CN114005722B - Digital ion detection method and device of mass spectrometry detection equipment - Google Patents
Digital ion detection method and device of mass spectrometry detection equipment Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/0027—Methods for using particle spectrometers
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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
- H01J49/022—Circuit arrangements, e.g. for generating deviation currents or voltages ; Components associated with high voltage supply
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- H—ELECTRICITY
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- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
- H01J49/40—Time-of-flight spectrometers
Abstract
The present disclosure relates to the field of mass spectrometry, and in particular, to a method and an apparatus for digital ion detection of a time-of-flight mass spectrometry detection device, the method including: an extraction electric field is formed by the voltage output by a first electrode and a second electrode of a high-voltage power supply, the output voltage of the first electrode is constant, the output voltage of the second electrode is larger than or equal to the output voltage of the first electrode, the output voltage of the second electrode is adjusted at a first set moment, the output voltage of the second electrode is smaller than the output voltage of the first electrode, and ions in the extraction electric field are extracted under the action of potential difference. According to the digital ion detection method and device of the mass spectrometry detection equipment, the extraction voltage is digitally and dynamically adjusted, so that ion extraction can be realized, and parameters such as the extraction voltage, the extraction time and the like can be adjusted and controlled at the beginning of ion extraction and in the process of ion extraction, so that the ion extraction quality is improved, and the resolution of a flight time mass spectrometry is improved.
Description
Technical Field
The present disclosure relates to the field of mass spectrometry, and in particular, to a method and an apparatus for digital ion detection in a time-of-flight mass spectrometry detection device.
Background
The flight time mass spectrum is a mass spectrometer, ions are excited and enter a drift tube after being accelerated, and then fly to an ion receiver, wherein the larger the mass of the ions is, the longer the time taken for the ions to reach the receiver is, the smaller the mass of the ions is, the shorter the time taken for the ions to reach the receiver is, and according to the principle, the ions with different masses can be separated according to the size of an m/z value. The flight time mass spectrometer has the advantages of large detectable molecular weight range, high scanning speed and simple instrument structure.
At present, when ions are extracted (ions enter a drift tube for operation), energy is stored by means of a high-voltage capacitor, an ion extraction pulse is provided, the edge of the high-voltage pulse is relatively gentle, the initial speeds of the ions with different masses caused by the ion extraction process possibly have large differences, and the improvement of the resolution ratio of a flight time mass spectrum is not facilitated.
Disclosure of Invention
In order to solve at least the above technical problems in the prior art, the embodiments of the present disclosure provide a method and an apparatus for digital ion detection of a mass spectrometry detection device.
One aspect of the embodiments of the present disclosure provides a digital ion detection method for a mass spectrometry detection apparatus, where the method includes: an extraction electric field is formed by the voltage output by a first electrode and a second electrode of a high-voltage power supply, the output voltage of the first electrode is constant, and the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode; and adjusting the output voltage of the second electrode at a first set moment to enable the output voltage of the second electrode to be smaller than the output voltage of the first electrode, and extracting ions in the extraction electric field under the action of the potential difference.
In some embodiments, before adjusting the output voltage of the second electrode at the first set time, the method further comprises: the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode in a set time, the output voltage of the first electrode is a constant voltage, and ions in the extraction electric field move to a specified position with an initial velocity of 0 at the specified position.
In some embodiments, the method further comprises: an accelerating electric field is formed by the voltage output by the second electrode of the high-voltage power supply and the first grounding electrode; after the output voltage of the second electrode is adjusted at the first set moment, the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode at the second set moment, and ions extracted by the extraction electric field move in an accelerated manner under the action of the potential difference of the acceleration electric field.
In some embodiments, the method further comprises: forming a focusing electric field through the voltage output by the third electrode of the high-voltage power supply, wherein the moving ions pass through the focusing electric field in an accelerated manner; adjusting an output voltage of the third electrode to change a focal position of the ions passing through the focusing electric field.
In some embodiments, the method further comprises: the voltage output by the fourth electrode of the high-voltage power supply is an ion capture excitation voltage; adjusting the ion trapping excitation voltage changes the sensitivity of the trapped ions.
In some embodiments, adjusting the ion trapping excitation voltage, changing the sensitivity of the trapped ions comprises: adjusting the ion trapping excitation voltage according to the output voltage of the third electrode; and when the output voltage of the third electrode is in a first preset range, the ion capture excitation voltage is reduced, and when the output voltage of the third electrode is in a second preset range, the ion capture excitation voltage is increased.
In some embodiments, the method further comprises: and monitoring the high-voltage output value and the output time of the high-voltage power supply through a digital-to-analog converter.
In some embodiments, the high voltage power supply is a digital power supply or an analog power supply.
In some embodiments, the first electrode and/or the second electrode outputs a voltage in the range of 10kV to 30kV, the third electrode outputs a voltage in the range of 1kV to 10kV, and the fourth electrode outputs a voltage in the range of 1kV to 5 kV.
In some embodiments, the voltage output by the first electrode and/or the second electrode is 20kV, the voltage output by the third electrode is 5kV, and the voltage output by the fourth electrode is 3 kV.
In some embodiments, the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode by a difference of 0 to 3 kV; and adjusting the output voltage of the second electrode at a first set moment to enable the output voltage of the second electrode to be smaller than the output voltage of the first electrode, wherein the difference value of the output voltage of the second electrode and the output voltage of the first electrode is 200V-5 kV.
In some embodiments, the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode, and the difference between the output voltage of the second electrode and the output voltage of the first electrode is 300V-500V; and adjusting the output voltage of the second electrode at a first set moment to enable the output voltage of the second electrode to be smaller than the output voltage of the first electrode, wherein the difference value of the output voltage of the second electrode and the output voltage of the first electrode is 2 kV-3 kV.
Another aspect of the disclosed embodiments provides a digital ion detection device for a mass spectrometry detection apparatus, the device including a high voltage power supply module and a timing control module; the voltage output by a first electrode and a second electrode of the high-voltage power supply module forms an extraction electric field, the output voltage of the first electrode is constant, and the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode; the time sequence control module is used for adjusting the output voltage of the second electrode at a first set moment to enable the output voltage of the second electrode to be smaller than the output voltage of the first electrode, and ions in the extraction electric field are extracted under the action of potential difference.
In some embodiments, the timing control module is further configured to, before adjusting the output voltage of the second electrode at the first set time, control the output voltage of the second electrode to be greater than or equal to the output voltage of the first electrode for a set time, and control the output voltage of the first electrode to be a constant voltage, and the ions in the extracted electric field move to a specified position and have an initial velocity at the specified position of 0.
In some embodiments, the voltage output by the second electrode of the high voltage power supply module and the first ground electrode form an accelerating electric field; the time sequence control module is used for adjusting the output voltage of the second electrode at a first set moment and then adjusting the output voltage of the second electrode to be larger than or equal to the output voltage of the first electrode at a second set moment, and ions led out by the lead-out electric field move in an accelerating mode under the action of the potential difference of the accelerating electric field.
In some embodiments, the voltage output by the third electrode of the high voltage power supply module forms a focusing electric field through which the moving ions are accelerated; and the time sequence control module is used for adjusting the output voltage of the third electrode and changing the focal position of the ions passing through the focusing electric field.
In some embodiments, the voltage output by the fourth electrode of the high voltage power supply module is an ion trapping excitation voltage; the time sequence control module is used for adjusting the ion capture excitation voltage and changing the sensitivity of the captured ions.
In some embodiments, the timing control module is to adjust the ion trapping excitation voltage, the varying the sensitivity of the trapped ions comprising: adjusting the ion trapping excitation voltage according to the output voltage of the third electrode; and when the output voltage of the third electrode is in a first preset range, the ion capture excitation voltage is reduced, and when the output voltage of the third electrode is in a second preset range, the ion capture excitation voltage is increased.
In some embodiments, the monitoring module comprises a digital-to-analog converter, and the high voltage output value and the output time of the high voltage power supply are monitored through the digital-to-analog converter.
According to the digital ion detection method and device for the mass spectrum detection equipment, the extraction voltage is digitally and dynamically adjusted, so that ion extraction can be realized, and parameters such as the extraction voltage, the extraction time and the like can be adjusted and controlled at the beginning of ion extraction and in the process of ion extraction, so that the extraction quality of ions is improved, and the resolution of a flight time mass spectrum can be improved.
Drawings
The above and other objects, features and advantages of exemplary embodiments of the present disclosure will become readily apparent from the following detailed description read in conjunction with the accompanying drawings. Several embodiments of the present disclosure are illustrated by way of example, and not by way of limitation, in the figures of the accompanying drawings and in which:
in the drawings, the same or corresponding reference numerals indicate the same or corresponding parts.
Fig. 1 is a schematic structural diagram of an ion extraction process in a digital ion detection method of a mass spectrometry detection apparatus according to an embodiment of the present disclosure;
fig. 2 is a schematic structural diagram of an embodiment of the present disclosure when ions are accelerated in a digital ion detection method of a mass spectrometry detection apparatus;
fig. 3 is a schematic structural diagram of an embodiment of the present disclosure when ions are focused in a digital ion detection method of a mass spectrometry detection apparatus;
fig. 4 is a schematic structural diagram of ion trapping in a digital ion detection method of a mass spectrometry detection apparatus according to an embodiment of the present disclosure;
FIG. 5 is a waveform diagram of the first electrode output voltage and the second electrode output voltage in the digital ion detection method of the mass spectrometry detection apparatus according to the embodiment of the disclosure;
FIG. 6 is a waveform diagram of the third electrode output voltage and the fourth electrode output voltage in the digital ion detection method of the mass spectrometry detection apparatus according to the embodiment of the disclosure;
FIG. 7 is a schematic timing diagram illustrating a digital ion detection method of a mass spectrometry detection apparatus according to an embodiment of the present disclosure;
FIG. 8 is a schematic diagram of a digital high voltage power supply in a digital ion detection method of a mass spectrometry detection apparatus according to an embodiment of the disclosure;
FIG. 9 is a schematic diagram of an analog high voltage power supply in the digital ion detection method of the mass spectrometry detection apparatus according to the embodiment of the disclosure;
FIG. 10 is a schematic diagram illustrating timing control in a digital ion detection method of a mass spectrometry detection apparatus according to an embodiment of the disclosure;
fig. 11 is a block diagram of a digital ion detection device of a mass spectrometry detection apparatus according to an embodiment of the disclosure;
fig. 12 is another block diagram of the digital ion detection device of the mass spectrometry detection apparatus according to the embodiment of the disclosure.
In the figure:
100: a digital ion detection device; 110: a high voltage power supply module; 120: a timing control module; 130: and a monitoring module.
Detailed Description
The invention provides a digital ion detection method and a digital ion detection device of mass spectrum detection equipment.
In order to make the objects, features and advantages of the present disclosure more apparent and understandable, the technical solutions in the embodiments of the present disclosure will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present disclosure, and it is apparent that the described embodiments are only a part of the embodiments of the present disclosure, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments disclosed herein without making any creative effort, shall fall within the protection scope of the present disclosure.
According to the digital ion detection method of the mass spectrometry detection device provided by the present disclosure, as shown in fig. 1, an extraction electric field is formed by voltages output by a first electrode and a second electrode of a high voltage power supply, in fig. 1, the voltage output by the first electrode is P1, the voltage output by the second electrode is P2, the extraction electric field is formed between P1 and P2, the output voltage P1 of the first electrode is a constant voltage, the value of the constant voltage is adjustable, and the output voltage P2 of the second electrode is greater than or equal to the output voltage P1 of the first electrode.
In some embodiments, the present disclosure provides a method for performing digital ion detection on positively or negatively charged ions, respectively, wherein the positive or negative logic voltages are required for the positive or negative ions during detection. For example, the digital ion detection provided by the present disclosure includes four voltages, which are respectively voltages output by the first electrode, the second electrode, the third electrode and the fourth electrode, and when positive charge ions are detected, the voltages output by the first electrode, the second electrode and the third electrode are set to positive high voltages, and the voltage output by the fourth electrode is set to negative high voltages; when detecting negative charge ions, the voltage output by the first electrode, the second electrode and the third electrode is set as negative high voltage, and the voltage output by the fourth electrode is set as positive high voltage.
In the following, the detection of positive charge ions is taken as an example, however, based on the digital ion detection method of the mass spectrometry detection device provided by the present disclosure, a method for detecting negative charge ions should also be within the protection scope of the present disclosure.
For example, in the positive charge ion detection, the voltages output by the first electrode and/or the second electrode are both positive high voltages, and the voltage range output by the first electrode and/or the second electrode is + 10kV to + 30kV, or, for example, when the output voltage of the first electrode and the output voltage of the second electrode are the same, the voltage output by the first electrode and/or the second electrode is + 20 kV. For example, the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode, and the difference between the two is 0-3 kV, or for example, the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode, and the difference between the two is 300-500V.
In some embodiments, the output voltage of the second electrode is adjusted at a first set time so that the output voltage of the second electrode is less than the output voltage of the first electrode, and ions in the extraction electric field are extracted under the action of the potential difference.
For example, the difference between the output voltage of the second electrode and the output voltage between the first electrodes is 200V to 5kV, or for example, the difference between the output voltage of the second electrode and the output voltage between the first electrodes is 2kV to 3 kV.
After the output voltage of the second electrode is reduced, the ions are accelerated out of the extracted ions in the extraction electric field to a certain degree, and then the operation of controlling the ion extraction by adjusting the voltage is realized. The first set time may be interpreted as: in the time-series control process, a time at which ion extraction starts is set, and the time has a certain time length.
The manner in which the output voltage of the second electrode becomes smaller is also in accordance with the set variation manner. For example, the change is made directly to the set value (the value after the final reduction), or the change is made to the set value in a change manner with a constant slope.
After the ions are controlled and excited in the ion source, time, space and speed discreteness may exist, and if the excited ions are directly extracted, the extraction speed of the ions is not easy to control. Therefore, in the embodiment of the present disclosure, a delay extraction manner is adopted.
In some embodiments, before adjusting the output voltage of the second electrode at the first set time, the method further comprises: the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode in a set time, and the output voltage of the first electrode is a constant voltage. The set time is interpreted as: and after the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode and is kept for a certain time, the output voltage of the second electrode is adjusted. In the set time, because the output voltage of the second electrode is not less than the output voltage of the first electrode, after the ions are controlled to be excited, the ions are bound on the ion source structural surface, the initial speed is reduced to 0, and similarly, the ions are bound on the ion source structural surface, and the dispersion of the ion space is only limited to the size of the excitation surface when the ions are excited, so that the ion speed and the dispersion of the space can be effectively reduced through the delayed extraction setting.
In some embodiments, the accelerating electric field is formed by the voltage output by the second electrode of the high voltage power supply and the first ground electrode; after adjusting the output voltage of the second electrode at a first set time, the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode at a second set time, which can be interpreted as: and after the first set moment, namely entering a second moment, adjusting the output voltage of the second electrode and keeping the state that the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode.
For example, the output voltage of the second electrode at the second time may be the same as or different from the output voltage of the second electrode before the first time. For example, the output voltage of the second electrode at the second timing is a constant voltage.
In some embodiments, the ions extracted by the extraction electric field are accelerated by the potential difference of the acceleration electric field, as shown in fig. 2, where the first grounded electrode is GND, and the ions extracted by the extraction electric field automatically enter the acceleration electric field, and in the acceleration electric field, the ion velocity depends on the potential difference between P2 and GND.
As shown in fig. 5, it can be seen from the waveform diagram shown in fig. 5 that the output voltage P1 of the first electrode is a constant value, the output voltage P2 of the second electrode is a constant value before the first time and also at the second time, the output voltage P2 of the second electrode decreases with a constant slope at the start of the first time, and increases with a constant slope after the minimum value is maintained for a certain time.
In some embodiments, a focusing electric field is formed by a voltage output by the third electrode of the high-voltage power supply, ions moving with acceleration pass through the focusing electric field when flying along the flight tube, and the ions are made to fly to the ion trap after being focused by the focusing electric field. Because the lighter ions pass through the focusing structure first and the heavier ions pass through the focusing structure later, the higher the focusing voltage, the closer the focus. Some light-weight ions lose the window of the ion detector when reaching the ion detector, so that part of ions can be screened from reaching the ion detector by dynamically adjusting the intensity of the output voltage of the third electrode, thereby improving the ion abundance curve in the time-of-flight mass spectrum detection range. As shown in fig. 3, the output voltage of the third electrode is shown as P3, and adjusting the output voltage of the third electrode changes the focal position of the ions passing through the focusing electric field.
For example, when the value of the third electrode output voltage P3 is increased, the focal point of ions passing through the focusing electric field is closer, or when the value of the third electrode output voltage P3 is decreased, the focal point of ions passing through the focusing electric field is farther. By adjusting the third electrode output voltage P3, screening of ions arriving at the ion detector can be achieved.
For example, the voltage output from the third electrode is a positive high voltage, the voltage output from the third electrode is + 1kV to + 10kV, or the voltage output from the third electrode is + 5kV, for example.
In some embodiments, as shown in fig. 4, the voltage output by the fourth electrode of the high voltage power supply is an ion trapping excitation voltage, schematically illustrated as P4; adjusting an ion trapping excitation voltage, and changing the sensitivity of the trapped ions, wherein the ion trapping excitation voltage is adjusted according to the output voltage of the third electrode when the ion trapping excitation voltage is adjusted; and when the output voltage of the third electrode is in a second preset range, the ion trapping excitation voltage is increased. The first preset range and the second preset range are interpreted as: and the preset regulation range is used for regulating the output voltage P3 of the third electrode.
For example, when the output voltage of the third electrode is high (first predetermined range), the ion abundance during this period of time is large, and a low ion trapping excitation voltage can be provided, or when the output voltage of the third electrode is low (second predetermined range), the ion abundance during this period of time is small, and the ion trapping excitation voltage can be further increased, so that the signal-to-noise ratio of the ions can be improved, and the ion detection sensitivity can be balanced and improved.
The voltage output by the fourth electrode is, for example, a negative high voltage and the voltage output by the fourth electrode is-1 kV to-5 kV, or, for example, the voltage output by the fourth electrode is-3 kV.
As shown in fig. 6, as can be seen from the waveform diagram shown in fig. 6, when the output voltage P3 of the third electrode is adjusted to be low, the corresponding ion trapping excitation voltage P4 is increased, wherein the output voltage P3 of the third electrode and the ion trapping excitation voltage P4 can be adjusted with a certain slope and can also be kept at a constant value.
The following will further describe the steps of ion confinement, ion extraction, ion acceleration, ion focusing, ion flying, ion capturing, ion detection, and the like involved in the digital ion detection method of the mass spectrometry apparatus with reference to fig. 7 and the above description.
As shown in fig. 7, time T1 is an ion confinement phase, at which time the ions are not excited, and at time T2 the ions are excited, and a delay extraction time is included after the excitation is completed. The excited ions are in an extraction electric field, the output voltage P2 of the second electrode is larger than or equal to the output voltage P1 of the first electrode in the delay extraction time period, the ions are bound on the ion source structural surface, and therefore the initial speed of the ions is reduced to 0, and the dispersion of the ions in speed and space is eliminated or reduced.
With continued reference to fig. 7, the time T3 is the ion extraction time, during which the output voltage P2 of the second electrode is adjusted to make the output voltage P2 of the second electrode smaller than the output voltage P1 of the first electrode, for example, the difference between P2 and P1 is 3 kV. The time T4 is the ion flight time, in which the ions fly along a straight line, and the ions can be accelerated and focused by adjusting the output voltage of the high-voltage power supply. After the ions are extracted, the output voltage P2 of the second electrode is adjusted to ensure that the output voltage P2 of the second electrode is greater than or equal to the output voltage P1 of the first electrode, after the output voltage P2 of the second electrode is increased, a potential difference exists between the second electrode and the first grounding electrode, and the extracted ions are accelerated under the action of the potential difference. Ion acceleration operation can dynamically change the mass range or shorten the flight tube length. After the ions are extracted and accelerated, the focuses among the ions may be dispersed, and in order to correct and adjust the focal positions of the ions, a focusing electric field is arranged on a flight channel of the ions. For example, the third electrode output voltage P3 is increased to make the focal position of the ions passing through the focusing electric field closer, thereby achieving the purpose of focusing. According to the focusing regulation mode, partial ions can be screened to reach the ion detector by dynamically regulating the intensity of P3, so that the ion abundance curve in the time-of-flight mass spectrum detection range is improved.
With continued reference to fig. 7, the time T5 is the ion detection time, and after the ions are extracted, accelerated, focused, and arrive at the ion detector. Wherein the output voltage P4 of the fourth electrode of the high voltage power supply is an ion trapping excitation voltage, and the adjustment of the ion trapping excitation voltage is coordinated with the adjustment of P3. For example, when the output voltage of the third electrode is high, the ion abundance during this period of time is large, and therefore, a low ion trapping excitation voltage can be provided, or, for example, when the output voltage of the third electrode is low, the ion abundance during this period of time is small, and the ion trapping excitation voltage can be further increased, so that the signal-to-noise ratio of the ions can be improved, and the ion detection sensitivity can be balanced and improved.
The digital ion detection method of the mass spectrum detection device is completed by sequentially controlling the high-voltage power supply through the digital time sequence controller, so that the input and the output of the high-voltage power supply and the time sequence controller are required to be set.
For example, fig. 8 is a schematic diagram of a digital high-voltage power interface, in which a digital high-voltage power input portion includes a low-voltage power input, a digital parameter input, a digital output enable, and an output logic state, and a digital high-voltage power output portion includes a high-voltage power output. For example, digital parameter inputs include, but are not limited to, output time, output voltage, voltage rise and fall slope.
In some embodiments, the digital high voltage power supply can be a digital high voltage power supply with digital interface preset parameters and pulse trigger output, as shown in fig. 8; or the analog power supply can be transformed by a latch-up digital interface, preset analog output voltage, and simulate automatic output or/and pulse trigger output, as shown in fig. 9.
In some embodiments, the digital high voltage power supply output monitors whether the high voltage output precision and time meet set parameters by using a digital-to-analog converter, thereby completing the closed loop monitoring of the control parameters. By adopting the measure of monitoring the output voltage, the precision of the output voltage and the time sequence is controlled in a closed loop manner, and the stability and the repeatability of the detection result are facilitated.
In some embodiments, as shown in fig. 10, the digital timing control includes P1, P2, P3 and P4 output monitor signal acquisition, ion excitation completion pulse input, ion detection pulse input, P1, P2, P3 and P4 parameter outputs, enable outputs of P1, P2, P3 and P4, ion detection pulse, extraction pulse and detection pulse output, and high voltage monitor signal output. For example, in order to realize the output characteristic and control the output curve of the digital high-voltage power supply, the timing signals of the digital timing controller at least provide the voltage magnitude and the enable signal of the P1, P2, P3 and P4 high-voltage power supply outputs, and the turn-on time, the rising and falling slope, the maintaining time and the ending time of the P2, P3 and P4 high-voltage power supplies. The digital timing controller provides digital control signals including output voltage values, on-voltage time and off-voltage time, and preferably also includes the enabling of a digital high-voltage power supply; providing the analog control signal includes outputting a height, a pulse width of the analog signal and, preferably, may also include enabling the digital high voltage power supply.
In some embodiments, the timing provided by the digital timing controller, a common time reference within the digital timing controller, is synchronized to each of the digital high voltage power supplies and provides an ion excitation pulse, an ion collection pulse, and may also provide an ion extraction pulse. For example, the digital timing controller and the time bases of the other controllers adopt a common time base signal.
In some embodiments, the digital timing controller can also provide programmable voltage response curves adapted to P3 and P4, so as to improve the abundance and sensitivity of ion detection; the ion flight time is generally ns and us-level time, the digital time sequence controller uniformly commands and coordinates the output curve of the high-voltage power supply, and the input reference frequency precision of the digital time sequence controller is better than 5ppm, preferably 0.1 ppm; the adjusting frequency of the digital time sequence controller is generally 1 Khz-100 Kz, 100 kHz-1 MHz and 1 MHz-100 MHz, the smaller the mass in the mass range, the higher the adjusting frequency, and the mass range is 50(m/z) -500K (m/z).
In some embodiments, after the ion focusing or/and ion capturing steps are ready, ion extraction and ion acceleration are performed according to the time sequence and the intensity provided by the controller, the ion acceleration automatically enters the ion focusing, the ion flying and the ion capturing, and the ion detection starting time and the detection gain are given according to the mass range, so that the mass range of the time-of-flight mass spectrum can be effectively and dynamically expanded, and the ion abundance response curve can be improved.
The digital ion detection device of the mass spectrometry detection equipment provided by the present disclosure, as shown in fig. 11, the device 100 includes a high voltage power module 110 and a timing control module 120; the voltage output by the first electrode and the voltage output by the second electrode of the high-voltage power supply module 110 form an extraction electric field, the output voltage of the first electrode is a constant voltage, and the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode; the timing control module 120 is configured to adjust the output voltage of the second electrode at a first setting time, so that the output voltage of the second electrode is smaller than the output voltage of the first electrode, and ions in the extraction electric field are extracted under the action of the potential difference.
In some embodiments, the timing control module 120 is further configured to control the output voltage of the second electrode to be greater than or equal to the output voltage of the first electrode for a set time before adjusting the output voltage of the second electrode at the first set time, and control the output voltage of the second electrode to be a constant voltage, and the ions in the extracted electric field move to a specified position and have an initial velocity at the specified position of 0. The timing control module 120 sets the delay extraction, which can effectively reduce the ion velocity and the spatial dispersion.
In some embodiments, the voltage output by the second electrode of the high voltage power supply module 110 and the first ground electrode form an accelerating electric field; the timing control module 120 is configured to adjust the output voltage of the second electrode at a first setting time, and then adjust the output voltage of the second electrode at a second setting time to be greater than or equal to the output voltage of the first electrode, so that ions extracted by the extraction electric field move in an accelerated manner under the action of the potential difference of the acceleration electric field. The speed of the ions in the accelerating electric field depends on the adjustment of the output voltage of the second electrode by the timing control module 120, and the mass range can be dynamically changed or the length of the flight tube can be shortened by the ion accelerating operation.
In some embodiments, the voltage output by the third electrode of the high voltage power module 110 forms a focusing electric field, which accelerates the moving ions through; the timing control module 120 is used for adjusting the output voltage of the third electrode to change the focal position of the ions passing through the focusing electric field. By dynamically adjusting the intensity of the voltage output by the third electrode, part of ions can be screened to reach the ion detector, so that the ion abundance curve in the time-of-flight mass spectrum detection range is improved.
In some embodiments, the voltage output by the fourth electrode of the high voltage power supply module 110 is an ion trapping excitation voltage; the timing control module 120 is used to adjust the ion trapping excitation voltage to change the sensitivity of the trapped ions. For example, the timing control module 120 is used to adjust the ion trapping excitation voltage, varying the sensitivity of the trapped ions including: adjusting an ion trapping excitation voltage according to an output voltage of the third electrode; and when the output voltage of the third electrode is in a second preset range, the ion trapping excitation voltage is increased.
For example, when the output voltage of the third electrode is high (first predetermined range), the ion abundance during this period of time is large, and a low ion trapping excitation voltage can be provided, or when the output voltage of the third electrode is low (second predetermined range), the ion abundance during this period of time is small, and the ion trapping excitation voltage can be further increased, so that the signal-to-noise ratio of the ions can be improved, and the ion detection sensitivity can be balanced and improved.
In some embodiments, as shown in fig. 11, the apparatus 100 further includes a monitoring module 130, and the monitoring module 130 includes a digital-to-analog converter, and monitors the high voltage output value and the output time of the high voltage power supply through the digital-to-analog converter. By adopting the measure of monitoring the output voltage, the precision of the output voltage and the time sequence is controlled in a closed loop manner, and the stability and the repeatability of the detection result are facilitated.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present disclosure, "a plurality" means two or more unless specifically limited otherwise.
The above is only a specific embodiment of the present disclosure, but the scope of the present disclosure is not limited thereto, and any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present disclosure, and shall be covered by the scope of the present disclosure. Therefore, the protection scope of the present disclosure shall be subject to the protection scope of the claims.
Claims (12)
1. A method of digital ion detection by a mass spectrometry detection apparatus, wherein the method comprises:
an extraction electric field is formed by the voltage output by a first electrode and a second electrode of a high-voltage power supply, the output voltage of the first electrode is constant, and the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode;
adjusting the output voltage of the second electrode at a first set moment to enable the output voltage of the second electrode to be smaller than the output voltage of the first electrode, and extracting ions in the extraction electric field under the action of a potential difference;
before the output voltage of the second electrode is adjusted at the first set moment, the method further comprises the following steps: the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode for a set time, and the output voltage of the first electrode is a constant voltage, the set time being interpreted as: after the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode and is kept for a certain time, the output voltage of the second electrode is adjusted, and in the set time, because the output voltage of the second electrode is not less than the output voltage of the first electrode, after the ions are controlled and excited, the ions are bound on the ion source structure surface, the initial speed is reduced to 0, and the first set time can be interpreted as: in the time-series control process, a time at which ion extraction starts is set, and the time has a certain time length.
2. The method of claim 1, wherein the method further comprises:
an accelerating electric field is formed by the voltage output by the second electrode of the high-voltage power supply and a first grounding electrode;
after the output voltage of the second electrode is adjusted at the first set moment, the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode at the second set moment, and ions extracted by the extraction electric field move in an accelerated manner under the action of the potential difference of the acceleration electric field.
3. The method of claim 2, wherein the method further comprises:
forming a focusing electric field through the voltage output by the third electrode of the high-voltage power supply, wherein the moving ions pass through the focusing electric field in an accelerated manner;
adjusting an output voltage of the third electrode to change a focal position of the ions passing through the focusing electric field.
4. The method of claim 3, wherein the method further comprises:
the voltage output by the fourth electrode of the high-voltage power supply is an ion capture excitation voltage;
adjusting the ion trapping excitation voltage changes the sensitivity of the trapped ions.
5. The method of claim 4, wherein adjusting the ion trapping excitation voltage, changing the sensitivity of the trapped ions comprises:
adjusting the ion trapping excitation voltage according to the output voltage of the third electrode;
and when the output voltage of the third electrode is in a first preset range, the ion capture excitation voltage is reduced, and when the output voltage of the third electrode is in a second preset range, the ion capture excitation voltage is increased.
6. The method of any of claims 1-5, wherein the method further comprises:
and monitoring the high-voltage output value and the output time of the high-voltage power supply through a digital-to-analog converter.
7. The method of any one of claims 1 to 5, wherein the high voltage power supply is a digital power supply or an analog power supply.
8. The method of claim 4 or 5, wherein the first and/or second electrode outputs a voltage in the range of 10kV to 30kV, the third electrode outputs a voltage in the range of 1kV to 10kV, and the fourth electrode outputs a voltage in the range of 1kV to 5 kV.
9. The method of claim 8, wherein the first electrode and/or the second electrode outputs a voltage of 20kV, the third electrode outputs a voltage of 5kV, and the fourth electrode outputs a voltage of 3 kV.
10. The method of claim 1, wherein the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode by a difference of 0 to 3 kV;
and adjusting the output voltage of the second electrode at a first set moment to enable the output voltage of the second electrode to be smaller than the output voltage of the first electrode, wherein the difference value of the output voltage of the second electrode and the output voltage of the first electrode is 200V-5 kV.
11. The method according to claim 10, wherein the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode by a difference of 300V to 500V;
and adjusting the output voltage of the second electrode at a first set moment to enable the output voltage of the second electrode to be smaller than the output voltage of the first electrode, wherein the difference value of the output voltage of the second electrode and the output voltage of the first electrode is 2 kV-3 kV.
12. A digital ion detection device of mass spectrum detection equipment is disclosed, wherein the device comprises a high-voltage power supply module and a time sequence control module;
the voltage output by a first electrode and a second electrode of the high-voltage power supply module forms an extraction electric field, the output voltage of the first electrode is constant, and the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode;
the timing control module is used for enabling the output voltage of the second electrode to be larger than or equal to the output voltage of the first electrode in a set time, the output voltage of the first electrode is a constant voltage, and the set time is interpreted as: after the output voltage of the second electrode is greater than or equal to the output voltage of the first electrode and is kept for a certain time, the output voltage of the second electrode is adjusted, and in the set time, because the output voltage of the second electrode is not less than the output voltage of the first electrode, after the ions are controlled and excited, the ions are bound on the ion source structure surface, the initial speed is reduced to 0, and the first set time can be interpreted as: in the time sequence control process, setting the moment of starting to extract ions, wherein the moment has a certain time length; and adjusting the output voltage of the second electrode at a first set moment to enable the output voltage of the second electrode to be smaller than the output voltage of the first electrode, and extracting ions in the extraction electric field under the action of the potential difference.
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