CN111380944A - Liquid chromatogram and ion mobility spectrometry combined analyzer - Google Patents
Liquid chromatogram and ion mobility spectrometry combined analyzer Download PDFInfo
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- CN111380944A CN111380944A CN202010220870.5A CN202010220870A CN111380944A CN 111380944 A CN111380944 A CN 111380944A CN 202010220870 A CN202010220870 A CN 202010220870A CN 111380944 A CN111380944 A CN 111380944A
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- ion mobility
- chromatographic column
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
- G01N27/622—Ion mobility spectrometry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
Abstract
The invention discloses a liquid chromatogram and ion mobility spectrometry combined analyzer, which comprises: sample injector, HPLC pump, chromatographic column, zero dead volume integral flow device, electrospray nozzle needle and ion mobility spectrometer; the sample injector is grounded, and the sample injector is connected with the chromatographic column by a PEEK tube or an elastic quartz capillary tube; HPLC pumps were used to pump the solution through a sample injector into the column. The chromatographic column is connected with the zero dead volume flow splitting device through a stainless steel pipe; the electrospray nozzle needle generates gaseous ions under the action of high pressure. The ion mobility spectrometer is connected with the chromatographic column through an electrospray nozzle needle, provides gas phase ion separation outside the chromatographic column separation, and completes signal detection. The invention has the advantages that: the cost is low, the advantages of two-dimensional separation are fully utilized, and the performance of the separator is greatly improved; the sensitivity is high, and the band diffusion is small; the resolution is high, and the resolution of the ion mobility spectrometer can reach more than 120-150.
Description
Technical Field
The invention relates to the technical field of food safety, natural product and drug analysis, in particular to an analysis device and method for integrating two different separation mechanisms, namely ion mobility spectrometry and liquid chromatography.
Background
An atmospheric Pressure Ion Mobility Spectrometry (AP-IMS), also called as Ion Mobility Spectrometry, is an analysis method for separating ions from neutral gas molecules under atmospheric Pressure by low-energy collision, and has the characteristics of simple structure, stability, reliability, high sensitivity, high analysis speed, low analysis cost and the like. At present, the ion mobility spectrometry is mainly applied to security inspection occasions such as airports, stations and the like, and is widely applied to the detection of chemicals which are easy to prepare drugs, the detection of chemical warfare agents and the like. Combined with a chromatograph and a mass spectrometer, the ion mobility spectrometry is more and more widely applied in the fields of food safety, drug analysis, environmental monitoring, metabonomics and the like. Ion mobility spectrometry is generally composed of an ion source, an ion gate, a mobility separation region, and a detector. Solid, liquid or gas samples are ionized in an ion source to generate ions, and commonly used ion sources comprise a radiation ionization source, an ultraviolet light ionization source, field ionization, corona discharge, dielectric barrier discharge, electrospray ionization and other modes. The ions are driven by the electric field to enter the drift region through the periodically opened ion gates and continuously collide with the neutral gas molecules drifting in a countercurrent mode. Because the ions have different migration rates in the electric field, different ions are separated according to different collision cross sections and different carried charges and then reach the collector to be detected. Thus, the presence of the analyte target substance can be determined by measuring the migration time, and the concentration of the corresponding substance can be determined using the peak area or peak height.
In the fields of food safety, natural products, pharmaceutical analysis, and the like, the sample composition is very complicated. At this time, the ion mobility spectrometry is used together with the liquid chromatogram through an electrospray interface, and the ion mobility spectrometry is used as a detector of the liquid chromatogram, so that the defects of an ultraviolet detector, a fluorescence detector, a differential refraction detector and the like commonly used by the liquid chromatogram can be overcome, the sensitivity of the ion mobility spectrometry is higher than that of the differential refraction detector, gradient elution can be used, the ion mobility spectrometry has good response on the ion mobility spectrometry for a compound lacking a chromophore on a molecular structure compared with the ultraviolet detector, the compound is not required to have fluorescence activity compared with the fluorescence detector, and the linear range is good compared with an evaporative light scattering detector. More importantly, the ion mobility spectrogram obtained by measuring the effluent of the chromatographic separation column simultaneously realizes two-dimensional separation based on the difference of hydrophobicity and ion mobility before electrospray ionization and after electrospray ionization, can provide richer chemical information for accurate identification of a complex sample system, and enhances the analysis value of the ion mobility spectrogram. Compared with a liquid chromatogram-mass spectrometer, the liquid chromatogram-ion mobility spectrometry combined instrument has the advantages of price and cost and is suitable for on-site rapid detection. Meanwhile, the ion mobility spectrometry is used for analyzing gaseous ions under normal pressure instead of the high vacuum condition required by a mass spectrometer, and the interface device for combining the liquid chromatogram with the ion mobility spectrometry is simple and easy to build and realize.
Although there are many reports on the combination of liquid chromatography and ion mobility spectrometry, the current technical solutions have major disadvantages. First, due to the mismatch between the flow rates of hplc and electrospray ion mobility spectrometry, a flow split between them is required. Because the flow velocity is very low after the split, the liquid after the column stays in the splitting device and the electrospray channel for a long time, the mixing is serious, and the chromatographic separation effect is seriously reduced; secondly, the ion mobility spectrometry works under high pressure, the high pressure of electrospray is superposed on the high pressure of a migration tube, and the voltage difference between a liquid chromatograph and an electrospray ion source is the sum of the electrospray voltage and the migration voltage, so that a serious electrophoresis phenomenon occurs in a pipeline. Thirdly, the traditional single-pulse ion mobility spectrometry working mode has low ion utilization rate and needs to be repeated for many times to improve the signal-to-noise ratio of a spectrogram, so that the sampling speed of the spectrogram is low and cannot keep up with the rapid chromatographic separation speed.
Therefore, how to improve the resolution and sensitivity of the combination of the chromatography and the ion mobility spectrometry, improve the interface between the ion mobility spectrometry and the liquid chromatography, and keep the separation efficiency of the chromatography as much as possible remains a technical problem which is urgently solved by those skilled in the art at present.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a liquid chromatogram and ion mobility spectrometry combined analyzer, which solves the defects in the prior art.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a liquid chromatography and ion mobility spectrometry combination analyzer, comprising: the device comprises a sample injector 1, an HPLC pump 2, a chromatographic column 3, a zero-dead-volume integral flow device 4, an electrospray nozzle needle 5, an ion mobility spectrometer 6 and a high-voltage power supply 7;
the sample injector 1 is grounded, and the sample injector 1 is connected with the chromatographic column 3 by a PEEK tube or an elastic quartz capillary tube; HPLC pump 2 is used to pump the solution through injector 1 into column 3.
The chromatographic column 3 is connected with the zero dead volume integral flow device 4 through a stainless steel pipe;
the high-voltage power supply 7 is connected with the chromatographic column 3, the zero-dead-volume integral flow device 4 and the electrospray nozzle needle 5, and the electrospray nozzle needle 5 generates gaseous ions under the action of high voltage.
The ion mobility spectrometer 6 is connected with the chromatographic column 3 through an electrospray nozzle needle 5, and the ion mobility spectrometer 6 provides gas phase ion separation outside the chromatographic column 3 separation and completes signal detection.
Further, the zero dead volume flow device 4 includes: a shell 9, a solution pipeline, an electrospray nozzle needle 5,
a solution pipeline is arranged in the shell 9, the solution of the chromatographic column 3 is fed in through an inlet 8 of the solution pipeline, the redundant solution is discharged from an outlet 10 of the solution pipeline, and the electrospray nozzle needle 5 penetrates through the shell 9 and is connected with the solution pipeline 8 in a nested mode. The nesting depth is determined by the split ratio.
Furthermore, the inner diameter of the electrospray nozzle needle 5 is 20-50 μm, the outer diameter is 150-365 μm, the length is 50-80 mm, the material is stainless steel or elastic quartz capillary, and two ends are conical;
further, the inner diameter of the outlet 10 and the inlet 8 or the inner diameter of the outlet 10 is larger than that of the inlet 8;
further, the control signal of the ion mobility spectrometer 6 adopts frequency modulation square wave or phase modulation square wave, and the acquired signal adopts Fourier transform, cross-correlation transform, Hadamard transform or improved Hadamard transform.
Further, the electrospray nozzle needle 5, the chromatographic column 3, and the zero-dead-volume flow integrating device 4 are placed in an equipotential state and suspended at an electrospray high pressure.
Further, the housing 9 is made of PEEK or stainless steel.
Furthermore, the inner diameter of the stainless steel pipe is 0.2 mm-0.6 mm, and the length of the stainless steel pipe is 30 mm-50 mm.
Compared with the prior art, the invention has the advantages that:
1. the cost is low. The invention can realize the zero dead volume adjustable shunting function by adopting the common three-way device, has large shunting proportion, low band diffusion after shunting and high column efficiency of combined analysis. The method provided by the invention can be applied to the existing liquid chromatograph and ion mobility spectrometer without hardware modification, so that the method is upgraded into a liquid chromatograph-ion mobility spectrometer, the advantage of two-dimensional separation is fully utilized, and the performance of the method is greatly improved.
2. The sensitivity is high. Because the band diffusion is small, the sensitivity is improved, the electrophoresis effect on a transmission channel between the chromatographic separation and the ion mobility spectrometry separation is reduced, and the sensitivity is further improved. The sensitivity of analysis is further improved by adopting a multiplexing sampling and data processing method on the ion mobility spectrometry.
3. The resolution is high. The coupling method provided by the invention can reach theoretical resolution without sacrificing sensitivity, the resolution is greatly improved compared with that of the traditional signal averaging method, and the resolution can reach more than 120-150 by using an ion mobility spectrometer.
Drawings
FIG. 1 is a schematic structural diagram of a liquid chromatography-ion mobility spectrometry analyzer according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of an electrospray ion source according to an embodiment of the present invention;
FIG. 3 is a two-dimensional combined analysis chart of liquid chromatography-ion mobility spectrometry of an extract solution of beans according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail below with reference to the accompanying drawings by way of examples.
As shown in fig. 1, an analyzer for liquid chromatography and ion mobility spectrometry includes: the device comprises a sample injector 1, an HPLC pump 2, a chromatographic column 3, a zero-dead-volume integral flow device 4, an electrospray nozzle needle 5, an ion mobility spectrometer 6 and a high-voltage power supply 7;
the sample injector 1 is grounded, and the sample injector 1 is connected with the chromatographic column 3 by a PEEK tube or an elastic quartz capillary tube; HPLC pump 2 is used to pump the solution through injector 1 into column 3.
The chromatographic column 3 is connected with the zero dead volume integral flow device 4 through a stainless steel pipe; the inner diameter of the stainless steel pipe is 0.2 mm-0.6 mm, and the length of the stainless steel pipe is 30-50 mm;
the high-voltage power supply 7 is connected with the chromatographic column 3, the zero-dead-volume integral flow device 4 and the electrospray nozzle needle 5, and the electrospray nozzle needle 5 generates gaseous ions under the action of high voltage.
The ion mobility spectrometer 6 is connected with the chromatographic column 3 through an electrospray nozzle needle 5, and the ion mobility spectrometer 6 provides gas phase ion separation outside the chromatographic column 3 separation and completes signal detection.
As shown in fig. 2, the zero dead volume flow device 4 includes: a shell 9, a solution pipeline, an electrospray nozzle needle 5,
a solution pipeline is arranged in the shell 9, the solution of the chromatographic column 3 is fed in through an inlet 8 of the solution pipeline, the redundant solution is discharged from an outlet 10 of the solution pipeline, and the electrospray nozzle needle 5 penetrates through the shell 9 and is connected with the solution pipeline 8 in a nested mode.
The flow dividing ratio is adjusted by adjusting the nesting depth of the electrospray nozzle needle 5 and the inlet 8;
the inner diameter of the electrospray nozzle needle 5 is 20-50 mu m, the outer diameter is 150-365 mu m, the length is 50-80 mm, the material is stainless steel or elastic quartz capillary, and two ends of the electrospray nozzle needle are made into a cone shape by a mechanical or chemical corrosion method;
the inner diameter of the outlet 10 and the inlet 8 or the inner diameter of the outlet 10 is larger than that of the inlet 8;
the control signal of the ion mobility spectrometer 6 adopts frequency modulation square wave or phase modulation square wave, and the acquired signal adopts Fourier transform, cross-correlation transform, Hadamard transform or improved Hadamard transform.
The electrospray nozzle needle 5, the chromatographic column 3 and the zero-dead-volume flow integrating device 4 are placed in an equipotential state and suspended at an electrospray high pressure.
The shell 9 is made of PEEK material or stainless steel material;
example one
The liquid chromatogram used in the embodiment is a binary high-pressure gradient liquid chromatograph, which comprises two high-pressure HPLC pumps and a post-pump mixer, a sample injector 1 is grounded, an ion mobility spectrometer 6 works under atmospheric pressure, an electrospray ion source integrating a chromatographic column 3 and a zero-dead-volume integral flow device 4 in the embodiment is used as an interface of the liquid chromatogram and the ion mobility spectrum, the temperature of the ion mobility spectrum is 120 ℃, the migration gas is high-purity air, and the flow rate is 600mL.min-1The total length of a migration tube of the ion mobility spectrometer is 31 cm, the migration tube is divided into two areas by a B-N type ion gate, the front end of the migration tube is an ionization area, the length of the ionization area is 10.2 cm, the rear end of the migration tube is a migration area, and the length of the migration tube is 16.0 cm. The migration voltage is 7.2KV, the ion gate voltage is 6.05KV, the ESI voltage is 10.2KV, and the amplification factor of the amplifier is ten million times. And signal acquisition is carried out in a linear frequency modulation matched filtering mode, the sampling time is 1 second, and the scanning frequency is 40-6000 Hz. The mobile phase of the liquid chromatogram is a methanol-water system, PCP RP C18The column (4.6mm 150mm,5 μm) was chromatographed with an initial gradient of 30: 70 methanol to water for 2min, and increased to 90:10 methanol to water for 5min within 30 min.
The sample is sophora alopecuroide alkaloid extract, 200g of plant samples of different parts of sophora alopecuroide are respectively weighed, 2000ml of 0.5% sulfuric acid aqueous solution is added according to the material-liquid ratio of 1:10, reflux extraction is carried out for 2 times, 2h each time, the extract is combined, a solvent is recovered under reduced pressure and concentrated to 500ml, the PH value is adjusted to 5-10, chloroform with the same volume is added for repeated extraction for 3 times, organic phases are combined, and the total alkaloid extract of each part is obtained after reduced pressure concentration to dryness. Accurately weighing 5mg of total biological extract of each part of the sophora alopecuroides, dissolving the total biological extract in 1mL of methanol solution, preparing the total biological extract into solution with the mass concentration of 5mg/mL, and filtering the solution through a 0.22 mu m pinhole filter membrane for later use.
10uL of sample is injected through a six-way sample injector, the high pressure of the electrospray ion source is opened after 5S of sample injection, data acquisition is started, and a spectrogram is shown in figure 3.
It will be appreciated by those of ordinary skill in the art that the examples described herein are intended to assist the reader in understanding the manner in which the invention is practiced, and it is to be understood that the scope of the invention is not limited to such specifically recited statements and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (8)
1. A liquid chromatography and ion mobility spectrometry analyzer, comprising: the device comprises a sample injector (1), an HPLC pump (2), a chromatographic column (3), a zero dead volume integral flow device (4), an electrospray nozzle needle (5), an ion mobility spectrometer (6) and a high-voltage power supply (7);
the sample injector (1) is grounded, and the sample injector (1) is connected with the chromatographic column (3) by a PEEK tube or an elastic quartz capillary tube; an HPLC pump (2) is used for pumping the solution into the chromatographic column (3) through the sample injector (1);
the chromatographic column (3) is connected with the zero dead volume integral flow device (4) through a stainless steel pipe;
the high-voltage power supply (7) is connected with the chromatographic column (3), the zero-dead-volume integral flow device (4) and the electrospray nozzle needle (5), and the electrospray nozzle needle (5) generates gaseous ions under the action of high voltage;
the ion mobility spectrometer (6) is connected with the chromatographic column (3) through the electrospray spray needle (5), and the ion mobility spectrometer (6) provides gas phase ion separation outside the separation of the chromatographic column (3) and completes signal detection.
2. The analyzer of claim 1, wherein: the zero dead volume flow device (4) comprises: a shell (9), a solution pipeline, an electric spray needle (5),
a solution pipeline is arranged in the shell (9), the solution of the chromatographic column (3) is fed in through an inlet (8) of the solution pipeline, the redundant solution is discharged from an outlet (10) of the solution pipeline, and the electrospray nozzle needle (5) penetrates through the shell (9) and is connected with the solution pipeline (8) in a nested manner; the nesting depth is determined by the split ratio.
3. The analyzer for liquid chromatography combined with ion mobility spectrometry of claim 2, wherein: the inner diameter of the electrospray nozzle needle (5) is 20-50 mu m, the outer diameter is 150-365 mu m, the length is 50-80 mm, the electrospray nozzle needle is made of stainless steel or elastic quartz capillary tubes, and two ends of the electrospray nozzle needle are conical.
4. The LC-MS-IMS of claim 3, wherein: the inner diameters of the outlet (10) and the inlet (8) or the inner diameter of the outlet (10) is larger than that of the inlet (8).
5. The LC-MS-IMS of claim 4, wherein: the control signal of the ion mobility spectrometer (6) adopts frequency modulation square wave or phase modulation square wave, and the acquired signal adopts Fourier transform, cross-correlation transform, Hadamard transform or improved Hadamard transform.
6. The LC-MS-IMS of claim 5, wherein: the electrospray nozzle needle (5), the chromatographic column (3) and the zero-dead-volume integral flow device (4) are placed in an equipotential state and suspended at an electrospray high pressure.
7. The LC-MS-IMS of claim 6, wherein: the shell (9) is made of PEEK material or stainless steel material.
8. The LC-MS-IMS of claim 7, wherein: the stainless steel pipe has an inner diameter of 0.2mm to 0.6mm and a length of 30 mm to 50 mm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114965831A (en) * | 2022-05-19 | 2022-08-30 | 厦门大学 | Zero dead volume interface device for combination of chromatograph and mass spectrum and application thereof |
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| CN107271575A (en) * | 2016-04-08 | 2017-10-20 | 株式会社岛津制作所 | The method and device of ion mobility spectrometry and mass spectrum parallel parsing |
| CN110146585A (en) * | 2019-06-22 | 2019-08-20 | 湘潭大学 | Prediction and the method for eliminating hadamard transformation Ion transfer spectral transformation ghost peak |
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| CN114965831A (en) * | 2022-05-19 | 2022-08-30 | 厦门大学 | Zero dead volume interface device for combination of chromatograph and mass spectrum and application thereof |
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