CN111508815A - Mass spectrum sample introduction device and method capable of being used for complex sample analysis - Google Patents
Mass spectrum sample introduction device and method capable of being used for complex sample analysis Download PDFInfo
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- H—ELECTRICITY
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- 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
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- G—PHYSICS
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- 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
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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
- H01J49/0431—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for liquid samples
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
- H01J49/0459—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components for solid samples
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Abstract
The invention discloses a mass spectrum sampling device and a method for analyzing complex samples, wherein the mass spectrum sampling device comprises an ion source, a sampling probe and a mass spectrum sampling channel, the ion source is positioned at the mass spectrum sampling channel, the front end of the sampling probe is a sampling end, the sampling end is positioned in the ion source or near the ion source, the mass spectrum sampling device also comprises a connecting arm and a motor, one end of the connecting arm is connected with the rear end of the sampling probe, and the other end of the connecting arm is connected with a rotating shaft of the motor. After the mass spectrum sample introduction device is combined with the mass spectrum, the ionization effect on a compound sample is good, the ionization effect on complex samples such as a medicine extract, a biological sample extract, an organic polymer and the like is good, the application range is wide, the universality is strong, the operation is simple, the sampling is convenient, the analysis time is greatly shortened, the practicability is strong, and the popularization and application value is high.
Description
Technical Field
The invention relates to a mass spectrum sample introduction device and a method for complex sample analysis, and belongs to the technical field of mass spectrum analysis.
Background
Mass Spectrometry (MS) is an important analytical tool that can analyze complex mixtures, providing information about molecular weight, elemental composition, and chemical structure of the analyte, with a high degree of specificity and sensitivity. In recent years, with continuous innovation and improvement of compound desorption and ionization technologies and mass analyzers, mass spectrometry becomes one of the most rapidly developed analysis technologies, and at present, the mass spectrometry technology is more and more widely applied in the fields of chemistry and chemical industry, biology and life sciences, medicine, pharmacy, material science, environmental protection and the like.
The basic principle of mass spectrometry is to ionize each component in a sample in an ion source to generate ions with different charge-mass ratios and positive charges, form an ion beam under the action of an accelerating electric field, enter a mass analyzer, and then in the mass analyzer, generate opposite velocity dispersion by using an electric field and a magnetic field, focus the two components respectively to obtain a mass spectrogram, thereby determining the mass of the sample.
Current mass spectrometry techniques disclose a variety of ion sources, such as electron impact sources (EI), chemical ion sources (CI), fast atom impact sources (FAB), electrospray ionization sources (ESI), atmospheric pressure chemical ionization sources (APCI), matrix assisted laser desorption ionization sources (MA L DI), field desorption, field ionization, desorption electrospray ionization sources (DESI), real time analysis sources (DART), spark sources, thermal energy sources, etc., different ion sources can be selected for different samples, allowing a wide range of samples to be analyzed, and from very small molecular weight gases to millions of proteins to be measured.
The traditional mass spectrometry mainly adopts a sample rod or a sample introduction probe to manually introduce samples, and the samples are directly loaded on the sample rod or the sample introduction probe, so that the method is only suitable for analyzing simple samples, and complex samples with complex components usually need complex sample pretreatment, otherwise, the analysis requirements are difficult to achieve. For complex samples, at present, the separation is mainly performed through gas chromatography or liquid chromatography, and then the separated components enter an ion source for subsequent mass spectrometry, but the method has the disadvantages of high analysis cost, long analysis time and no contribution to rapid analysis.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is to provide a mass spectrometry sampling apparatus and method for complex sample analysis.
In order to solve the problems, the invention adopts the following technical scheme:
the utility model provides a mass spectrum sampling device that can be used for complicated sample analysis, includes ion source, advances kind probe and mass spectrum sampling channel, and the ion source is located mass spectrum sampling channel department, and the front end of advancing kind probe is the sampling end, and the sampling end is arranged in the ion source or near the ion source, still includes linking arm and motor, and the one end of linking arm links to each other with the rear end of advancing kind probe, and the other end links to each other with the axis of rotation of motor.
Preferably, the motor is connected to a rotation speed control means, and the rotation speed control means is connected to a power supply device.
As a further preferred aspect, the power supply device includes a USB power supply.
Preferably, the rotation speed of the motor is 20 to 1000rpm, and more preferably 50 to 600 rpm.
Preferably, the ion source is an open ion source, including but not limited to a direct analysis ion source (DART), a desorption electrospray ion source (DESI), a dielectric barrier discharge ion source (DBDI), an atmospheric solid analysis probe ion source (ASAP), a low temperature plasma probe ion source (L TP), an extraction electrospray ion source (EESI), a paper based electrospray ion source (PSI), and a plasma assisted desorption ion source (PADI).
As a further preferred version, the ion source is a DART ion source.
Preferably, the ion source is coupled with an auxiliary gas, preferably an inert gas, such as: nitrogen, argon, helium, preferably helium.
Preferably, the temperature of the assist gas at the outlet of the ion source is 50 to 550 ℃.
As the preferred scheme, the sampling ends of the ion source and the sampling probe are both positioned in front of the port of the mass spectrum sampling channel.
As a further preferred scheme, an included angle between the axis of the sampling end and the axis of the mass spectrum sample feeding channel is 0-90 degrees or 270-360 degrees.
As a further preferred scheme, the distance between the port of the sampling end and the port of the mass spectrum sample feeding channel is 0.1-20 mm.
Preferably, the outer diameter of the sampling end is 0.1-2 mm.
As a preferred scheme, the sample injection probe is a high-temperature-resistant (such as high-temperature-resistant carbon fiber, aluminum-magnesium brick, alloy, metal, quartz or glass) probe, and a high-temperature-resistant glass rod is preferred, so that the sample injection probe can be conveniently cleaned and recycled.
As preferred scheme, the port department of mass spectrum introduction passageway is equipped with the drainage cover, the import of drainage cover is located mass spectrum introduction passageway's axis.
As a further preferable scheme, the outlet of the drainage hood is connected with a diaphragm pump.
As a further preferred scheme, the distance between the port of the sampling end and the inlet of the drainage cover is 0.1-20 mm.
As an implementation scheme, the ion source, the sampling end and the mass spectrum sample introduction channel are in a separated state, and the mutual positions of the ion source, the sampling end and the mass spectrum sample introduction channel can be adjusted.
A mass spectrometry sample introduction method for complex sample analysis comprises the following operations:
loading a sample to a sampling end of a sampling probe, and then enabling the sampling probe to be in a rotating state, or loading the sample to the sampling end by using the sampling probe in the rotating state; the sample carrying sampling tip in a rotated state is then placed in or near the ion source, causing the sample to be ionized by the ion source.
Preferably, the rotation speed of the sample injection probe is 20 to 1000rpm, and more preferably 50 to 600 rpm.
Compared with the prior art, the invention has the beneficial technical effects that:
1. the sampling device creatively utilizes the rotatable sampling probe to sample, is beneficial to uniformly loading a sample and a sampling end of the sampling probe, is beneficial to fully and uniformly contacting the sample on the sampling probe with an ion source, can realize full desorption and ionization of the sample, can remarkably improve the sensitivity and universality of mass spectrometry after being combined with mass spectrometry, can realize ionization of both liquid samples and solid samples without carrying out complex pretreatment on the sample, has good ionization effect on a compound sample, has good ionization effect on complex samples such as a medicine extract, a biological sample extract, an organic polymer and the like, has wide application range and strong universality, is simple to operate and convenient to sample, and greatly shortens the analysis time;
2. the device can be compatible with common mass spectrometers (such as triple quadrupole mass spectrometers, time-of-flight mass spectrometers, ion trap mass spectrometers and the like), can also be popularized and applied to other mass spectrometry, and has wide application range and strong practicability;
3. the sample to be analyzed can be subjected to sample application analysis and can be directly dipped for analysis, especially, drilling sampling at a certain depth can be realized on a proper sample, and rapid synchronous analysis is realized.
Drawings
FIG. 1 is a schematic structural diagram of a mass spectrometry sample injection device capable of being used for complex sample analysis according to the present invention;
FIG. 2 is a schematic structural diagram of a mass spectrometer sampling device with a flow guide cover according to the present invention;
FIG. 3 is a schematic diagram of a mass spectrometer sampling apparatus according to the present invention using a DART ion source;
FIG. 4 is a graph showing mass spectrometry of sample 1 obtained in inventive example 1;
FIG. 5 is a graph showing mass spectrometry of sample 2 obtained in inventive example 1;
FIG. 6 is a graph showing mass spectrometry of sample 3 obtained in inventive example 1;
FIG. 7 is a graph showing mass spectrometry of tobacco powder extract 1 obtained in example 2 of the present invention;
FIG. 8 is a graph showing mass spectrometry of tobacco powder extract 2 obtained in example 2 of the present invention;
FIG. 9 is a graph showing mass spectrometry of the plasma sample 1 obtained in example 3 of the present invention;
FIG. 10 is a graph showing mass spectrometry of the plasma sample 2 obtained in example 3 of the present invention;
FIG. 11 is a graph showing mass spectrometry of an organic polymer 1 obtained in inventive example 4;
FIG. 12 is a graph showing mass spectrometry of an organic polymer 2 obtained in inventive example 4;
the numbers in the figures are as follows: 1. an ion source; 11. an outlet of the ion source; 2. a sample introduction probe; 21. a sampling end; 3. a mass spectrometry sample introduction channel; 4. a connecting arm; 5. a motor; 6. a rotational speed control mechanism; 7. a power supply device; 71. a USB power supply; 8. a drainage cover; 81. an inlet of the drainage mask; 82. an outlet of the flow-directing hood; 9. a diaphragm pump.
Detailed Description
The technical scheme of the invention is further described in detail and completely by combining the attached drawings.
As shown in fig. 1 to 3: the invention provides a mass spectrum sampling device capable of being used for complex sample analysis, which comprises an ion source 1, a sampling probe 2 and a mass spectrum sampling channel 3, wherein the ion source 1 is positioned at the mass spectrum sampling channel 3, the front end of the sampling probe 2 is a sampling end 21, the sampling end 21 is positioned in the ion source 1 or near the ion source 1, the mass spectrum sampling device also comprises a connecting arm 4 and a motor 5, one end of the connecting arm 4 is connected with the rear end of the sampling probe 2, and the other end of the connecting arm is connected with a rotating shaft of the motor 5.
Further, a rotation speed control means 6 is connected to the motor 5, and a power supply device 7 is connected to the rotation speed control means 6. The rotation speed control mechanism 6 may be a commercially available motor or a rotation speed control device of an electric motor, for example, a rotation speed controller, which further controls the rotation speed of the motor 5 through the rotation speed control mechanism 6, further controls the rotation speed of the sample injection probe 2, further optimizes the sampling of the sample and the ionization of the sample, and thus effectively improves the sensitivity of the sample analysis. The motor 5 may be a commercially available motor, and for portability, the motor 5 may be a commercially available micro motor. The power supply device 7 can continuously supply power for the sample introduction device to ensure that the sample introduction device continuously introduces samples
The power supply device 7 comprises a USB power supply 71, and the movable USB power supply 71 enables the sample injection device to have good mobility and facilitates outdoor field sample injection analysis.
The rotation of the sample introduction probe 2 is driven by the motor 5, and the rotation speed of the sample introduction probe 2 is determined by the rotation speed of the motor 5, so that the rotation speed of the motor 5 is 20-1000 rpm, preferably 50-600 rpm, so as to ensure that the sample is uniformly loaded on the sampling end of the sample introduction probe, ensure that the sample on the sample introduction probe is fully and uniformly contacted with the ion source, and further ensure that the full desorption and ionization of the sample are realized.
The ion source 1 is an open type ion source, including but not limited to DESI ion source, DART ion source. In this embodiment, the ion source 1 is preferably a DART ion source.
The ion source 1 is connected with an auxiliary gas, which may be an inert gas, such as: nitrogen, argon, helium, preferably helium. The temperature of the assist gas at the outlet of the ion source 1 is 50 to 550 ℃. In mass spectrometry, through discharge and heating, the normal temperature auxiliary gas is changed into high temperature metastable helium flow to promote desorption and ionization in the sample.
As shown in FIG. 3, the DART ion source 1 is taken as an example in the invention, the ion source 1 is selected as a DART ion source 1, helium is connected to the tail end of the DART ion source 1, so that in mass spectrometry, the helium at normal temperature is converted into high-temperature metastable helium gas flow (the working state temperature is generally 350-550 ℃) through discharging and heating, the metastable state is a long-life electronic excited state, the helium gas has higher internal energy which is higher than the ionization energy of most organic compounds, and the high-temperature metastable helium gas flow is helpful for promoting desorption and ionization of organic molecules in a sample.
The sampling ends 21 of the ion source 1 and the sampling probe 2 are both positioned in front of the port of the mass spectrum sampling channel 3. So that the sample can smoothly enter the mass analyzer for analysis through the mass spectrum sample introduction channel 3 after being ionized.
The included angle α between the axis of the sampling end 21 and the axis of the mass spectrum sample feeding channel 3 is 0-90 degrees or 270-360 degrees.
The distance d between the port of the sampling end 21 and the port of the mass spectrum sample introduction channel 3 is 0.1-20 mm.
The outer diameter of the sampling end 21 is 0.1-2 mm.
In the invention, the sample injection probe 2 is a high temperature resistant (such as high temperature resistant carbon fiber, aluminum-magnesium brick, alloy, metal, quartz or glass) probe, preferably a high temperature resistant glass rod, and can be conveniently cleaned and recycled.
As shown in fig. 2 and fig. 3, a port of the mass spectrometry sample introduction channel 3 is provided with a flow guide cover 8, an inlet 81 of the flow guide cover 8 is located on an axis of the mass spectrometry sample introduction channel 3, and an outlet 82 of the flow guide cover 8 is connected with a diaphragm pump 9. Install the port department at mass spectrum sampling channel 3 with flow guide cover 8, the cooperation has diaphragm pump 9 to provide certain negative pressure for flow guide cover 8, can effectively introduce the mass spectrum instrument with the air current high efficiency that contains the sample ion, and auxiliary gas is mostly taken away by diaphragm pump 9 simultaneously, and the sample after can further guaranteeing the ionization is abundant, effectual entering mass spectrograph is detected, has further improved mass spectrometry's sensitivity.
As shown in fig. 3, the high-temperature metastable helium gas flow starts from the outlet 11 of the DART ion source 1, desorbs and ionizes the sample on the sampling probe 2, and then the ionized sample enters the mass spectrum sampling channel 3 along with the high-temperature metastable helium gas flow under the action of the flow guide cover 8, and the helium gas is pumped away by the diaphragm pump 9, so that the ionized sample enters the mass spectrometer for mass spectrometry.
Further, the distance D between the port of the sampling end 21 and the inlet 81 of the drainage cover 8 is 0.1-20 mm.
The core point of the invention is that the position relationship of the rotary sample introduction probe 2, the sampling end 21 of the ion source 1, the sample introduction probe 2 and the mass spectrum sample introduction channel 3 is within the range and convenient to operate.
This sampling device is used jointly with the mass spectrum, when carrying out the analysis to the sample, with the sample introduce advance the sampling end 21 of appearance probe 2 can, can be directly with the sample load at sampling end 21, also can directly dip in the sample with the sampling end 21 of appearance probe 2, perhaps also can bore and get the sampling. The sample to be analyzed can be in a solid state or a liquid state, can be the sample to be detected, and can also be a solution prepared by dissolving with a proper solvent; the liquid sample can be dissolved by a proper solvent to prepare a solution, or can be directly the sample, and the solid sample can be dissolved by a proper solvent to prepare a solution. The solvent includes but is not limited to water, methanol, ethanol, propylene glycol, glycerol, acetonitrile, dichloromethane, chloroform, hexane, and petroleum ether.
A mass spectrometry sample introduction method for complex sample analysis comprises the following operations:
after a sample is loaded to the sampling end 21 of the sampling probe 2, the sampling probe 2 is in a rotating state, or the sampling probe 2 in the rotating state is used for loading the sample to the sampling end 21; the sample carrying sampling end 21 in a rotated state is then placed in or near the ion source 1, so that the sample is ionized by the ion source.
When the motor 5 is adopted, the mass spectrum sample injection method specifically comprises the following operations:
loading a sample to a sampling end 21 (which can be spotted or dipped) of a sample injection probe 2, then starting a motor 5, wherein the motor 5 drives the sample injection probe 2 to rotate (when the sample is a sample solution, the rotation can also drive a solvent in the sample to be rapidly volatilized), or starting the motor 5, wherein the motor 5 drives the sample injection probe 2 to rotate, and then the sample injection probe 2 in a rotating state loads the sample to the sampling end 21 (which can be dipped or drilled) of the sample injection probe 2; the sample carrying sampling end 21 in a rotated state is then placed in or near the ion source 1, so that the sample is ionized by the ion source. And then, the ionized sample can enter a mass spectrometer from the mass spectrum sample introduction channel 3 for mass spectrum analysis, and after the sample introduction is finished, the rotation is closed, and the sample introduction probe 2 is moved away.
During sample injection, the rotation speed of the sample injection probe 2 is 20 to 1000rpm, preferably 50 to 600rpm, and correspondingly, the rotation speed of the motor 5 is 20 to 1000rpm, preferably 50 to 600 rpm.
The technical effects achieved by the present invention will be further described below with reference to specific application examples.
Example 1
The mass spectrum sampling device and the mass spectrometer (the mass analyzer is a Fourier transform ion cyclotron resonance mass spectrometer) which can be used for complex sample analysis are adopted to carry out (1) on the compound sample
Molecular weight 211.08), sample 2 (M.B.)
Molecular weight 326.07), sample 3 (M.E.)
Molecular weight 342.07) was analyzed by mass spectrometry:
respectively dissolving samples 1-3 in a methanol solution to prepare sample solutions with the concentration of about 20 mug/m L for later use, adopting a DART ion source 1, adopting helium as auxiliary gas, wherein the working temperature of the helium is 350 ℃, the distance D between a port of a sampling end 21 of a sampling probe 2 and an inlet 81 of a drainage cover 8 is 10mm, directly sampling by a sampling end 21, the sampling amount is 4 mug L, then rotating the sampling probe 2, placing the sampling probe 2 near the DART ion source 1, ionizing the samples, and allowing the ionized samples to enter a mass spectrometer through a mass spectrum sampling channel 3 for mass spectrum analysis, wherein the analysis results are shown in figures 4-6.
FIG. 4 is a graph of the resulting mass spectrum analysis of sample 1, showing the appearance of the characteristic mass spectrum signal peaks for sample 1: m/z 212 gives [ M + H]+And the M/z 194 signal is [ M+H-H2O]+(ii) a FIG. 5 is a graph of the resulting mass spectrum analysis of sample 2 showing the appearance of the characteristic mass spectrum signal peaks for sample 2: m/z 327 gives [ M + H]+(ii) a FIG. 6 is a graph of the resulting mass spectrum analysis of sample 3, showing the appearance of the characteristic mass spectrum signal peaks for sample 1: m/z 343 to [ M + H]+(ii) a And in fig. 4 to 6, there is substantially no interference of ion peaks of other impurities except the related ion peaks of the above-mentioned compounds, which indicates that the device and method of the present invention have good ionization efficiency for the compound sample.
Example 2
The mass spectrum sampling device and the mass spectrometer (the mass analyzer is a Fourier transform ion cyclotron resonance mass spectrometer) which can be used for analyzing the complex sample are adopted to carry out mass spectrum analysis on the tobacco powder extract 1 and the tobacco powder extract 2:
respectively placing 0.01g of tobacco powder extracts 1 and 2 in a 1.5ml sample tube, adding 0.5m L ethanol containing 1% acetic acid, fully oscillating for 1 minute, carrying out ultrasonic extraction for 10 minutes, standing for 1 minute, taking supernatant for later use, adopting a DART ion source 1, adopting helium as auxiliary gas, the working temperature of the helium is 350 ℃, the distance D between the port of the sampling end 21 of the sampling probe 2 and the inlet 81 of the drainage cover 8 is 10mm, rotating the sampling probe 2, respectively loading 4 mu L samples on the sampling end 21 of the sampling probe 2, then placing the sampling probe 2 near the DART ion source 1, ionizing the samples, and allowing the ionized samples to enter a mass spectrometer through a sampling channel 3 for mass spectrometry, wherein the analysis results are shown in figures 7 to 8.
FIG. 7 is a mass spectrum analysis chart of the obtained tobacco powder extract 1, wherein characteristic mass spectrum signal peaks of main components Nornicotine (Nornicotine) and Nicotine (Nicotine) in the tobacco powder extract 1 appear: m/z 149 to give [ Nornicotine + H ]]+And m/z 163 to obtain [ Nicotine + H ]]+The signal of (a); FIG. 8 is a mass spectrum analysis chart of the obtained tobacco powder extract 2, wherein characteristic mass spectrum signal peaks of main components Nornicotine (Nornicotine) and Nicotine (Nicotine) in the tobacco powder extract 2 are also shown: m/z 149 to give [ Nornicotine + H ]]+And m/z 163 to obtain [ Nicotine + H ]]+The signal of (a); and in fig. 7 to 8, there is substantially no interference of other impurity ion peaks except the related ion peaks of the above main components, which illustrates that the device and method of the present invention has good ionization efficiency for complex samples of tobacco powder extract (drug extract); in addition, the relative proportion of nornicotine and nicotine signals in fig. 7 and fig. 8 can reflect the difference of the relative content of nornicotine and nicotine in the two samples, which shows that the relative proportion of nornicotine and nicotine in the tobacco powder sample can be rapidly and clearly distinguished by adopting the device and the method of the invention, and the residual fine particles in the extracting solution are adsorbed on the sampling probe, thus not influencing the measurement and polluting a mass spectrometer.
Example 3
The mass spectrum sampling device and the mass spectrometer (the mass analyzer is a Fourier transform ion cyclotron resonance mass spectrometer) which can be used for complex sample analysis are adopted to carry out mass spectrum analysis on the plasma sample 1 and the plasma sample 2:
the plasma sample 1 and the plasma sample 2 both contain 237 molecular weight drug K, 0.1m L of the plasma samples 1 and 2 are respectively added with 20 mu L internal standard solution and 0.2m L organic solvent precipitated protein (methanol/acetonitrile is 1:1), vortexed for 5 minutes and uniformly mixed, centrifuged at 12000 r/min for 10 minutes, supernatant is taken for standby, DART ion source 1 is adopted, helium is adopted as auxiliary gas, the working temperature of the helium is 350 ℃, the distance D between the port of the sampling end 21 of the sampling probe 2 and the inlet 81 of the drainage hood 8 is 10mm, the sampling end 21 directly samples, the sample loading amount is 4 mu L, then the sampling probe 2 is rotated, the sampling probe 2 is placed near the DART ion source 1, the sample is ionized, the ionized sample enters a mass spectrometer through a mass spectrum sampling channel 3 for mass spectrum analysis, and the analysis result is shown in fig. 9 to fig. 10.
Fig. 9 is a diagram of mass spectrometry of the obtained plasma sample 1, in which characteristic mass spectrum signal peaks of the main component drug K in the plasma sample 1 appear: m/z 238 to obtain [ M + H ] of drug K]+Signal, M/z 242 is [ M + H ] of internal standard]+A signal; FIG. 10 is a graph of the obtained mass spectrometric analysis of plasma sample 2 showing the characteristic mass spectrum of the drug K, the main component, in plasma sample 2Number peak: m/z 238 to obtain [ M + H ] of drug K]+Signal, M/z 242 is [ M + H ] of internal standard]+A signal; and in fig. 9 to 10, there is substantially no interference of other impurity ion peaks except for the related ion peaks of the above-mentioned main component and internal standard substance, which indicates that the device and method of the present invention has good ionization efficiency for complex samples such as plasma samples (biological sample extract); in addition, the relative ratio of the signal of the drug K and the internal standard substance in FIG. 9 and FIG. 10 reflects the difference between the concentration of the drug K and the concentration of the internal standard substance in the two samples, which means that the device and the method of the present invention can rapidly and clearly distinguish the relative ratio of the drug K and the internal standard substance in the plasma sample.
Example 4
The mass spectrum sampling device and the mass spectrometer (the mass analyzer is a Fourier transform ion cyclotron resonance mass spectrometer) which can be used for complex sample analysis are adopted to carry out mass spectrum analysis on the organic polymer sample 1 and the organic polymer sample 2:
the organic polymer sample 1 and the organic polymer sample 2 are two organic polymers with slightly different polymerization degrees, are viscous liquids, are not easy to dissolve in solvents such as water and methanol, are polypropylene glycol with two ends capped by glycidyl ether, and have the structure C2H3OCH2-(OC3H6)X-OCH2C2H3O, polypropylene glycol continuous units (OC)3H6) The distribution range is generally (X: 4-10).
Adopting a DART ion source 1, adopting helium as auxiliary gas, wherein the working temperature of the helium is 450 ℃, and the distance D between the port of the sampling end 21 of the sampling probe 2 and the inlet 81 of the drainage cover 8 is 10 mm; rotating the sampling probe 2, directly dipping the end 21 of the sampling probe 2 for sampling, placing the sampling probe 2 near the DART ion source 1, ionizing the sample, and allowing the ionized sample to enter a mass spectrometer through the mass spectrum sampling channel 3 for mass spectrometry, wherein the analysis result is shown in figures 11 to 12.
FIG. 11 is a graph of mass spectrometry analysis of the obtained organic polymer sample 1, in which characteristic mass spectrum signal peaks of polymers of different polymerization degrees in the organic polymer sample 1 appear: m/z 380 is a continuous unit (OC)3H6) (iii) number X ═ 4 of polymeric molecules [ M + NH4]+Signal M/z 438 is [ M + NH ] with X ═ 54]+Signal M/z 496 is [ M + NH ] of X-64]+The signal M/z554 is [ M + NH ] with X ═ 74]+The signal M/z 612 is [ M + NH ] of X-84]+A signal; FIG. 12 is a graph of mass spectrometry of the obtained organic polymer sample 2, in which characteristic mass spectrum signal peaks of polymers of different polymerization degrees in the organic polymer sample 2 appear: m/z 438 is a continuous unit (OC)3H6) (iii) number X ═ 5 of polymeric molecules [ M + NH4]+Signal M/z 496 is [ M + NH ] of X-64]+The signal M/z554 is [ M + NH ] with X ═ 74]+The signal M/z 612 is [ M + NH ] of X-84]+Signal M/z 670 is [ M + NH ] of X ═ 94]+A signal; and in fig. 11 to 12, there is substantially no interference of other impurity ion peaks except for the related ion peaks of the polymers with different polymerization degrees, which illustrates that the device and the method of the present invention have good ionization efficiency for the complex samples of organic polymers; in addition, the difference in the distribution of the species with different degrees of polymerization in the two samples can be clearly distinguished from FIG. 11 and FIG. 12, the range of the polymer molecule X in sample 1 is mainly 4-8, and the continuous unit (OC) in the structure corresponding to the highest signal m/z 496 in sample 13H6) The number X is 6; the range of the polymer molecules X in sample 2 is mainly between 5 and 9, and the highest signal m/z554 in sample 2 corresponds to a continuous unit (OC) in the structure3H6) The number X is 7, which illustrates that the apparatus and method of the present invention can also be used to rapidly and clearly distinguish the polymer molecular distribution range of different organic polymers.
In summary, the following steps: the mass spectrum sample introduction device can realize sufficient desorption and ionization of samples, can obviously improve the sensitivity and universality of mass spectrum analysis after being combined with mass spectrum, can realize ionization of both liquid samples and solid samples without carrying out complex pretreatment on the samples, has good ionization effect on compound samples, has good ionization effect on complex samples such as medicine extracts, biological sample extracts, organic polymers and the like, has wide application range and strong universality, is simple to operate, is convenient to sample, greatly shortens the analysis time, and has strong practicability and popularization and application values.
It is finally necessary to point out here: the above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (10)
1. The utility model provides a mass spectrum sampling device that can be used for complicated sample analysis, includes ion source, advances kind probe and mass spectrum sampling channel, and the ion source is located mass spectrum sampling channel department, and the front end that advances kind probe is the sampling end, and the sampling end is arranged in the ion source or near the ion source, its characterized in that: the sampling probe is characterized by further comprising a connecting arm and a motor, wherein one end of the connecting arm is connected with the rear end of the sampling probe, and the other end of the connecting arm is connected with a rotating shaft of the motor.
2. The mass spectrometry sample introduction device capable of being used for complex sample analysis according to claim 1, wherein: the motor is connected with a rotating speed control mechanism, and the rotating speed control mechanism is connected with a power supply device.
3. The mass spectrometry sample introduction device capable of being used for complex sample analysis according to claim 2, wherein: the power supply device comprises a USB power supply.
4. The mass spectrometry sample introduction device capable of being used for complex sample analysis according to claim 1, wherein: the ion source is an open ion source.
5. The mass spectrometry sample introduction device capable of being used for complex sample analysis according to claim 4, wherein: the ion source is a DART ion source.
6. The mass spectrometry sample introduction device capable of being used for complex sample analysis according to claim 1, wherein: the ion source is connected with an auxiliary gas.
7. The mass spectrometry sample introduction device capable of being used for complex sample analysis according to claim 1, wherein: the sampling ends of the ion source and the sampling probe are both positioned in front of the port of the mass spectrum sampling channel.
8. The mass spectrometry sample introduction device capable of being used for complex sample analysis according to claim 1, wherein: the port department of mass spectrum introduction channel is equipped with the drainage cover, the import of drainage cover is located mass spectrum introduction channel's axis.
9. The mass spectrometry sample introduction device capable of being used for complex sample analysis according to claim 8, wherein: the outlet of the drainage cover is connected with a diaphragm pump.
10. A mass spectrum sampling device method for complex sample analysis is characterized by comprising the following operations: loading a sample to a sampling end of a sampling probe, and then enabling the sampling probe to be in a rotating state, or loading the sample to the sampling end by using the sampling probe in the rotating state; the sample carrying sampling tip in a rotated state is then placed in or near the ion source, causing the sample to be ionized by the ion source.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113192818A (en) * | 2021-03-26 | 2021-07-30 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Microwave plasma torch-solid phase micro extraction-flight time mass spectrum combined system |
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| JP2005044817A (en) * | 2004-11-01 | 2005-02-17 | Hitachi Ltd | Working observation method for minute sample and apparatus |
| CN105470095A (en) * | 2016-01-12 | 2016-04-06 | 黑龙江大学 | Thermal shock gasifying electrospray ionization source and mass spectrometry (MS) system |
| CN209544278U (en) * | 2019-01-30 | 2019-10-25 | 姜虹 | A kind of mass spectrum sampling device that can be used for complex sample analysis |
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| JP2005044817A (en) * | 2004-11-01 | 2005-02-17 | Hitachi Ltd | Working observation method for minute sample and apparatus |
| CN105470095A (en) * | 2016-01-12 | 2016-04-06 | 黑龙江大学 | Thermal shock gasifying electrospray ionization source and mass spectrometry (MS) system |
| CN209544278U (en) * | 2019-01-30 | 2019-10-25 | 姜虹 | A kind of mass spectrum sampling device that can be used for complex sample analysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113192818A (en) * | 2021-03-26 | 2021-07-30 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Microwave plasma torch-solid phase micro extraction-flight time mass spectrum combined system |
| CN113192818B (en) * | 2021-03-26 | 2022-07-08 | 广东省科学院测试分析研究所(中国广州分析测试中心) | Microwave plasma torch-solid phase micro extraction-flight time mass spectrum combined system |
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