro-area (5) and falls on the black tetrafluoro sample feeding cloth (9); one slot of the heat-preservation fixed shell (6) can be inserted with black tetrafluoro sample-entering cloth (9) to enter the heatable thermal desorption micro-area (5), and the other round hole is used for connecting the sweeping and air-intake of the gas of the pulse valve (7);
the heatable thermal desorption micro-area (5) is a hollow cylinder with openings at the left end and the right end, a heat-preservation fixing shell (6) is arranged and fixed on the outer side of the hollow cylinder, a quartz optical lens (3) is arranged at the left opening end of the hollow cylinder, the peripheral edge of the quartz optical lens (3) is hermetically connected with the end face of the left opening end, and the left side of the quartz optical lens (3) faces the halogen lamp (1); a stainless steel top head (12) capable of moving left and right is arranged at the opening end of the right end of the cylinder, the stainless steel top head (12) is connected with a stepping motor shaft (13) of a stepping motor (18), the stepping motor (18) controls the stainless steel top head (12) to move left and right, the stainless steel top head (12) moves left to enable the left side wall surface of the stainless steel top head to be in sealing butt joint with the end surface of the right opening end of the cylinder, and black PTFE sample injection cloth (9) is arranged between the stainless steel top head (12) and the right opening end of the cylinder;
a micro-area air inlet (10) is arranged on the side wall surface of the upper part of the cylinder, the micro-area air inlet (10) is connected with a sweeping gas source through a pulse valve (7), a micro-area air outlet (11) is arranged on the side wall surface of the lower part of the cylinder and leads to an ionization cavity (15), the micro-area air inlet (10) and the micro-area air outlet (11) are coaxially opposite, but the diameter of the air outlet is slightly larger than that of the air inlet;
the ionization cavity (15) is a closed hollow cavity, a radio frequency lamp (2) is arranged on the side wall surface of the ionization cavity, light emitted by the radio frequency lamp (2) irradiates the cavity, an air inlet and a device air outlet (14) are arranged on the side wall surface of the ionization cavity, a sample vapor phase transmitted from the heatable thermal analysis micro-area (5) enters the ionization cavity from the air inlet and is subjected to photoionization, and the device air outlet (14) is connected with a detection instrument.
2. The method of claim 1, wherein:
the device also comprises a high temperature resistant fluorine O ring (4), an acetone carrier gas (8), a stepping motor fixing piece (17) and a radio frequency lamp fixing sleeve (16);
a high-temperature-resistant fluorine O ring (4) is arranged between the quartz optical lens (3) and the left opening end of the cylinder, and the quartz optical lens (3) mechanically seals and presses the high-temperature-resistant fluorine O ring (4) to keep the air tightness of the heating thermal desorption micro-area (5); the purge gas is acetone carrier gas (8), and the acetone reagent has a very high lifting effect on photochemically ionized some basic sample molecules; the stepping motor is fixedly connected with the heatable thermal desorption micro-area (5) through a stepping motor fixing piece (17); the radio frequency lamp is fixedly connected with the ionization cavity (15) through a radio frequency lamp fixing clamping sleeve (16);
after the black tetrafluoro sample feeding cloth (9) is inserted into the heatable thermal desorption micro-area from the bottom of the right side of the heatable thermal desorption micro-area, the stainless steel top head can move to the left under the action of a stepping motor (18) to jack up the black tetrafluoro sample feeding cloth so as to seal the thermal desorption micro-area; the light of the halogen lamp (1) enters a heatable thermal desorption micro-area through the quartz optical lens (3) and irradiates on the black tetrafluoro sample feeding cloth, and the light flashes to desorb a sample on the black tetrafluoro sample feeding cloth; then, at the moment when the halogen lamp is extinguished, the pulse valve (7) controlled by the time sequence is automatically opened, the steam phase sample is instantly blown into the ionization cavity (15) to be ionized, and finally the steam phase sample is detected by a detection instrument at the tail end.
3. The method according to claim 1 or 2, characterized in that:
the light source adopted by the flash analysis is a halogen lamp (1), 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 at a focusing spot with the diameter of 2mm can reach more than 250 ℃ after the halogen light is flashed for 2s, and the halogen light can finally reach 500 ℃ after being continuously heated to 7 s.
4. The method according to claim 1 or 2, characterized in that:
the quartz optical lens (3) is a high-temperature-resistant high-light-transmittance quartz optical lens, and light of the halogen lamp (1) can penetrate through the lens and be projected on the black tetrafluoro sample cloth (9); in order to ensure high light transmittance, the thickness of the quartz optical lens (3) should be less than 1.8 mm; meanwhile, the distance between the lamp holder of the halogen lamp (1) and the black tetrafluoro sample feeding cloth (9) is adjusted according to the focal length of the halogen lamp, then the distance between the halogen lamp (1) and the black tetrafluoro sample feeding cloth (9) is slightly adjusted according to the size of sample spots stained on the black tetrafluoro sample feeding cloth (9), and therefore the radius of a focus on the black tetrafluoro sample feeding cloth is approximately equal to the radius of the sample spots;
the black polytetrafluoroethylene sample feeding cloth is made of polytetrafluoroethylene, the thickness of the black polytetrafluoroethylene sample feeding cloth is 1 mm-2 mm, and the black polytetrafluoroethylene sample feeding cloth is processed to be black so as to improve the heat absorption rate; the solid sample to be detected can be dissolved in the solvent and then spotted on the black tetrafluoro sample cloth through the sample injection needle or the surface of the solid sample to be detected is directly wiped through the black 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 according to claim 1 or 2, characterized in that:
in order to ensure effective flash heat illumination, the radius of a hollow cylinder in the heatable thermal desorption micro-area (5) should be not less than 6mm, the smaller the height is, the better the height is, and the volume in the cylinder needs to be 0.3-0.4 mL; a micro-area air inlet (10) on the upper side wall surface of the cylinder is used for pulse blowing air inlet, and an air outlet (11) on the lower side wall surface of the cylinder is communicated to an ionization cavity (15) where the radio frequency lamp (2) is located and is used for transmitting a sample vapor phase; in order to ensure better pulse purging efficiency, the diameter of a micro-area air inlet (10) is 2mm-2.5mm, and the diameter of a micro-area air outlet (11) is 3mm-4 mm;
the bottom of the heatable thermal desorption micro-area (5) is communicated with the outside atmosphere when the stainless steel top head (12) is not lifted, but when the bottom of the heatable thermal desorption micro-area is lifted up at the stainless steel top head (12), a closed cavity can be formed in the heatable thermal desorption micro-area, and a sample obtained by flash thermal desorption is guaranteed to be efficiently transmitted to the ionization cavity (15);
meanwhile, in order to reduce the residue of the sample and ensure the transmission efficiency, a certain heating element is attached to the outer surface of the heating thermal desorption micro-area (5) for preheating, and the constant temperature is 80-100 ℃.
6. The method according to claim 1 or 2, characterized in that:
the air outlet (14) of the device is a round hole with the inner diameter of 2mm-3mm, which is positioned on the ionization cavity (15), the inside of the ionization cavity is also a hollow cylinder, the inner diameter is 8-9 mm, the height is 10-12 mm, and the volume of the ionization cavity is 0.5mL-0.7 mL; in order to reduce the loss of the sample after pulse purging, the volume of the ionization cavity is ensured to be larger than the volume of a hollow cylinder in the heatable thermal desorption micro-area (5);
the air outlet (14) of the device is connected with a mass spectrum detection device or a mobility spectrum plasma detection device at the rear end.
7. The method according to claim 1 or 2, characterized in that:
the pulse valve (7) is an axial flow path, and the working frequency and the opening time width of the pulse valve (7) can be controlled by using a pulse signal time sequence provided from the outside; when the stepping motor moves rightwards, namely the heating thermal desorption micro-area is communicated with the external atmospheric pressure, the pulse valve is in a fully opened state and is used for removing residues in the device;
the opening time of the pulse valve (7) is controlled in millisecond level, the opening time is too small or too large, the signal intensity of the sample is reduced, the time is too short, the sample cannot be effectively blown into the ionization cavity (15) from the heatable thermal desorption micro-area (5), the time is too long, and continuous gas blowing can cause larger loss.
8. The method according to claim 1 or 2, characterized in that:
in order to ensure the density of ions in the ionization cavity and simultaneously reduce the blowing loss caused by overlarge pulse flow velocity, the relationship among the volume of the ionization cavity (15), the volume of the heatable thermal analysis micro-area (5) and the dead volume of pipeline transmission must be matched, so that the volume of the ionization cavity is larger than the sum of the volume of the heatable thermal analysis micro-area (5) and the volume of pipeline transmission;
the dead volume of the pipeline transmission mainly comprises the dead volume of a transmission pipeline from the pulse valve (7) to the micro-area air inlet (10) and the dead volume of a transmission pipeline from the micro-area air outlet (11) to the ionization cavity (15); theoretically, the shorter the tube transport distance, the better, but the smaller the inner diameter of the tube, the smaller the tube transport distance, because too small a volume reduces the transport efficiency of the gas, and too large a volume dilutes the sample, and it should be ensured that the dead volume transported by the tube is not more than 0.2 mL.
9. The method according to claim 1 or 2, characterized in that:
the flash thermal analysis-pulse sampling for rapid and high-sensitive detection of the drug on site works according to a specific time sequence, and the specific steps are as follows:
(1) the ionization source of the radio frequency lamp (2) is turned on;
(2) sampling by using black tetrafluoro sampling cloth: inserting black tetrafluoro sample-entering cloth (9) stained with a sample into the heatable thermal desorption micro-area (5);
(3) sealing the heatable thermal desorption micro-area: the stepping motor (18) can be automatically started to move leftwards, and simultaneously drives the stainless steel top head (12) to fix the black tetrafluoro sample cloth, so that the heatable thermal desorption micro-area (5) is sealed;
(4) turning on a halogen lamp: the halogen lamp (1) 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 heatable thermal desorption micro-area (5);
(5) opening a pulse valve: at the moment that the halogen lamp (1) is extinguished, the pulse valve which is also controlled by a time sequence can be automatically opened for a period of time, and then a sample vapor phase in the heatable thermal desorption micro-area (5) is swept and enters the ionization cavity (15) at the rear end;
(6) sampling by an analytical instrument: at the moment when the pulse valve is closed, an analysis and detection instrument at the air outlet of the device guides ions in the ionization cavity (15) into the instrument;
(7) analysis of instrument signals: analyzing and recording the signal intensity of the sample detected by the instrument;
(8) removing residues: software controls the stepping motor to move rightwards, the thermal desorption micro-area can be heated after unsealing, and meanwhile, the black tetrafluoro sample inlet cloth is taken out, and at the moment, the pulse valve is completely opened to remove residual samples in the device;
(9) and (5) repeating the steps (2) to (8) to finally obtain instrument signals of different pulse valve front end pressures and different pulse opening times.
10. The method of claim 9, wherein:
the volume flow of the pulse scavenging gas can be controlled by adjusting the gas pressure at the front end of the pulse valve; when the pressure of the front end is 0.05MPa-0.10MPa, the volume flow of the heated thermal desorption micro-area (5) at the opening moment of the valve is 1.5L/min-2.5L/min, and the opening time of the selected pulse valve is 10ms-30 ms.
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