CN113628952B - Quadrupole rod mass analyzer based on single-path radio frequency drive - Google Patents

Quadrupole rod mass analyzer based on single-path radio frequency drive Download PDF

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CN113628952B
CN113628952B CN202110870019.1A CN202110870019A CN113628952B CN 113628952 B CN113628952 B CN 113628952B CN 202110870019 A CN202110870019 A CN 202110870019A CN 113628952 B CN113628952 B CN 113628952B
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pole
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quadrupole
radio frequency
mass
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CN113628952A (en
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贾滨
程平
刘吉星
徐丽
谢春光
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Shanghai Haike Spectrometer Co ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/26Mass spectrometers or separator tubes
    • H01J49/34Dynamic spectrometers
    • H01J49/42Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/4205Device types
    • H01J49/422Two-dimensional RF ion traps
    • H01J49/4225Multipole linear ion traps, e.g. quadrupoles, hexapoles
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62Investigating 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
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/022Circuit arrangements, e.g. for generating deviation currents or voltages ; Components associated with high voltage supply

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Abstract

The invention discloses a quadrupole rod mass analyzer based on single-path radio frequency driving, namely a novel power-on mode of the quadrupole rod mass analyzer is provided. The method does not need two-way radio frequency driving, so that the manufacturing problems that two-way radio frequency needs to keep consistent amplitude, consistent resonant frequency, phase synchronization and the like are solved, the debugging process is simplified, the manufacturing difficulty and cost of the quadrupole rod radio frequency power supply are reduced, and the performance consistency of quadrupole rod mass analyzers in batches is improved. Meanwhile, by adopting the power-up mode, all the ion operation modes commonly used by the quadrupole rod, such as a scanning mode, a selective ion monitoring mode, an all-pass transmission mode and the like, can be completed, and the negative influence on the performance such as the precision of mass analysis is avoided.

Description

Quadrupole rod mass analyzer based on single-path radio frequency drive
Technical Field
The invention relates to the field of quadrupole mass spectrometry, in particular to a quadrupole mass analyzer driven by a single-path radio frequency voltage.
Background
The name of Quadrupole Mass Spectrometer (quadrupolole Mass Spectrometer) comes from its Quadrupole Mass selector (QMA). In the quadrupole rods, four electrode rods are divided into two groups, and Radio Frequency (RF) inverse alternating voltages are applied to the four electrode rods respectively. The voltage on the electrode rods forms a quadrupole radio frequency electric field in the region between the rods. When the equipment is operated, ions generated by the ion source enter the quadrupole field along the central axis of the quadrupole rod, only ions with a certain mass-to-charge ratio (the ratio of the mass of the ions to the number of carried charges, m/z) are allowed to pass through the quadrupole rod along the axial direction of the quadrupole rod, and other ions are thrown out by the radio frequency field of the quadrupole rod. The ions passing axially can reach the ion detector at the rear end of the rod and be recorded. The selection of the Mass-to-charge ratio of ions passing through the Quadrupole rod can be achieved by controlling the ac amplitude and the dc component of the rf voltage on the Quadrupole rod, and is also known as a Quadrupole Mass selector (QMF).
The quadrupole mass spectrometer has a simpler structure and circuit than other mass spectrometers. The cost is also relatively low. Quadrupole Mass spectrometers are widely used in Chromatography-Mass spectrometry (Chromatography-Mass spectrometry) combinations. Multiple Mass Spectrometry (Tendem Mass Spectrometry, tendem MS) can be realized by using a plurality of quadrupole rods in series (such as triple quadrupole Mass Spectrometry), so that the structural information of the object to be detected is obtained.
As described above, the quadrupole mass selector has four electrode rods, with opposing two in a set. Usually two applied voltages phi are placed on the x-axis x Two voltages Φ y are placed on the y-axis, and the voltages applied to them are:
Figure GDA0003838942490000021
at the moment, the electric potential distribution in the region enclosed by the four pole rods meets the following conditions:
Figure GDA0003838942490000022
in the mass selection theory of the quadrupole, the derivation of the ion kinetic equation is carried out based on the potential energy distribution condition. This process is described in textbooks and will not be described in detail herein. In a word, the radio frequency amplitude V and the direct current component U in the equation (1) are set, so that the ions can be screened according to the mass-to-charge ratio.
However, according to the above equation, + Φ 0 And phi 0 In the two paths of radio frequency voltages, the amplitude V is strictly consistent, and the phase angle difference of 180 degrees is also strictly synchronous, so that a positive-negative two-path RF voltage is formed. However, in the process of manufacturing the high-voltage radio-frequency power supply of the quadrupole rod, the analog circuit of the radio-frequency power supply needs a radio-frequency boosting coil (L), the quadrupole rod is equivalent to a load capacitor (C), and the whole power supply system is an LC oscillating circuit. The circuit can involve complicated resonant frequency tuning and impedance matching problems in the manufacturing process. Meanwhile, when the quadrupole rod adopts a two-way radio frequency (one way + phi) 0 One way is-phi 0 ) When the circuit is used, the resonance point and the impedance of the oscillation circuit are affected by the small difference between the selected devices in the two radio frequency circuits. The difference between the resonance point and the impedance of the two radio frequencies directly causes the amplitude, the phase and the like of the two radio frequencies to be obviously different. Thus, the electricityHigh-voltage-resistant adjustable devices such as adjustable capacitors and adjustable inductors are also needed in the circuit to modulate and compensate the difference between the two radio frequency loops. Therefore, the two radio frequency amplitudes are kept consistent. The radio frequency of the quadrupole rod is required to keep resonance and impedance matching so as to achieve the required high voltage; and the two paths of parameters are finely adjusted to make the two paths of amplitudes consistent, so that the manufacturing difficulty of the quadrupole rod radio frequency circuit is obviously increased. Meanwhile, due to the difference of devices, each quadrupole rod radio-frequency power supply needs to be specially modulated by advanced professionals, which affects the manufacturing cost (high-end labor cost) and the performance stability of the quadrupole rods in the mass production process.
Disclosure of Invention
The invention aims to provide a new power-on mode of a quadrupole mass analyzer, namely a new single-path radio-frequency-driven quadrupole mass analyzer is designed. The device does not need double-circuit radio frequency driving, so that the modulation problems of double-circuit radio frequency amplitude consistency, resonant frequency consistency, phase synchronism and the like are avoided, the debugging process is simplified, the manufacturing difficulty and cost of the quadrupole rod radio frequency power supply are reduced, and the performance consistency among batches is improved. At the same time, the design has no negative effect on the specific function of the quadrupole.
The invention is realized by the following technical scheme:
the utility model provides a quadrupole rod mass analyzer based on single pass radio frequency drive, includes four polar rods, is polar rod one, polar rod two, polar rod three and polar rod four respectively, polar rod one is a set of with polar rod three, polar rod one is connected with the first wire of polar rod tee bend, polar rod two is a set of with polar rod four, polar rod two is connected with polar rod cross second wire, first wire is connected with radio frequency power supply, the second wire is connected with DC power supply. The first pole rod and the third pole rod are connected with a radio frequency power supply through first leads to apply radio frequency voltage; and the second pole rod and the fourth pole rod are connected with a direct-current power supply through second conducting wires to apply direct-current voltage. It should be noted that only one rf voltage is applied to the first pole and the third pole, and only dc voltages are applied to the second pole and the fourth pole. The power-up mode can be used for realizing various common working modes of quadrupole rods, such as Selective Ion Monitoring (SIM), mass scanning (Scan), ion transmission and the like, without two-way radio frequency.
As a preferred embodiment of the present invention: the first pole rod, the second pole rod, the third pole rod and the fourth pole rod are hyperbolic poles; in addition, it should be noted that the shapes of the first pole, the second pole, the third pole and the fourth pole can also be round poles, square poles (flat poles) or other pole shapes which can be similar to generate a hyperboloid quadrupole field.
As a preferred embodiment of the present invention: the Z axis of the central axis of the first pole rod, the second pole rod, the third pole rod and the fourth pole rod is linear; furthermore, it should be noted that the z-axis may also be curved, such as arcuate, semi-circular.
As a preferred embodiment of the present invention: the first pole rod, the second pole rod, the third pole rod and the fourth pole rod are made of stainless steel, molybdenum or ceramic gold plating; in addition, it should be noted that the first pole, the second pole, the third pole and the fourth pole can also adopt other pole materials which can be used for manufacturing a quadrupole mass analyzer.
The specific process of the quadrupole rod mass analyzer based on the single-path radio frequency drive comprises the following steps:
1. the potentials applied to the two groups of pole rods are respectively as follows:
Figure GDA0003838942490000031
wherein: the RF voltage is applied to one group of (two) pole rods on the x axis, the amplitude is V (t), the DC component is U (t)/2, and the pole potential is U DCbias . Two pole rods on the y-axis apply only the DC potential-U (t)/2 and the rod potential U DCbias
2. The mass selection of the quadrupole rods is related to the potential on the rods by the following steps:
Figure GDA0003838942490000041
that is, by controlling the amplitude V and the DC component U of the RF voltage, the mass-to-charge ratio can be realized(m/z) where m is the mass of the ion, z is the number of charges, m/z is the mass-to-charge ratio, and e is the amount of the basic charge (i.e., about 1.6X 10) -19 C) Omega is the angular frequency of the radio frequency voltage, r 0 The radius of the inscribed circle of the quadrupole rod.
3. When the quadrupole rods need to operate in a Selective Ion Monitoring (SIM) mode, U and V are set to constants with reference to equation (3); only ions of a certain mass to charge ratio are allowed to pass through, and the detector at the back end of the rod only records the intensity of the ions.
4. When the quadrupole is operated in the spectrogram Scan (Scan) mode, U (t) and V (t) are functions of time. Referring to the formula (3), when U (t) and V (t) change from small to large with time, the mass-to-charge ratio (m/z) of the passing ions also changes from small to large with time, and the peak position and peak height recorded by the rod back end detector can be converted into a mass spectrum.
5. When the quadrupole rod needs to work in the full-pass mode, the U is set to be zero; in this case, the quadrupole allows all ions in its Mass transmission range (Mass range) to pass through, and in this case, the quadrupole is mainly used as a Mass spectrometer element such as an ion transmission rod and a collision cell.
The feasibility and formula calculation demonstration process of the technical scheme of the invention comprises the following steps:
defining: one group (two) of pole rods on the x axis are a pole rod I and a pole rod III, and one group (two) of pole rods on the y axis are a pole rod II and a pole rod IV.
1. Derivation of the ion kinetic equation in the quadrupole field of single-pass rf drive:
suppose that the applied potential on the two poles of the x-axis is phi 0 The potential applied to the two poles of the y axis is 0V, and a quadrupole field surrounded by 4 poles has the following boundary conditions:
1) At y =0, x = ± r 0 Where Φ (x, y) = Φ 0
2) At x =0,y = ± r 0 Where Φ (x, y) =0
3) At x = ± y,
Figure GDA0003838942490000042
according to the boundary conditions, an electric potential distribution equation of the quadrupole field can be obtained:
Figure GDA0003838942490000051
wherein: phi 0 (t)=U-Vcosωt………(4)
According to newton's equation of motion:
Figure GDA0003838942490000052
obtaining:
Figure GDA0003838942490000053
the partial differential equation, taken into Φ (x, y), yields:
Figure GDA0003838942490000054
so far, the kinetic equation (Paul equation) of ions in the quadrupole field under the common quadrupole two-way radio frequency drive is compared with the constant term in the formula (4)
Figure GDA0003838942490000055
In the process of calculating the partial derivative, the partial derivative is equal to 0, so that the constant term has no influence on the evolution of the kinetic equation of F = ma, and only the coefficient 1/2 of the increase of the quadratic term is represented in equation (5): 2ze becomes ze.
2. Solving the relationship between voltage and mass-to-charge ratio
Similar to the conventional quadrupole rod power-up method, the following calculation is performed to:
Figure GDA0003838942490000056
equation (5) above can be converted to marek equation (Mathieu equation):
Figure GDA0003838942490000057
wherein unlike conventional power-up, a and q are converted to:
Figure GDA0003838942490000058
similar to the existing two-way rf power-up method, we can use the vertex of the first stable region (q =0.706, a = 0.237) of the first quadrant of the mahalanobis equation to make the quadrupole rod work in the ion mass selection mode.
At this time, the relationship between the amplitude V and the dc component U of the quadrupole rf power source and the mass-to-charge ratio m/z can be expressed as:
Figure GDA0003838942490000061
thus, equation (3) is obtained.
3. Correction of DC component and setting of DC bias voltage
In practical application, ions enter the quadrupole rod through the small hole, move along the z-axis and then are output through the small hole at the other end. In this process, the average potential experienced by an ion moving near the origin (z-axis) is what we commonly say as a quadrupole direct current bias (DC bias). The setting and adjustment of the direct current bias voltage of the rod can influence factors such as axial kinetic energy of ions entering and exiting the rod, and the like, and the device is applied to the practical application of the quadrupole rod. In particular, in instruments of the triple quadrupole, QTOF, etc. type, which require control and regulation of the rod potential, DC bias is usually not 0. Therefore, the quadrupole rod mass selector driven by the single-path radio frequency also needs to correct the direct current component U of the radio frequency voltage and perform direct current bias (direct current potential) U on the rod DCbias Setting is performed.
In the design of the present invention, if derived as described above, the rf voltages applied to x and y are:
Figure GDA0003838942490000062
the average potential energy (rod dc bias) felt by the ions near the z-axis at this time becomes U/2. Therefore, in practical applications, the quadrupole rods of the single-path rf also need to correct the dc component. Namely, the DC voltage on the four rods is reduced by U/2, so that the bias is changed into 0 (namely the bias voltage is independent of the RF DC component); plus the actually required U DCbias . Thus, the pole-on potential evolves to:
Figure GDA0003838942490000063
wherein the voltage to mass-to-charge ratio relationship satisfies formula (3):
Figure GDA0003838942490000064
when the quadrupole is operating in scan mode, U (t) and V (t) require turn-on voltages and amplitude scan mode. At this time, the actual voltage on the quadrupole may also be set as a function of time, i.e., equation (2):
Figure GDA0003838942490000065
the invention discloses a quadrupole rod mass analyzer based on single-path radio frequency driving, which is compared with the prior art:
the invention does not need two-way radio frequency drive, so as to avoid the manufacturing difficulties that the two-way radio frequency needs to keep consistent amplitude, consistent resonant frequency, phase synchronization and the like, simplify the debugging process, reduce the manufacturing difficulty and cost of the quadrupole rod radio frequency power supply and improve the performance consistency of the quadrupole rod mass analyzer in batches.
Meanwhile, by adopting the power-up mode of the invention, all the ion operation modes commonly used by the quadrupole rod, such as a Scan mode (Scan), a selective ion monitoring mode (SIM), an all-pass transmission mode and the like, can be completed, and the performance of quality analysis, such as precision and the like, is not negatively influenced.
Drawings
Fig. 1 is a schematic structural diagram of a quadrupole mass analyzer driven by a single rf power supply according to the present invention.
Wherein: 1. a first pole rod; 2. a second pole rod; 3. a pole rod III; 4. a pole rod four; 5. a first conductive line; 6. a second conductive line; 7. a radio frequency power supply; 8. a direct current power supply.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Wherein the showings are for the purpose of illustration only and are shown by way of illustration only and not in actual form, and are not to be construed as limiting the present patent; to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The first embodiment is as follows:
referring to fig. 1, a quadrupole mass analyzer based on single-channel rf driving comprises four electrode poles, which are a first pole 1, a second pole 2, a third pole 3 and a fourth pole, wherein the first pole 1 and the third pole 3 are connected together by a first wire 5, and a rf voltage Φ is applied by an rf power source 7 x (ii) a The second pole rod 2 and the fourth pole rod 4 are connected together through a second lead 6, and a direct current power supply 8 applies direct current voltage phi on the second pole rod 2 and the fourth pole rod 4 y 。Φ x And phi y Set according to the following equation:
Figure GDA0003838942490000081
wherein:
Figure GDA0003838942490000082
preferably, the radio frequency voltage phi applied by the radio frequency power supply 7 is applied to the pole rod one 1 and the pole rod three 3 x The amplitude is V (t), the DC component is U (t)/2, and the rod potential is U DCbias
Preferably, the DC voltage phi applied to the second pole 2 and the fourth pole 4 by the DC power supply 8 y The DC potential is-U (t)/2 and the rod potential is U DCbias
Preferably, the selection of the mass-to-charge ratio (m/z) can be realized by controlling the amplitude V (t) and the DC component U (t)/2 of the radio frequency power supply and the DC potential-U (t)/2 of the DC power supply 8.
Preferably, when the quadrupole is required to operate in a Selective Ion Monitoring (SIM) mode, U and V are set to constants with reference to equation (3); only ions of a certain mass to charge ratio are allowed to pass through. A rod back detector, only the intensity of this ion is recorded.
Preferably, U (t) and V (t) are functions of time when the quadrupole is operated in a spectrogram Scan (Scan) mode. Referring to equation (3), when U (t) and V (t) vary with time (typically from small to large), the mass-to-charge ratio (m/z) of the passing ions also becomes small to large with time. At the moment, the detector at the rear end of the rod records the intensity of the ion signal, and the intensity can be converted into the peak position and the peak height of the mass spectrum, so that a mass spectrum spectrogram is obtained.
Preferably, when the quadrupole rods need to work in the full-pass mode, the U is set to be zero; at this point, the quadrupole allows all ions within its Mass transmission range (Mass range) to pass through. In this mode, the quadrupole rods are mainly used as mass spectrometry components such as ion transmission rods and collision chambers.
The above embodiments should not be construed as limiting the scope of the invention. The key of the invention is: the quadrupole rod mass analyzer only applies single-path radio frequency high voltage to one group of the quadrupole rods so as to reduce the difficulty of radio frequency power supply design, debugging, manufacturing and mass production. Any changes made to the invention without departing from the spirit thereof should fall within the scope of the invention.
The theoretical derivation process of the present invention uses the shape of the classical linear hyperboloid quadrupole electrode, but should not be construed as limiting the scope of the present invention. In the prior art, there are structures such as round rods, flat rods (square rods) and the like to generate an approximate quadrupole field, which can control the ion motion. The key point of the invention is to provide a new way of applying power to the rod, and the changes of the shape, the length and the like of the rod can be within the protection scope of the invention without departing from the spirit of the invention.

Claims (5)

1. The utility model provides a quadrupole rod mass analyzer based on single track radio frequency drive, includes four poles, is pole one (1), pole two (2), pole three (3) and pole four (4) respectively, pole one (1) and pole three (3) are a set of, pole one (1) and pole three (3) are connected through first wire (5), pole two (2) and pole four (4) are a set of, pole two (2) and pole four (4) are connected through second wire (6), its characterized in that: the first lead (5) is connected with a radio frequency power supply (7), the second lead (6) is connected with a direct current power supply (8), and the specific flow of the quadrupole mass analyzer is as follows:
1) And the electric potentials applied to the two groups of pole rods are respectively as follows:
Figure FDA0003843111920000011
wherein: the two pole rods on the x axis are provided with radio frequency voltage with amplitude of V (t), DC component of U (t)/2 and rod potential of U DCbias In the y-axis, only the DC potential-U (t)/2 and the rod potential U are applied to the two poles DCbias
2) The relation between the mass selection of the quadrupole rods and the electric potential on the rods meets the following conditions:
Figure FDA0003843111920000012
that is, by controlling the amplitude V and DC component U of the RF voltage, the selection of mass-to-charge ratio (m/z) can be achieved, m being the ion mass, z being the charge number, m/z being the mass-to-charge ratio, e being the amount of the basic charge, ω being the angular frequency of the RF voltage, r 0 The radius of a circle inscribed in the quadrupole rod is shown, and a and q are two coefficients in a Marsey equation;
3) When the quadrupole rod needs to work in a Selective Ion Monitoring (SIM) mode, setting U and V as constants according to a formula (3); only ions with a certain mass-to-charge ratio are allowed to pass through at the moment, and the detector at the rear end of the rod only records the intensity of the ions;
4) When the quadrupole rod works in a spectrogram scanning (Scan) mode, U (t) and V (t) are functions of time, referring to a formula (3), when the U (t) and the V (t) change from small to large along with time, the mass-to-charge ratio (m/z) of passing ions also changes from small to large along with time, and the peak position and the peak height recorded by a detector at the rear end of the rod can be converted into a mass spectrogram;
5) When the quadrupole rod needs to work in the full-pass mode, the U is set to be zero; the quadrupole rods now allow all ions within their Mass transmission range (Mass range) to pass through, and now they act primarily as ion transmission rods, collision cells.
2. The quadrupole mass analyzer based on single-pass radio frequency driving of claim 1, wherein: the shape of the first pole rod (1), the second pole rod (2), the third pole rod (3) and the fourth pole rod (4) is a hyperbolic pole, a round pole or a square pole.
3. The quadrupole mass analyzer based on single-pass radio frequency driving of claim 1, wherein: the central axes of the first pole rod (1), the second pole rod (2), the third pole rod (3) and the fourth pole rod (4) are linear or arc.
4. The quadrupole mass analyzer based on single-pass radio frequency driving of claim 1, wherein: the first pole rod (1), the second pole rod (2), the third pole rod (3) and the fourth pole rod (4) are made of stainless steel or molybdenum.
5. The quadrupole mass analyzer based on single-pass radio frequency driving of claim 1, wherein: the first pole rod (1), the second pole rod (2), the third pole rod (3) and the fourth pole rod (4) are made of ceramic gold plating.
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