CN205280676U - Liquid chromatogram fraction is liquid phase of cutting detection in succession - gaseous phase two dimension chromatogram on line - Google Patents
Liquid chromatogram fraction is liquid phase of cutting detection in succession - gaseous phase two dimension chromatogram on line Download PDFInfo
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- BXYPVKMROLGXJI-JTQLQIEISA-N 3-[(2s)-1-nitrosopiperidin-2-yl]pyridine Chemical compound O=NN1CCCC[C@H]1C1=CC=CN=C1 BXYPVKMROLGXJI-JTQLQIEISA-N 0.000 description 2
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Abstract
The utility model relates to a liquid chromatogram fraction is liquid phase of cutting detection in succession - gaseous phase two dimension chromatogram on line, its gaseous phase chromatogram analytical equipment (20) who includes liquid chromatogram analytical equipment (16) and be located its low reaches, be equipped with two at least online enrichment facilities between liquid chromatogram analytical equipment (16) and the gaseous phase chromatogram analytical equipment (20), online enrichment facility be used for with liquid chromatogram analytical equipment (16) according to the multistage outflow fraction of retention time cutting in proper order or advance appearance after the hocket concentration more respectively and arrive in gas chromatograph device (20). The utility model discloses still relate to and use this liquid phase - gaseous phase stratographic analytical approach of two dimension and application. The utility model discloses a apparatus and method for can all can cut each section fraction through liquid chromatogram separation and enter into gas chromatography, realizes complete two -dimentional chromatography mode for sensitivity is hanged down, is had the restriction, can not cut the scheduling problem in succession to the component the solvent volume that changes the gas chromatography introduction port over to in solving prior art.
Description
Technical Field
The utility model belongs to the technical field of chemical equipment, further belong to chemical analysis technical field, concretely relates to liquid chromatogram fraction can online continuous cutting detect liquid phase-gas phase two dimension chromatogram and application.
Background
Tobacco Specific Nitrosamines (TSNAs) are an important harmful component in blood of smokers, and 8 TSNAs are reported at present, wherein 4N-nitrosonornicotine (NNN), 4- (methylnitrosamine) -1- (3-pyridyl) -1-butanone (NNK), N-Nitrosoanatabine (NAT) and N-Nitrosoanabasine (NAB) are deeply researched. NNK is once listed as a blood safety evaluation index of smokers in China. 4- (methylnitrosamino) -1- (3-pyridyl) -1-butanol (NNAL) is the major metabolite of NNK and has similar oncogenic activity as NNK; therefore, accurate determination of NNK and NNAL in the blood of smokers is of great significance for further understanding the relationship between smoking and health.
At present, the content of nitrosamine and metabolic products thereof specific to tobacco is determined by gas chromatography, and solid phase extraction or column chromatography separation and purification is adopted for sample pretreatment; the method for purifying the sample needs to concentrate and transfer for many times, is complex to operate, pollutes the environment due to the use of a large amount of organic solvents in an open environment, and has great harm to the health of experiment operators. Therefore, it is very urgent to find a simpler and faster sample pretreatment method. The on-line liquid-gas two-dimensional chromatography is a new analysis technology developed in recent years, and a sample is separated and purified by Liquid Chromatography (LC), and then the effluent fraction containing the component to be detected is cut on line and enters Gas Chromatography (GC) for analysis. The online combination of the liquid chromatogram and the gas chromatogram can fully exert the complementarity of the two-stage chromatograms, on one hand, the high column efficiency of the liquid chromatogram greatly improves the purification effect of the sample, can realize the separation of trace components to be detected and interfering substances in a complex matrix, and the online switching between the two-dimensional chromatograms can also reduce the concentration and transfer in the pretreatment process of the sample, reduce the artificial analysis error and greatly improve the accuracy and the precision of the analysis result.
The existing commercial on-line liquid phase-gas phase two-dimensional chromatograph can only realize the center cutting of liquid phase chromatogram fractions, and has the defects that only a certain part of the liquid phase chromatogram fractions can be cut into the gas phase chromatogram by one sample injection, the rest fractions are all taken as waste liquid to be discharged, and each section of fractions separated by the liquid phase chromatogram cannot be cut into the gas phase chromatogram.
In view of the above-mentioned shortcomings of the prior art, the present invention is provided.
SUMMERY OF THE UTILITY MODEL
The utility model aims at providing a liquid-gas two-dimensional chromatogram which can continuously cut and detect the liquid chromatogram fraction on line; another aspect is to provide an analytical method using the liquid-gas two-dimensional chromatography and its application in trace sample detection.
The purpose of the utility model is realized through the following technical scheme.
The utility model discloses a first aspect relates to a liquid-gas two-dimensional chromatogram that liquid chromatogram fraction can cut the detection in succession on line, it includes liquid chromatogram analytical equipment 16 and locates at its downstream gas chromatogram analytical equipment 20; at least two online concentration devices are arranged between the liquid chromatographic analysis device 16 and the gas chromatographic analysis device 20, and the online concentration devices are used for concentrating the multi-section effluent fractions cut by the liquid chromatographic analysis device 16 according to the retention time in sequence or alternately and then respectively injecting the concentrated effluent fractions into the gas chromatographic analysis device 20. The downstream of the two-dimensional chromatographic device is connected with a mass spectrometer or a direct gas chromatograph is directly changed into a gas chromatograph-mass spectrometer.
In a preferred embodiment of the present invention, the in-line concentration device comprises the following components in sequential fluid communication: a first material inlet and outlet 3, a solvent evaporation device and a second material inlet and outlet 9.
The solvent evaporation device comprises a fraction collection bin 6, a plunger rod 4 which is inserted into the fraction collection bin 6 in a sealed manner, and a temperature control heating device 5 which is positioned on the outer wall of the fraction collection bin 6; wherein the plunger rod 4 can move up and down along the inner wall of the fraction collecting bin 6 under the action of the buoyancy of the sample to be concentrated or the gravity of the sample to be concentrated; the plunger rod 4 is provided with a through passage for communicating the first material inlet/outlet 3 and the fraction collecting bin 6;
a solvent discharge pipe 1 crossed with the first material inlet and outlet 3 is arranged on the first material inlet and outlet 3, a first control valve 2 is arranged at the crossed position of the first material inlet and outlet and is used for controlling the cut fraction to be discharged from the solvent discharge pipe 1 through the solvent volatilized during the input and concentration of the first material inlet and outlet 3;
and a second control valve 8 for controlling the output of the concentrated sample is arranged on the second material inlet/outlet 9, and a tail pipe 7 is arranged between the fraction collection bin 6 and the second control valve 8 and used for storing the concentrated sample.
The plunger rod 4 moves up and down along with the volume change of the liquid in the bin body of the fraction collecting bin 6, when the liquid flows into the bin body, the plunger rod 4 moves up, and the bin body is enlarged; during concentration, the plunger rod 4 moves downwards along with the reduction of the volume of the liquid in the cartridge body, and the cartridge body is shrunk. In a preferred embodiment of the present invention, the tail pipe 7 has a volume of 0.01 to 200. mu.L. In a preferred embodiment of the present invention, the on-line concentration device is connected to a vacuum extractor.
In a further preferred embodiment of the present invention, a numerical control ten-way valve 15 is provided between the liquid chromatography device 16 and the gas chromatography device 20; a first interface of the numerical control ten-way valve 15 is used for flowing the outflow fraction of the liquid chromatographic analysis device 16; the third and eighth interfaces are respectively connected with the first material inlet and outlet 3 and the second material inlet and outlet 9 of the first online concentration device 21, the fifth and tenth interfaces are respectively connected with the first material inlet and outlet 3 and the second material inlet and outlet 9 of the second online concentration device 22, and the two online concentration devices are used for respectively carrying out online concentration on the effluent fractions continuously cut by the liquid chromatography device 16 according to the retention time; the sixth interface is connected to a second mobile phase container 18, and the second mobile phase is used for bringing the on-line concentrated outflow fraction containing the component to be measured into the gas chromatography device 20; the fourth interface is used for vacuumizing and discharging the solvent; the ninth interface is connected to the sample inlet of the gas chromatography device 20; the second interface and the seventh interface are directly connected by pipelines.
The second aspect of the present invention relates to the method for analyzing a liquid-gas two-dimensional chromatogram according to the first aspect of the present invention, comprising the steps of:
a. separating a sample to be detected by the liquid chromatographic analysis device 16, and performing online cutting by the numerical control ten-way valve 15 to obtain a plurality of sections of effluent fractions containing components to be detected;
b. the effluent fraction containing the components to be detected sequentially or alternately enters the first online concentration device 21 and the second online concentration device 22 for concentration through the switching of the numerical control ten-way valve 15, and the concentrated effluent fraction containing the components to be detected is sequentially or alternately obtained;
c. and sequentially or alternately enabling the concentrated outflow fraction containing the components to be detected to enter the gas chromatography analysis device 20 for analysis and detection, and obtaining the content of the components to be detected by adopting an internal standard method.
In a preferred embodiment of the present invention, the in-line cutting is performed as follows: the effluent fraction of the liquid chromatography device 16 is subjected to fraction cutting according to retention time by using a numerical control ten-way valve 15, so that the effluent fraction containing the component to be measured with specific retention time is fed into an on-line concentration device.
In a preferred embodiment of the present invention, when the sample to be tested is blood or urine of a smoker, the method further comprises the following pretreatment steps: extracting a smoker blood or urine sample by using dichloromethane or chloroform solution containing a corresponding internal standard substance of a component to be detected; and standing for layering, and then taking an organic layer for filtering to obtain a sample to be detected.
The third aspect of the present invention relates to the use of a liquid-gas two-dimensional chromatograph according to the first aspect of the present invention or an analysis method according to the second aspect of the present invention for determining the content of tobacco-specific nitrosamines or metabolites thereof in the blood of a smoker. Such as the content of 4- (methylnitrosamine) -1- (3-pyridyl) -1-butanone (NNK) or 4- (methylnitrosamine) -1- (3-pyridyl) -1-butanol NNAL in blood.
In the preferred embodiment of the present invention, the chromatographic column used in the liquid chromatography device 16 is an alumina column, and the alumina column is a spherical alumina chromatographic column filled with alumina microspheres with a diameter of 3 to 5 μm.
Compared with the prior art, the utility model, its beneficial effect does:
1. the traditional liquid-gas two-dimensional chromatography adopts liquid chromatography fraction center cutting, and has the defects that only a certain part of liquid chromatography fractions can be cut into the gas chromatography by one sample injection, the rest fractions are discharged as waste liquid, and each section of fractions separated by the liquid chromatography cannot be cut into the gas chromatography. And the utility model discloses then the accessible is controlled liquid chromatography separation speed, on-line concentration speed and gas chromatography analysis speed and is matchd, can all cut through each section fraction of liquid chromatography separation and enter into gas chromatography, realizes full two-dimentional chromatographic analysis mode for solve among the prior art sensitivity low, to the solvent volume of turning into gas chromatography introduction port have the restriction, can not cut the scheduling problem in succession to the component.
2. The utility model discloses a liquid phase-gas phase two dimension chromatogram can fully realize that the bigger volume of one-Level Chromatogram (LC) advances kind and the bigger volume of one-level chromatogram fraction cuts in second Grade Chromatogram (GC), to low content sample, can let the sample advance kind in succession and carry out selective continuous cutting through numerical control ten-way valve, shift to gas chromatography analysis again after the component content that waits to detect accumulates to the ideal analysis volume, improved analytical sensitivity and instrument application scope greatly when realizing that the sample high efficiency purifies. The device and the method of the utility model can meet the analysis requirement of the NNK and the NNAL with ultra-low content in the blood of smokers, and solve the bottleneck that the current standard method can not meet the analysis of the content of the tobacco-specific nitrosamine in the blood of smokers; and through the utility model discloses the method purifies the back, and the chromatographic peak of disturbing impurity obviously reduces, and the chromatography of the component that awaits measuring is outstanding and has better peak type, explains that sample purifying effect is showing and is improving.
3. The utility model discloses a device and method have avoided pretreatment steps such as concentration, transfer, constant volume among the sample pretreatment process, have reduced experimental error, because sample treatment manual operation link significantly reduces, the reproducibility of method also obtains obviously improving. Meanwhile, the online operation reduces the transfer and the loss of components to be measured in the sample processing process, and the precision of the sample analysis result is greatly improved.
Drawings
FIG. 1 is a schematic structural diagram of a liquid-gas two-dimensional chromatograph for on-line continuous cutting detection of liquid chromatogram fractions, wherein the arrow direction represents the material conveying direction;
FIG. 2 is a schematic diagram of an on-line concentration device in a liquid-gas two-dimensional chromatograph according to the present invention;
fig. 3 is a schematic flow path diagram of the numerical control ten-way valve in the liquid-gas two-dimensional chromatography according to the present invention in two different modes; wherein the first in-line concentrator receives the fraction (shown in dashed lines), the second in-line concentrator is in a state of being eluted by the second mobile phase and injected into the gas chromatograph (shown in solid lines), and the second in-line concentrator receives the fraction, and the first in-line concentrator is in a state of being eluted by the second mobile phase and injected into the gas chromatograph.
FIG. 4 is a chromatogram of the separation of NNK and NNAL from basic alumina chromatography column of example 1;
FIG. 5 is a mass spectrum of NNK (FIG. 5a) and NNAL (FIG. 5b) in example 1;
figure 6 is a selective ion chromatogram of NNK (figure 6a) and NNAL (figure 6b) in example 1.
The reference symbols in the figures have the following meanings: 1-solvent drain pipe; 2-a first control valve; 3-a first material inlet and outlet; 4-a plunger rod; 5-temperature control heating device; 6-fraction collection bin; 7-tail pipe; 8-a second control valve; 9-second material inlet and outlet; 10-a valve; 11-a first pump; 12-a second pump; 13-a first degassing device; 14-a second degassing device; 15-a numerical control ten-way valve; 16-a liquid chromatography device; 161-column oven; 162-a liquid chromatography column; 163-ultraviolet detector; 164-a sample injector; 17-a first mobile phase vessel; 18-a second mobile phase vessel; 19-a waste liquid discharge port; 20-a gas chromatography apparatus; 21-a first in-line concentration unit; 22-second in-line concentration unit.
Detailed Description
The following further description of the present invention is provided in conjunction with the accompanying drawings and examples, but the present invention is not limited in any way, and any changes or substitutions made based on the teachings of the present invention are all within the protection scope of the present invention.
Example 1
A liquid-gas two-dimensional chromatogram as shown in fig. 1, which comprises a liquid chromatogram analysis device 16 and a gas chromatogram analysis device 20 located downstream thereof; a numerical control ten-way valve 15 is arranged between the liquid chromatographic analysis device 16 and the gas chromatographic analysis device 20; a first interface of the numerical control ten-way valve 15 is used for flowing the outflow fraction of the liquid chromatographic analysis device 16; the third and eighth interfaces are respectively connected with the first material inlet and outlet 3 and the second material inlet and outlet 9 of the first online concentration device 21, the fifth and tenth interfaces are respectively connected with the first material inlet and outlet 3 and the second material inlet and outlet 9 of the second online concentration device 22, and the two online concentration devices are used for sequentially or alternately carrying out online cutting, collection and concentration on the effluent fraction continuously cut by the liquid chromatography device 16 according to the retention time; the sixth interface is connected to a second mobile phase container 18, and the second mobile phase is used for bringing the on-line concentrated outflow fraction containing the component to be measured into the gas chromatography device 20; the fourth interface is used for vacuumizing and discharging the solvent; the ninth interface is connected to the sample inlet of the gas chromatography device 20.
The on-line concentration device comprises the following components which are sequentially communicated by fluid: a first material inlet and outlet 3, a solvent evaporation device and a second material inlet and outlet 9. The solvent evaporation device comprises a fraction collection bin 6, a plunger rod 4 which is inserted into the fraction collection bin 6 in a sealed manner, and a temperature control heating device 5 which is positioned on the outer wall of the fraction collection bin 6; wherein the plunger rod 4 can move up and down along the inner wall of the fraction collecting bin 6 under the action of the buoyancy of the sample to be concentrated or the gravity of the sample to be concentrated; the plunger rod 4 is provided with a through passage for communicating the first material inlet/outlet 3 and the fraction collecting bin 6; a solvent discharge pipe 1 crossed with the first material inlet/outlet 3 is arranged on the first material inlet/outlet 3, a first control valve 2 is arranged at the cross position of the first material inlet/outlet 3 and controls the fraction to be cut to be input by the first material inlet/outlet 3 and the discharge of the solvent volatilized during concentration through the solvent discharge pipe 1 by the first control valve 2; and a second control valve 8 for controlling the output of the concentrated sample is arranged on the second material inlet/outlet 9, and a tail pipe 7 is arranged between the fraction collection bin 6 and the second control valve 8 and used for storing the concentrated sample. The volume of the tail pipe 7 is 0.01-200 mu L. The online concentration device is connected with a vacuum pumping device.
The working principle of the two-dimensional chromatogram is as follows: first, the first pump 11 is started to allow the first mobile phase to enter the liquid chromatography device 16 through the first degassing device 13; the sample to be measured enters the liquid chromatography device 16 through the sample injector 164 and is separated through the liquid chromatography column 162; the effluent fraction from the liquid chromatographic analysis device 16 enters a numerical control ten-way valve 15 through a first interface according to retention time, and the effluent fraction to be concentrated containing the component to be detected is transferred to a first online concentration device 21 for concentration through the numerical control ten-way valve 15; after the transfer is finished, the numerical control six-way valve 15 is switched, and the fractions to be concentrated containing the components to be measured with other retention time are transferred into the second online concentration device 22 for concentration through the numerical control ten-way valve 15; after the material concentration in one on-line concentration device is finished, starting the second pump 12 to enable the second mobile phase 18 to enter the numerical control six-way valve 15 through the second degassing device 14; the second mobile phase 18 discharges the effluent fraction containing the component to be measured after being concentrated in the on-line concentration device through the ninth interface of the numerical control six-way valve 15 and transmits the effluent fraction to the sample inlet of the gas chromatography device 20 for gas chromatography. When the number of the cut fractions to be detected is more than two, the two online concentration devices work alternately, one on the other is eluted and sample-introduced to the gas chromatography during concentration, and the processes are alternately carried out, so that the fractions flowing out in sequence according to different retention times in the liquid chromatography can be sequentially collected, concentrated and sample-introduced to the gas chromatography.
Wherein, the operating principle of the online concentration device is as follows: rotating the first control valve 2 to close the first pipeline and communicating the solvent discharge pipe 1 with the fraction collection bin 6; rotating a second control valve 8 to enable a sample to be concentrated to enter a fraction collection bin 6 through a second pipeline, enabling the plunger rod 4 to move upwards, and starting a temperature control heating device 5 and a vacuumizing device; and after the sample introduction of the concentrated sample is finished, closing the second control valve 8 for concentration. In the concentration process, the solvent in the sample to be concentrated is discharged through the solvent discharge pipe 1, the sample volume in the fraction collection bin 6 is reduced, and the plunger rod 4 moves downwards. After the sample is concentrated, the concentrated sample is stored in a tail pipe 7, the first control valve 2 and the second control valve 8 are opened, so that the second mobile phase enters the fraction collecting bin 6, and the concentrated sample is driven to be discharged out of the online concentration device through the second channel.
Example 2
The method for analyzing the ultra-low content of NNK and NNAL in the blood of a smoker by using the liquid-gas two-dimensional chromatography in the example 1 comprises the steps of sample pretreatment and instrument analysis, and specifically comprises the following steps:
a: sample extraction: taking 50mL of a blood sample into a 100mL test tube, and adding 10mL of dichloromethane containing deuterium-depleted NNK and NNAL internal standard (the concentration is 50 ng/L); shaking with a high speed homogenizer at 20000 rpm for 5min, standing for layering, collecting the lower clear liquid (dichloromethane layer) 1.0mL, filtering with 0.25 μm filter head to obtain the sample for next liquid chromatography.
B: analyzing by an instrument: the structure schematic diagram of the online liquid-gas two-dimensional chromatographic device is shown in fig. 1, a sample enters a high performance liquid chromatograph through a sample injector 164, a first mobile phase 17 is conveyed by a first pump 11 and is separated through a liquid chromatographic column 162, required fractions (containing NNK and NNAL parts) are sequentially transferred into a first online concentration device 21 and a second online concentration device 22 (shown in fig. 2) through a numerical control ten-way valve 15, and after the transfer is finished, the numerical control ten-way valve 15 is switched to discharge a first mobile phase waste liquid from a waste liquid discharge port; starting a temperature control heating device 5 of the online concentration device for heating, vacuumizing to remove the solvent, and performing online concentration on the cut fraction of the liquid chromatogram until the volume is less than 200 mu L; after the concentration is finished, a second pump 12 is started to convey a second mobile phase 18 to convey the concentrated fraction in the on-line concentration device to a gas chromatography pre-column, a solvent discharge valve is arranged between the gas chromatography pre-column and an analysis column, the liquid chromatography is switched into a sample to be evaporated in vacuum to discharge the solvent, then the temperature is raised and the gas is gasified, the gas is conveyed into a capillary separation column by carrier gas, and the capillary separation column is separated and then detected by mass spectrometry. The more specific process is as follows:
b1: liquid chromatography separation: a liquid-phase chromatographic band ultraviolet detector 163 with a detection wavelength of: 254nm, and the liquid chromatography separation column is: a spherical alumina column (the column is formed by filling 3-5 μm spherical alumina, the inner diameter of the column is 3.9mm, the length of the column is 150mm, and due to the fact that the difference between NNK and NNAL and main coexisting substances in blood is large, most of interference components can be separated by using an alkaline alumina normal phase chromatography, and therefore purification of a sample is achieved); the column temperature is controlled by 30 ℃ through a column temperature box, and the constant temperature is kept. Considering that the fraction cut from the liquid chromatography to the gas chromatography needs to be subjected to gas chromatography analysis after solvent is removed, the liquid chromatography preferably adopts volatile mobile phase, so that the mobile phase of the liquid chromatography is dichloromethane-acetone (90/10, volume ratio) and the flow rate is 0.8 mL/min; the double pump system, the first pump 11 is used for providing the first mobile phase 17 of liquid chromatogram separation, the second pump 12 is used for controlling the switch between HPLC and GC, and the cut fraction to be detected is transferred into gas chromatogram. The injection volume of the liquid chromatography is 400 mu L. Under this condition, the chromatogram for the separation of NNK and NNAL is shown in FIG. 4; the peak of NNK is between 7.8 and 8.4min, the peak time of NNAL is between 10.0 and 10.8min, in order to avoid that the component to be measured can not be completely collected due to the slight fluctuation of retention time, the utility model discloses in 7.6-8.6 min outflow fraction shift to first online enrichment facility 21, collect NNK, shift 9.8-11.0 min outflow fraction to second online enrichment facility 22, collect NNAL; the volumes of the liquid chromatographic cut into the two in-line concentration devices were 0.8mL and 0.96mL, respectively, due to a flow rate of 0.8 mL/min. The specific operation is as follows: 7.6-8.6 min outflow fraction (containing NNK part) enters from the port 1 of the numerical control ten-way valve 15, passes through the ports 2 and 7, flows out from the port 8, enters the first online concentration device 21, and is concentrated in vacuum through the ports 3 and 4, and the second pump 12 is closed (as shown in figure 3 a); after the fraction is cut, the fraction flows out from the inlet of the port 1 and the outlet of the port 10 again by switching the numerical control ten-way valve 15 for 9.8-11.0 min, enters the second online concentration device 22, and is subjected to vacuum concentration by the ports 5 and 4 (as shown in figure 3 b). During the cut of the distillate into the second in-line concentration device 22; second pump 12 is activated and second mobile phase 18 enters at port 6, passes through ports 7 and 2, exits at port 3, and elutes the fractions from first in-line concentration unit 21 into gas chromatography via ports 8 and 9. When the numerically controlled ten-way valve 15 is switched again to cut the distillate into the first online concentration device 21, the second pump 12 is started, the second mobile phase 18 flows out from the 6-port inlet and the 5-port inlet, passes through the second online concentration device 22, then flows out from the 10-port inlet and the 9-port inlet, and the components in the second online concentration device 22 elute into the gas chromatography, wherein the second mobile phase 18 does not enter the gas chromatography analysis device 20. Due to the switching of the numerical control ten-way valve 15, two online concentration devices alternately collect the effluent fractions of the liquid chromatogram, and the continuous cutting can be realized. By controlling the matching of the liquid chromatography separation speed, the on-line concentration speed and the gas phase analysis speed, each section of fraction separated by the liquid chromatography can be cut and enter the gas chromatography, and the full two-dimensional chromatographic analysis mode is realized. The flow paths in the two different modes of the digitally controlled ten way valve 15 are listed in figure 3.
B2: and (3) online concentration: the online concentration device is shown in figure 2, a plunger rod 4 moves up and down along with the volume change of liquid in a bin body of the fraction collection bin 6, when the liquid flows into the bin body, the plunger rod 4 moves up, and the bin body is enlarged; during concentration, as the volume of liquid in the bin body is reduced, the plunger rod 4 moves downwards, the bin body is shrunk, a concentrated sample is collected in the tail pipe 7 with the volume of 200 mu L, and when the plunger rod 4 is contacted with the bottom of the fraction collection bin 6 (the concentrated fraction completely enters the tail pipe 7), the solvent discharge is automatically stopped. Because the online two-dimensional chromatogram of the embodiment is modified on the Shimadzu gel gas chromatograph-mass spectrometer, the maximum fraction volume cut into the gas chromatogram by the liquid chromatogram is 200 muL; the volumes of fractions which need to be collected by two chromatographic peaks in the utility model are 0.8mL and 0.96mL respectively. Experimental results show that the online concentration device is heated to 45 ℃, the solvent is discharged by vacuumizing, and the volume of the effluent fraction of the liquid chromatogram can be concentrated to be less than 200 mu L by controlling the time to be 4.5 min. After the concentration, the vacuum solvent outlet 4 on the numerical control ten-way valve 15 is closed, and the channels leading to the liquid chromatography and the gas chromatography are opened at the same time, and the concentrated sample is transferred into the gas chromatography analysis device 20 by the second pump 12 in fig. 1.
B3: gas chromatography mass spectrometry: and after the sample completely enters the gas chromatography, closing the liquid chromatography channel, and removing the solvent in the inert quartz tube through a solvent discharge valve in the gas chromatography. And after the solvent is completely removed, closing a solvent discharge port, and starting the gas chromatography to heat for gas chromatography analysis. With the aim of completely separating NNK and NNAL and of minimizing the analysis time, the following chromatographic conditions were finally selected: the gas chromatograph with the quartz lining tube capable of removing the solvent on the column head has the pre-reserved column specifications as follows: 5 m.times.0.25 mm.d.times.0.25. mu. mdf, DB-5ms (J & W); the analytical column specification is: AgilentDB-35MSUI capillary chromatography column (30m 250 μm 0.25 μm); the carrier gas is helium and a constant-current mode is adopted; the flow rate is 1.2 mL/min; sample inlet temperature: 290 ℃; temperature program of chromatographic column: the initial temperature was 50 deg.C (held for 1.0min), ramped to 170 deg.C at a rate of 30 deg.C/min, then ramped to 230 deg.C at a rate of 5 deg.C/min, and ramped to 290 deg.C at a rate of 30 deg.C/min.
Mass spectrum conditions: the aim of achieving the highest response of NNK and NNAL is to optimize the mass spectrum condition, and finally, the ionization mode is selected: an EI source; ionization energy: 30 eV; temperature of the ion source: 250 ℃; the transmission line temperature is 250 ℃; scanning mass range 50-300 amu; the scanning interval is 0.5 s; quadrupole temperature: 120 ℃; scanning mode: selecting an ion detection (SIM) mode, and quantifying by adopting a method of extracting single ions from a total ion flow diagram, wherein according to mass spectrograms (figure 5a and figure 5b), quantitative ions of NNK and NNAL are m/z177 and 209 respectively; the quantitative ions of the isotope internal standard are m/z181 and 213 respectively; under selected conditions, selective ion chromatograms of NNK and NNAL are shown in fig. 6a and 6 b.
Example 3 determination of working curves, detection limits and quantitation limits
Preparation of a standard solution:
preparation of standard stock solutions: respectively weighing 0.1g of NNK and NNAL (accurate to 0.1mg) in a 100mL volumetric flask, dissolving with dichloromethane, fixing the volume, preparing a mixed standard stock solution with the concentration of each component being 1.0mg/mL, sealing and storing at-20 ℃ in a dark place.
Internal standard stock solution: 100mg of d4-NNK and d4-NNAL (accurate to 0.1mg) are respectively weighed in a 100mL volumetric flask, dissolved by dichloromethane and fixed to volume to scale to prepare a mixed internal standard stock solution with the concentration of each component of 0.1mg/mL, and the mixed internal standard stock solution is sealed and stored at the temperature of minus 20 ℃ in a dark place.
Standard working solution: diluting the standard stock solution with chloroform step by step to obtain 6-stage standard working solution, wherein the concentrations of the components to be detected are 0.01ng/mL, 0.05ng/mL, 0.1ng/mL, 0.5ng/mL, 1.0ng/mL and 5.0ng/mL, and the concentration of the internal standard substance is 0.05 ng/mL.
Sample extraction solution: internal standard stock solutions were prepared as dichloromethane solutions containing 0.05ng/mL internal standard.
Preparing a series of standard solutions with different TSNAs concentrations (the internal standard concentrations are all 0.05ng/mL), analyzing according to the selected instrument conditions of the embodiment 2, and performing linear regression by using the peak areas (A) and the concentrations (C) of the standard samples to obtain a linear regression equation; the results are shown in Table 1. Continuously injecting the standard solution with the lowest concentration for 10 times, measuring the standard deviation of the standard solution, taking 3 times of the standard deviation as a detection limit, and taking 10 times of the standard deviation as a quantification limit; specific results are shown in table 1.
Table 1: working curve, correlation coefficient, detection limit and quantification limit of measuring method
The sensitivity of a measurement instrument is measured in terms of its limit of detection (LOD), which refers to the minimum concentration or amount of an element required to analyze a signal that can be reliably detected; wherein the limit of quantitation refers to the lowest amount of the analyte in the sample that can be quantitatively determined.
The value of the detection limit is known to be 3 times the standard deviation and the value of the quantitation limit is known to be 10 times the standard deviation.
The results in table 1 show that the inventive analysis device has a high sensitivity.
Example 4 method recovery and reproducibility
The precision in the day is as follows: blood samples from the same smoker were measured 7 times in the same day under the same conditions of example 2 and the Relative Standard Deviation (RSD) of the 7 replicates was calculated, giving RSD for the four NNKs and NNAL in the range of 4.3% -4.8%; indicating that the method is accurate.
The daytime precision is as follows: the RSD of NNK and NNAL was found to be in the range of 5.2% to 6.0% by measuring the blood of smokers whose daily frequency of smoking number was kept consistent 1 time per day for 7 days under the same conditions as in example 2 and calculating the relative standard deviation of the results of the 7 measurements; indicating that the method precision is still good when measured at different times.
During measurement, 4 parts of the same sample are weighed for each sample, wherein 1 part of the sample is not added with a standard substance, the other 3 parts of the sample are respectively added with known amounts of NNK and NNAL (the addition amounts are respectively 0.03, 0.06 and 0.09 ng; the sample is processed according to the selected sample pretreatment condition, sample injection analysis is carried out according to the selected instrument condition, the amount (background) measured by adding a standard sample is subtracted from the amount measured by adding the standard sample, and then the recovery rate is calculated by dividing the amount added by the standard, so that the recovery rate of TSNAs is 73.5-82.9 percent, and the method is high in recovery rate.
Example 5
The measurements of NNK and NNAL in the blood of smokers were carried out using the method of example 2 and the results are shown in Table 2. From the analysis results, it can be seen that, although the ultra-high-sensitivity analysis method and device are adopted, the tobacco-specific nitrosamine concentration in the blood of only mixed-type cigarette smokers is above the quantitative limit of the analysis method, and most of the tobacco-specific nitrosamine content in the blood of the tobacco-type cigarette smokers is still below the quantitative limit. The tobacco-specific nitrosamine content in blood of cigarette smokers, both mixed cigarette smokers and flue-cured cigarette smokers, is far below the concentration level harmful to human bodies.
Table 2: TSNAs assay results in representative samples
Remarking: "-" indicates that the content is below the limit of quantitation
Example 6
The measured sample is a blood sample of a mixed type cigarette heavy smoker, 50mL of the blood sample is taken and put into a 100mL test tube, and 10mL of dichloromethane containing the deuterium-depleted NNK and NNAL internal standard (the concentration is 50ng/L) is added; shaking with a high speed homogenizer at 20000 rpm for 5min, standing for layering, collecting the lower clear liquid (dichloromethane layer) 1.0mL, filtering with 0.25 μm filter head, and separating by liquid chromatography. The sample enters a high performance liquid chromatograph through a sample injector, the experimental conditions are the same as those of example 2, 7.6-8.6 min of effluent fraction is transferred into a first online concentration device 21, NNK is collected, 9.8-11.0 min of effluent fraction is transferred into a second online concentration device 22, and cut fraction is concentrated into tail pipes with the volume of less than 200 mu L in the two online concentration devices. After the concentration, the mixture enters a gas chromatography device, and the gas chromatography is started to heat for gas chromatography analysis. The measurement result shows that the total NNK content of the blood sample is 4.04ng/L, and the NNAL content is 3.86 ng/L.
Example 7
The measured sample is a blood sample of a mixed type cigarette light smoker, 50mL of the blood sample is taken and put into a 100mL test tube, and 10mL of dichloromethane containing deuterium-depleted NNK and NNAL internal standard (the concentration is 50ng/L) is added; shaking with a high speed homogenizer at 20000 rpm for 5min, standing for layering, collecting the lower clear liquid (dichloromethane layer) 1.0mL, filtering with 0.25 μm filter head, and separating by liquid chromatography. The sample enters a high performance liquid chromatograph through a sample injector, the experimental conditions are the same as those of example 2, 7.6-8.6 min of effluent fraction is transferred into a first online concentration device 21, NNK is collected, 9.8-11.0 min of effluent fraction is transferred into a second online concentration device 22, and cut fraction is concentrated into tail pipes with the volume of less than 200 mu L in the two online concentration devices. After the concentration, the mixture enters a gas chromatography device, and the gas chromatography is started to heat for gas chromatography analysis. The measurement result shows that the total NNK content of the blood sample is 2.93ng/L, and the NNAL content is 1.87 ng/L.
Example 8
The measured samples are blood samples of a flue-cured cigarette heavy smoker, a flue-cured cigarette heavy smoker and an electronic cigarette smoker respectively, 50mL of the blood samples are taken in a 100mL test tube respectively, and 10mL of dichloromethane containing a deuterium-depleted NNK and NNAL internal standard (the concentration is 50ng/L) is added; shaking with a high speed homogenizer at 20000 rpm for 5min, standing for layering, collecting the lower clear liquid (dichloromethane layer) 1.0mL, filtering with 0.25 μm filter head, and separating by liquid chromatography. The sample enters a high performance liquid chromatograph through a sample injector, the experimental conditions are the same as those of example 2, 7.6-8.6 min of effluent fraction is transferred into a first online concentration device 21, NNK is collected, 9.8-11.0 min of effluent fraction is transferred into a second online concentration device 22, and cut fraction is concentrated into tail pipes with the volume of less than 200 mu L in the two online concentration devices. After the concentration, the mixture enters a gas chromatography device, and the gas chromatography is started to heat for gas chromatography analysis. The results of the measurements showed that none of the above 3 smokers detected NNK and NNAL in their blood.
Claims (3)
1. A liquid-gas two-dimensional chromatograph in which the liquid chromatographic fractions can be cut and detected on-line continuously, characterized in that it comprises a liquid chromatographic analysis device (16) and a gas chromatographic analysis device (20) located downstream thereof; be equipped with two at least online enrichment facility between liquid chromatography analytical equipment (16) and gas chromatography analytical equipment (20), online enrichment facility be used for with multistage outflow fraction that liquid chromatography analytical equipment (16) cut according to retention time advances kind respectively after concentrating in gas chromatography analytical equipment (20) in proper order or in turn.
2. The liquid-gas two-dimensional chromatogram of claim 1, characterized in that the in-line concentration device comprises the following components in fluid communication in sequence: a first material inlet and outlet (3), a solvent evaporation device and a second material inlet and outlet (9); wherein,
the solvent evaporation device comprises a fraction collection bin (6), a plunger rod (4) which is inserted into the fraction collection bin (6) in a sealed manner, and a temperature control heating device (5) which is positioned on the outer wall of the fraction collection bin (6); wherein the plunger rod (4) can move up and down along the inner wall of the fraction collecting bin (6) under the action of the sample to be concentrated on the buoyancy or the gravity of the sample to be concentrated; the plunger rod (4) is provided with a through passage which is communicated with the first material inlet and outlet (3) and the fraction collecting bin (6);
A solvent discharge pipe (1) crossed with the first material inlet and outlet (3) is arranged on the first material inlet and outlet, a first control valve (2) is arranged at the crossed position of the first material inlet and outlet and controls the input of cutting fractions from the first material inlet and outlet (3) and the discharge of the volatilized solvent through the solvent discharge pipe (1) during concentration by the first control valve (2);
and a second control valve (8) for controlling the output of the concentrated sample is arranged on the second material inlet and outlet (9), and a tail pipe (7) is arranged between the fraction collecting bin (6) and the second control valve (8) and is used for storing the concentrated sample.
3. The liquid-gas two-dimensional chromatogram of claim 2, characterized in that a numerically controlled ten-way valve (15) is provided between the liquid chromatogram analysis device (16) and the gas chromatogram analysis device (20); a first interface of the numerical control ten-way valve (15) is used for flowing in the outflow fraction of the liquid chromatographic analysis device (16); the third interface and the eighth interface are respectively connected with a first material inlet and outlet (3) and a second material inlet and outlet (9) of the first online concentration device (21), the fifth interface and the tenth interface are respectively connected with the first material inlet and outlet (3) and the second material inlet and outlet (9) of the second online concentration device (22), and two online concentration devices are used for respectively carrying out online concentration on the effluent fractions continuously cut by the liquid chromatography device (16) according to the retention time; the sixth interface is connected to a second flowing phase container (18) which is used for bringing the on-line concentrated outflow fraction containing the component to be tested into the gas chromatographic analysis device (20); the fourth interface is used for vacuumizing and discharging the solvent; the ninth interface is connected to a sample inlet of the gas chromatography device (20); the second interface and the seventh interface are directly connected by pipelines.
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| CN105510489B (en) * | 2015-12-22 | 2018-03-13 | 云南中烟工业有限责任公司 | A kind of liquid chromatogram cut can on-line continuous cutting detection liquid phase gas phase Two way chromatograms and its application |
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