CN210272251U - Device for directly ionizing sample by adopting solvent and gas dual auxiliary flames - Google Patents
Device for directly ionizing sample by adopting solvent and gas dual auxiliary flames Download PDFInfo
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Abstract
The utility model discloses an adopt device of solvent and gaseous dual auxiliary flame direct ionization sample, including flame, the sample that awaits measuring, mass spectrum sampling channel, auxiliary solvent passageway and auxiliary sheath gas channel, the outside of auxiliary solvent passageway is located to auxiliary sheath gas channel cover, and the exit end of auxiliary sheath gas channel and the exit end of auxiliary solvent passageway all are located near flame, and the sample that awaits measuring is located between the exit end of auxiliary sheath gas channel and the exit end and the mass spectrum sampling channel of auxiliary solvent passageway. The utility model discloses not only can realize effective component, macromolecular compound and the ionization mass spectrometry of difficult volatile, the compound of easily splitting among the actual sample, can be used to quantitative analysis moreover, especially can also directly on-line analysis organic reaction, the universality is strong.
Description
Technical Field
The utility model relates to an adopt device of solvent and gaseous dual auxiliary flame direct ionization sample belongs to mass spectrometry technical field.
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. 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. Therefore, ionization techniques have a significant impact on mass spectrometry results. 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 term plasma (plasma) was first proposed by Thomson and Lameux in 1929. The plasma is a fourth state of matter following the solid, liquid, gaseous state, when the applied voltage reaches the breakdown voltage, the gas molecules are ionized, creating a mixture comprising electrons, ions, atoms, and radicals. Plasma has unique physical and chemical properties, so plasma-based ionization technology has been greatly developed and widely applied in the field of organic mass spectrometry.
The conventional plasma-based mass spectrometry ionization technology mainly includes an atmospheric pressure chemical ionization technology (APCI) for forming plasma based on high-voltage induced corona discharge (coronas discharge) and a real-time direct analysis ionization technology (DART) developed on the basis of the atmospheric pressure chemical ionization technology (APCI). Because the requirements on sample pretreatment are low, the high flux and the high sensitivity are realized, and the real-time online monitoring can be realized, the mass spectrum ionization technology is widely concerned by academia and is widely applied to the fields of chemistry, food analysis, biological analysis, pharmacy and the like.
However, the above-mentioned plasma-based mass spectrometry techniques suffer from a number of drawbacks, such as: certain dangerousness exists when plasma is generated by high-voltage ionized gas, and the high voltage may affect the personal safety of operators; the ionization device is difficult to miniaturize, the volume of a high-voltage generation module of the ion source is difficult to reduce, and the miniaturization trend of the existing mass spectrum is in conflict with the miniaturization trend; the cost is high, for example, DART usually adopts helium as ionized gas, and the cost of helium is high, so that the cost of analysis and test is high, and meanwhile, DART experimental equipment is complex and the operation is complex; the range of compounds analyzed is limited, for example, high voltage easily catalyzes some redox reactions, so that the technology has poor detection effect on some substances which are easy to generate redox reactions; for another example, DART has a small temperature adjustment range, usually 50-550 ℃, so that most of DART can be detected as small molecules, and some macromolecular compounds are difficult to analyze.
In order to overcome the above drawbacks, the present applicant disclosed ionization devices using a special plasma flame as an ion source in chinese patents CN201520544461.5, cn201520861732.x and CN201510730846.5, respectively. The flame plasma-based ionization technique described above has several advantages over conventional plasma-based ionization techniques, as follows: the flame plasma generation is simple and easy to obtain, high voltage is not needed, only some fuel gas is needed, the safety is good, and meanwhile, the whole ionization device can be miniaturized due to the elimination of a heavy high-voltage module; by selecting proper fuel, the temperature adjustment range of the flame is large, usually 50-1500 ℃, so that macromolecular substances can be analyzed; the possibility of catalyzing the redox reaction is low, and the detection of substances which are easy to generate the redox reaction is not influenced. However, the flame ionization device still has some defects, such as: the detection range of macromolecular substances is still limited, and actually, when the flame ionization device is used for mass spectrometry, signals with the molecular weight larger than 1000 are difficult to detect, in addition, the flame ionization device has poor ionization efficiency for some substances which are difficult to volatilize and easy to crack, the existing ionization device can only carry out qualitative analysis when being used for mass spectrometry, and cannot carry out quantitative analysis well, and the existing ionization device cannot directly carry out online catalytic detection on organic reactions when being used for mass spectrometry. Both of these defects affect the application of flame ionization technology.
Disclosure of Invention
To the above-mentioned problem that prior art exists, the utility model aims at providing an adopt the device of the direct ionization sample of the dual supplementary flame of solvent and gas.
In order to solve the above problem, the utility model adopts the following technical scheme:
a device for directly ionizing a sample by adopting solvent and gas dual-auxiliary flame comprises flame, a sample to be detected and a mass spectrum sample introduction channel, wherein the flame is positioned in front of a port of the mass spectrum sample introduction channel, and the sample to be detected is positioned between the flame and the mass spectrum sample introduction channel; still including the supplementary solvent passageway that is used for introducing supplementary solvent and the supplementary sheath gas passageway that is used for introducing supplementary sheath gas, the outside of supplementary solvent passageway is located to supplementary sheath gas passageway cover, the exit end of supplementary sheath gas passageway and the exit end of supplementary solvent passageway all are located near flame, the sample that awaits measuring is located between the exit end of supplementary sheath gas passageway and the exit end of supplementary solvent passageway and the mass spectrum sampling channel.
Preferably, a fuel supply is connected to the flame.
As a further preferable mode, the fuel supply device includes a fuel tank and a fuel delivery pipe.
More preferably, a flow rate regulating valve is provided in the fuel tank, and a flow rate trim valve is provided in the fuel delivery pipe.
Preferably, an auxiliary solvent supply device is connected to the auxiliary solvent channel.
As a further preferable mode, the auxiliary solvent supply device includes an auxiliary solvent storage tank and an auxiliary solvent transfer pipe.
As a further preferable mode, a flow rate regulating valve is provided on the auxiliary solvent storage tank, and a flow rate fine adjustment valve is provided on the auxiliary solvent transfer pipe.
Preferably, an auxiliary sheath gas supply device is connected to the auxiliary sheath gas channel.
As a further preferred aspect, the auxiliary sheath gas supply device includes an auxiliary sheath gas storage tank and an auxiliary sheath gas delivery pipe.
As a further preferable mode, a flow regulating valve is provided on the auxiliary sheath gas storage tank, and a flow fine adjustment valve is provided on the auxiliary sheath gas transmission pipe.
Preferably, the device further comprises a sample carrier or a sample introduction device for introducing a sample to be detected, and the position of the sample loading end of the sample carrier or the outlet end of the sample introduction device is the position of the sample to be detected.
As a further preferred scheme, the sample carrier includes, but is not limited to, a sample rod, an ultrasonic atomization sheet, and the sample injection device includes, but is not limited to, liquid chromatography, gas chromatography, a syringe pump, and capillary electrophoresis.
Preferably, the outlet end of the auxiliary solvent channel is flush with the outlet end of the auxiliary sheath gas channel.
As a preferred scheme, the distance between the outlet end of the auxiliary solvent channel and the mass spectrum sample feeding channel is 20-80 mm.
As the preferred scheme, the distance between the outlet end of the auxiliary solvent channel and the flame is 1-5 mm.
As the preferred scheme, the included angle between the axis of the auxiliary solvent channel and the flame center axis of the flame is 0-90 degrees.
As the preferred scheme, the distance between the flame and the sample to be measured is 10-40 mm.
Preferably, the inner diameter of the auxiliary solvent channel is 50-300 micrometers, and the outer diameter is 150-500 micrometers.
Preferably, the auxiliary solvent channel is a capillary tube, and when the auxiliary solvent channel is a capillary tube, the inner diameter of the capillary tube is 50-300 micrometers, and the outer diameter of the capillary tube is 150-500 micrometers.
Preferably, the flow rate of the auxiliary solvent in the auxiliary solvent channel is 5-70 microliter/min.
Preferably, the flow rate of the auxiliary sheath gas in the auxiliary sheath gas channel is 15-40 liters/hour.
Preferably, the auxiliary solvent channel and the auxiliary sheath gas channel are made of high-temperature resistant materials, and the high-temperature resistant materials include, but are not limited to, high-temperature resistant glass, ceramic or metal materials.
Preferably, the auxiliary solvent is at least one selected from water, methanol, ethanol and acetonitrile.
Preferably, the auxiliary sheath gas is selected from any one of air, carbon dioxide, nitrogen, helium and argon.
Compared with the prior art, the utility model has the advantages of:
the utility model discloses not only can realize the ionization mass spectrometry to active ingredient, molecular weight be higher than 1000 macromolecular compound and difficult volatile, the easy schizolysis compound in the actual sample, can be used to quantitative analysis moreover, especially can also directly on-line analysis organic reaction, the universality is strong, can provide convenient way for organic chemistry worker provides material analysis and reaction mechanism research, for prior art, has apparent progress and practical value.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for directly ionizing a sample by using a dual auxiliary flame of a solvent and a gas according to the present invention;
FIG. 2 is a graph of mass spectrometry of terbinafine hydrochloride cream obtained in example 1 of the utility model;
fig. 3 is a graph showing mass spectrometry of angiotensin obtained in example 2 of utility model;
FIG. 4 is a TIC diagram of muscone obtained in example 3 of the present invention;
fig. 5 is a graph showing a quantitative standard curve obtained in example 3 of the present invention;
FIG. 6 is a graph showing mass spectrometry of the Borsche-Drechsel reaction obtained in example 4 of the present invention;
the numbers in the figures are as follows: 1. a flame; 2. a sample to be tested; 3. a mass spectrometry sample introduction channel; 4. an auxiliary solvent channel; 5. an auxiliary sheath gas channel; 6. an ionization region; 7. a fuel supply device; 71. a fuel tank; 72. a fuel delivery pipe; 73. a flow rate regulating valve of the fuel supply device; 74. a flow rate trim valve of the fuel supply device; 8. an auxiliary solvent supply device; 81. an auxiliary solvent storage tank; 82. an auxiliary solvent transfer pipe; 83. a flow rate regulating valve of the auxiliary solvent supply device; 84. a flow rate trim valve of the auxiliary solvent supply device; 9. an auxiliary sheath gas supply device; 91. an auxiliary sheath gas storage tank; 92. an auxiliary sheath gas delivery tube; 93. a flow rate regulating valve of the auxiliary sheath gas supply device; 94. a flow rate fine adjustment valve of the auxiliary sheath gas supply device.
Detailed Description
The technical solution of the present invention will be further described in detail and fully with reference to the accompanying drawings.
As shown in fig. 1: the utility model provides an adopt device of solvent and gaseous dual auxiliary flame direct ionization sample, including flame 1, the sample 2 that awaits measuring and mass spectrum sampling channel 3, flame 1 is located the port of mass spectrum sampling channel 3 the place ahead, the sample 2 that awaits measuring is located between flame 1 and mass spectrum sampling channel 3; still including the supplementary solvent passageway 4 that is used for introducing supplementary solvent and the supplementary sheath gas passageway 5 that is used for introducing supplementary sheath gas, supplementary sheath gas passageway 5 cover is located the outside of supplementary solvent passageway 4, the exit end of supplementary sheath gas passageway 5 and the exit end of supplementary solvent passageway 4 all are located near flame 1, the sample 2 that awaits measuring is located between the exit end of supplementary sheath gas passageway 5 and the exit end of supplementary solvent passageway 4 and mass spectrum sampling channel 3.
The device can be compatible with common mass spectrometers (such as triple quadrupole mass spectrometers, time-of-flight mass spectrometers, ion trap mass spectrometers, etc.), also can be popularized and applied to other mass spectrometry, when being used for mass spectrometry, with common mass spectrometers ally oneself with usefulness can, the range of application is wide, the practicality is strong.
Adopt the device realizes the method of ionization, is that the energy that makes flame 1 produce and active species are pushed under the common propelling movement of supplementary solvent and supplementary sheath gas to 2 departments of the sample that awaits measuring, make the sample 2 ionization that awaits measuring.
Referring to fig. 1, in the ionization process, the flame 1 is pushed to the sample 2 to be detected under the common pushing of the auxiliary solvent and the auxiliary sheath gas, and the sample 2 to be detected is located in front of the port of the mass spectrum sample introduction channel 3, so that the active species and energy generated by the flame 1 are pushed to the front of the port of the mass spectrum sample introduction channel 3, that is, an ionization region 6 is generated in front of the port of the mass spectrum sample introduction channel 3, and therefore the sample 2 to be detected is located in the ionization region 6, and then the active species and energy generated by the flame 1 are pushed to the ionization region 6 and collide with the sample 2 to be detected, so that the sample 2 to be detected is ionized, and then the ionized sample enters the mass spectrometer through the mass spectrum sample introduction channel 3 to perform subsequent mass spectrometry. It can be seen from above that, this application the device compares in traditional flame ionization device, because of sample 2 and the flame 1 direct contact that awaits measuring, therefore can effectively avoid the sample 2 direct contact high temperature that awaits measuring, and then can effectively avoid the sample 2 that awaits measuring to be carbonized by pyrolysis, and the sample 2 schizolysis that awaits measuring is less, even consequently also can have good ionization effect to the compound of easy schizolysis. In addition, in this application, flame 1 is as neotype plasma, the flame 1 of burning can produce a large amount of energy and active species, supplementary sheath gas and auxiliary solvent can be with energy and the active species propelling movement of flame 1 production to the sample 2 department that awaits measuring, auxiliary solvent can also assist sample desorption simultaneously, in the ionization process, energy and the active species that flame 1 produced are by propelling movement to the sample 2 department that awaits measuring back, auxiliary solvent is earlier to the sample 2 desorption that awaits measuring, then energy and the active species that flame 1 produced assist the sample 2 ionization that awaits measuring again, make ionization efficiency high, sensitivity is good, the mass spectrogram of production is easy to be analyzed, the miscellaneous peak is less, the spectrogram is comparatively clean. In addition, the auxiliary solvent and the auxiliary sheath gas also have a certain cooling effect, so that the sample 2 to be detected can be effectively prevented from being damaged by high-temperature flame, and the device also has a good ionization effect on macromolecular compounds (compounds with molecular weight larger than 1000).
Referring to fig. 1, a fuel supply 7 is connected to the flame 1. The fuel supply device 7 includes a fuel tank 71 and a fuel transfer pipe 72. Further, a flow rate regulating valve 73 is provided in the fuel tank 71, and a flow rate trim valve 74 is provided in the fuel transfer pipe 72. When mass spectrometry is carried out, the fuel supply device 7 is opened to output gas fuel, then the gas fuel is ignited to generate flame 1, and in the gas fuel conveying process, the flow of the gas fuel can be adjusted through the flow adjusting valve 73 and the flow fine adjustment valve 74, so that the size, the height and the temperature of the flame 1 are adjusted, the flame 1 is matched with the sample 2 to be detected, and the ionization effect is ensured. The fuel used is inorganic fuel or organic fuel, the inorganic fuel includes but not limited to hydrogen, the organic fuel includes but not limited to hydrocarbon fuel, alcohol fuel, ketone fuel, ether fuel or ester fuel, the hydrocarbon fuel includes but not limited to saturated alkane, unsaturated alkane or mixture composed of a plurality of hydrocarbon, preferably hydrogen.
The auxiliary solvent passage 4 is connected to an auxiliary solvent supply device 8. The auxiliary solvent supply device 8 includes an auxiliary solvent storage tank 81 and an auxiliary solvent transfer pipe 82. A flow rate regulating valve 83 is provided in the auxiliary solvent storage tank 81, and a flow rate fine adjustment valve 84 is provided in the auxiliary solvent transfer pipe 82. Correspondingly, an auxiliary sheath gas supply device 9 is connected to the auxiliary sheath gas channel 5. The auxiliary sheath gas supply device 9 includes an auxiliary sheath gas storage tank 91 and an auxiliary sheath gas delivery pipe 92. A flow rate regulating valve 93 is provided on the auxiliary sheath gas storage tank 91, and a flow rate fine adjustment valve 94 is provided on the auxiliary sheath gas transmission pipe 92. When mass spectrometry is performed, the auxiliary solvent supply device 8 and the auxiliary sheath gas supply device 9 are opened, so that the auxiliary solvent and the auxiliary sheath gas are respectively introduced to the vicinity of the flame 1 through the auxiliary solvent channel 4 and the auxiliary sheath gas channel 5, and in the process of introducing the auxiliary solvent and the auxiliary sheath gas, the flow rates of the auxiliary solvent and the auxiliary sheath gas can be adjusted by adjusting the flow adjusting valve 83, the flow fine adjustment valve 84, the flow adjusting valve 93 and the flow fine adjustment valve 94, for example, in the present application, the flow rate of the auxiliary solvent in the auxiliary solvent channel 4 is 5 to 70 microliters/minute, the flow rate of the auxiliary sheath gas in the auxiliary sheath gas channel 5 is 15 to 40 liters/hour, so that the auxiliary solvent and the auxiliary sheath gas push the flame 1 to the sample 2 to be measured, ionize the sample 2 to be measured, and simultaneously, the temperature of the flame 1 is conveniently adjusted through the auxiliary solvent and the auxiliary sheath gas, the desorption effect of the sample 2 to be detected is adjusted, and the ionization effect of the sample 2 to be detected is further ensured.
The device may further comprise a sample carrier or sample introduction device (not shown) for introducing the sample 2 to be tested, and the position of the sample loading end of the sample carrier or the outlet end of the sample introduction device is the position of the sample 2 to be tested. The sample carrier or the sample introduction device may be a general carrier or a general device as long as the sample 2 to be detected can be introduced to the front of the port of the mass spectrum sample introduction channel 3, for example, the sample carrier includes but is not limited to a sample rod and an ultrasonic atomization sheet, and the sample introduction device includes but is not limited to a continuous sample introduction device such as a liquid chromatography, a gas chromatography, an injection pump, a capillary electrophoresis, and the like. In this application, because flame 1 and the sample 2 that awaits measuring are not direct contact, consequently do not do too much requirement to the high temperature resistance of sample carrier or sampling device, for example, when the sample carrier is the sample stick, do not require the sample stick to be high temperature resistant sample stick, practice thrift the cost. Meanwhile, when the sample introduction device is a continuous sample introduction device such as a liquid chromatogram, a gas chromatogram, an injection pump and the like, the device can be used for continuous sample introduction when being used for mass spectrometry, and the stability of signals is ensured.
In this application, the exit end of supplementary solvent passageway 4 is parallel and level with the exit end of supplementary sheath gas passageway 5 to guarantee the synchronism of supplementary solvent and supplementary sheath gas.
In this application, be the separation state between flame 1, the sample 2 that awaits measuring, mass spectrum sampling channel 3, supplementary solvent passageway 4 and the supplementary sheath gas passageway 5, and flame 1, the sample 2 that awaits measuring, mass spectrum sampling channel 3 and supplementary solvent passageway 4 and supplementary sheath gas passageway 5 between mutual position can be adjusted.
For example, in the present application, the distance d1 between the outlet end of the auxiliary solvent channel 4 (also equivalent to the outlet end of the auxiliary sheath gas channel 5) and the mass spectrometry sample introduction channel 3 is 20-80 mm. Further, the distance d2 between the exit end of supplementary solvent passageway 4 (also being equivalent to the exit end of supplementary sheath gas passageway 5) and the flame 1 is 1 ~ 5mm, so that with the propelling movement of flame 1 to the sample 2 department that awaits measuring through supplementary solvent and supplementary sheath gas, compare in traditional flame ionization device simultaneously, the distance between flame 1 and the mass spectrum sampling passageway 3 is great in this application, it is little to mass spectrometer that mass spectrum sampling passageway 3 and correspond, the high temperature that flame 1 produced is also less to mass spectrum sampling passageway 3 and the influence of the mass spectrometer that corresponds simultaneously, mass spectrometry effect and mass spectrometer's life has been guaranteed.
The included angle α between the axis of the auxiliary solvent channel 4 (also equivalent to the auxiliary sheath gas channel 5) and the flame core axis of the flame 1 is 0-90 degrees, the axis of the auxiliary solvent channel 4 is parallel to the axis of the auxiliary sheath gas channel 5, the distance d3 between the flame 1 and the sample 2 to be measured is 5-40 mm, the inner diameter of the auxiliary solvent channel 4 is 50-300 micrometers, and the outer diameter is 150-500 micrometers.
In the present application, the auxiliary solvent channel 4 and the auxiliary sheath gas channel 5 are made of high temperature resistant materials, which include, but are not limited to, high temperature resistant glass, ceramic or metal materials. In this application, the auxiliary sheath airway 5 is a sheath airway.
In the present application, the auxiliary solvent is at least one selected from water, methanol, ethanol, and acetonitrile, and is mainly used to assist desorption of the sample 2 to be detected.
In this application, supplementary sheath gas is mainly used for 1 propelling movement of flame to 2 departments of the sample that awaits measuring, consequently, does not have high expectations to supplementary sheath gas, supplementary sheath gas can be selected from any one in air, oxygen, nitrogen gas, helium, the argon gas, can choose expensive helium, argon gas for use, also can choose cheap air, carbon dioxide, oxygen, nitrogen gas for use, compare in the expensive helium gas of the commonly used among DART, can be to a certain extent greatly reduced analysis cost.
The technical effects that the present invention can achieve are further described below with reference to specific application examples.
Example 1
Adopt the device carries out mass spectrometry with mass spectrograph (mass analyzer is triple quadrupole) to actual sample terbinafine hydrochloride cream:
the gas fuel is hydrogen, the auxiliary solvent is methanol, the flow rate of the auxiliary solvent is 20 microliter/min, the auxiliary sheath gas is nitrogen, and the flow rate of the auxiliary sheath gas is 25 liters/h.
Directly dipping a small amount of terbinafine hydrochloride cream by using a sample rod, and then fixing a sample loading end (namely the terbinafine hydrochloride cream) of the sample rod in front of a port of a mass spectrum sample injection channel 3; igniting the gas to burn to generate a flame 1, wherein the distance between the flame 1 and the sample loading end of the sample rod is 30 mm; an auxiliary solvent methanol and an auxiliary sheath gas are respectively introduced through a capillary tube and a sheath gas tube, the auxiliary solvent and the auxiliary sheath gas are sprayed along the axial direction of the capillary tube and push the flame 1 to the terbinafine hydrochloride cream, so that the terbinafine hydrochloride cream is ionized, and the mass analyzer is always in an acquisition state.
Fig. 2 is a mass spectrometric analysis diagram of the terbinafine hydrochloride cream, in which a relevant ion peak (m/z)292 of the main chemical component terbinafine in the terbinafine hydrochloride cream appears, and no interference of other impurity ion peaks is present, which illustrates that the device of the present invention can realize good ionization effect on effective chemical components in practical samples.
Example 2
Adopt the device carries out mass spectrometry to the angiotensin of difficult volatility, easy schizolysis, macromolecular weight with mass spectrograph (mass analyzer is triple quadrupole):
the gas fuel is hydrogen, the auxiliary solvent is methanol, the flow rate of the auxiliary solvent is 20 microliter/min, the auxiliary sheath gas is nitrogen, and the flow rate of the auxiliary sheath gas is 20 liters/h.
Taking methanol as a solvent, preparing an angiotensin sample solution with the concentration of 10ppm, and introducing the angiotensin sample solution to the front of a port of a mass spectrum sample injection channel 3 through liquid chromatography; igniting the gas to burn to generate a flame 1, wherein the distance between the flame 1 and the angiotensin sample solution is 30 mm; the auxiliary solvent methanol and the auxiliary sheath gas are respectively introduced through the capillary tube and the sheath gas tube, the auxiliary solvent and the auxiliary sheath gas are sprayed along the axial direction of the capillary tube and push the flame 1 to the angiotensin sample solution, so that the angiotensin sample solution is ionized, and the mass analyzer is always in an acquisition state.
Fig. 3 is a diagram of mass spectrometry of the obtained angiotensin, in which relevant ion peaks (m/z)1046, 1068 of the angiotensin appear, and there is no interference of other impurity ion peaks, which illustrates that the device of the present invention can achieve good ionization effect for compounds with difficult volatilization, easy cracking and large molecular weight.
Example 3
Adopt the device carries out quantitative analysis to muscone with mass spectrograph (mass analyzer is triple quadrupole):
drawing a standard curve of the musk ketone standard solution: the method comprises the steps of respectively preparing standard solutions with the concentrations of 0.1ppm, 0.2ppm, 0.5ppm, 1ppm, 2ppm, 5ppm, 10ppm, 20ppm, 50ppm and 100ppm from muscone, respectively carrying out mass spectrometry on 10 mu L of the muscone standard solutions with different concentrations according to the analysis conditions described in example 1, respectively taking m/z 239- >95 as a detection ion pair and a TIC ion flow graph with the collision energy of 28eV under the SRM mode of the mass spectrometry, drawing a standard curve of the muscone standard solutions, then preparing a muscone sample to be actually tested into a sample solution with a certain concentration, and carrying out mass spectrometry under the same test conditions, thus measuring the content of muscone in the actual sample and realizing the quantitative analysis of muscone.
FIG. 4 is a TIC ion flow diagram of the obtained standard solution (1ppm) of muscone, wherein SN represents the signal-to-noise ratio, RT represents the time, and AA represents the peak area; as can be seen from FIG. 4, the TIC ion flow diagram shows good peak shape, which indicates that the mass spectrometry method of the present embodiment is stable and good in reproducibility.
Fig. 5 is the standard curve of the obtained muscone standard solution, and as can be seen from fig. 5, the obtained standard curve is good in linearity, which illustrates that the device of the present invention can realize good quantitative analysis of samples.
Example 4
Adopt the device carries out mass spectrometry to Borsche-Drechsel reaction with mass spectrograph (mass analyzer is triple quadrupole):
the Borsche-Drechsel reaction is as follows:
FIG. 6 is a graph of mass spectrometry of the resulting Borsche-Drechsel reaction; besides the related ion peaks (m/z)99 and 109 of the compounds 1 and 2, the related ion peaks (m/z)172 and 189 of the reaction intermediate compound 3 and the reaction product compound 4 appear in the spectrogram, and no interference of other impurity ion peaks exists, which indicates that the device can accelerate the Borsche-Drechsel reaction, can directly analyze the organic reaction on line, and provides a convenient way for the research of the reaction mechanism.
In summary, it can be seen that: adopt after device and mass spectrum ally oneself with usefulness, not only can show sensitivity and the universality that improves mass spectrometry, to actual sample, the macromolecular compound that the molecular weight is higher than 1000 and difficult volatility, the compound of easily splitting all has good ionization effect, the range of application is wide, the universality is strong, not only can be used to the qualitative analysis of compound, still can be used to the quantitative analysis of sample, especially can directly on-line analysis organic reaction, provide convenient way for organic chemistry worker provides material analysis and reaction mechanism research, for prior art, have apparent progress and practical value.
It is finally necessary to point out here: the above description is only for the preferred embodiment of the present invention, but the protection 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 should be covered by the protection scope of the present invention.
Claims (10)
1. The utility model provides an adopt device of solvent and gaseous dual auxiliary flame direct ionization sample, includes flame, the sample and the mass spectrum sampling channel that await measuring, its characterized in that: the flame is positioned in front of the port of the mass spectrum sample introduction channel, and the sample to be detected is positioned between the flame and the mass spectrum sample introduction channel; still including the supplementary solvent passageway that is used for introducing supplementary solvent and the supplementary sheath gas passageway that is used for introducing supplementary sheath gas, the outside of supplementary solvent passageway is located to supplementary sheath gas passageway cover, the exit end of supplementary sheath gas passageway and the exit end of supplementary solvent passageway all are located near flame, the sample that awaits measuring is located between the exit end of supplementary sheath gas passageway and the exit end of supplementary solvent passageway and the mass spectrum sampling channel.
2. The apparatus of claim 1, wherein: the flame is connected with a fuel supply device.
3. The apparatus of claim 1, wherein: the auxiliary solvent channel is connected with an auxiliary solvent supply device.
4. The apparatus of claim 1, wherein: the auxiliary sheath gas channel is connected with an auxiliary sheath gas supply device.
5. The apparatus of claim 1, wherein: the distance between the outlet end of the auxiliary solvent channel and the mass spectrum sample feeding channel is 20-80 mm.
6. The apparatus of claim 1, wherein: the distance between the outlet end of the auxiliary solvent channel and the flame is 1-5 mm.
7. The apparatus of claim 1, wherein: the inner diameter of the auxiliary solvent channel is 50-300 microns.
8. The apparatus of claim 1, wherein: the flow rate of the auxiliary solvent in the auxiliary solvent channel is 5-70 microliter/min.
9. The apparatus of claim 1, wherein: the flow velocity of the auxiliary sheath gas in the auxiliary sheath gas channel is 15-40 liters/hour.
10. The apparatus of claim 1, wherein: the auxiliary sheath gas is selected from any one of air, carbon dioxide, nitrogen, helium and argon.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110400740A (en) * | 2019-07-23 | 2019-11-01 | 中国科学院上海有机化学研究所 | A kind of method and apparatus using solvent and gas double auxiliary flame direct ion sample |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110400740A (en) * | 2019-07-23 | 2019-11-01 | 中国科学院上海有机化学研究所 | A kind of method and apparatus using solvent and gas double auxiliary flame direct ion sample |
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