CN108172494B - Method and device for improving mass spectrum sensitivity - Google Patents

Method and device for improving mass spectrum sensitivity Download PDF

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CN108172494B
CN108172494B CN201711366703.6A CN201711366703A CN108172494B CN 108172494 B CN108172494 B CN 108172494B CN 201711366703 A CN201711366703 A CN 201711366703A CN 108172494 B CN108172494 B CN 108172494B
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time
flight
detector
voltage value
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CN108172494A (en
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刘平
喻佳俊
朱星高
黄利勇
林利泉
曾真
陈颖
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Guangzhou Hsin Kang Yuan Medical Technology Co Ltd
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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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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 invention relates to a method and a device for improving sensitivity of a mass spectrum, which are used for a time-of-flight mass spectrum, and the method comprises the following steps of obtaining an initial time value of th ions reaching an ion detector, a reference voltage value of the ion detector and a voltage adjusting function of the ion detector, wherein the voltage adjusting function is used for recording a corresponding relation of working voltage applied to the ion detector along with change of ion flight time, calculating a target voltage value continuously changing in a preset ion flight time range according to the initial time value, the reference voltage value and the voltage adjusting function, and sending the target voltage value to a control circuit of the time-of-flight mass spectrum so that the control circuit adjusts the working voltage applied to the ion detector according to the target voltage value.

Description

Method and device for improving mass spectrum sensitivity
Technical Field
The invention relates to the technical field of mass spectrometry and application, in particular to methods and devices for improving mass spectrometry sensitivity.
Background
A mass spectrometer is also called as a mass spectrometer, is instruments for separating and detecting substances according to the mass difference of substance atoms, molecules or molecular fragments according to the principle that charged particles can deflect in an electromagnetic field, is very in the field of life sciences, and particularly, a time-of-flight mass spectrometer promotes the application and development of a mass spectrometry technology in in the field of life sciences by virtue of the specific high sensitivity and high quality detection range, such as drug metabolism research, ribonucleic acid detection, polypeptide and protein analysis and the like.
The time-of-flight mass spectrometry is based on the principle that the mass-to-charge ratio of ions is proportional to the square of time, and the mass-to-charge ratio can be calculated as long as the time-of-flight of the ions is measured.
Disclosure of Invention
Based on this, it is necessary to provide methods and apparatuses for improving mass spectrometry sensitivity to solve the problems that the current mass spectrometer increases the intensity of fragment ions when detecting large molecules, and is easy to cause oversaturation of the detector when detecting small molecules.
A method for improving the sensitivity of mass spectrometry, comprising the steps of:
acquiring an th ion arrival time value at an ion detector, a reference voltage value of the ion detector and a voltage adjusting function of the ion detector, wherein the voltage adjusting function is used for recording the corresponding relation of working voltage applied to the ion detector along with the change of ion flight time;
and calculating a target voltage value which continuously changes in a preset ion flight time range according to the initial time value, the reference voltage value and the voltage regulation function, and sending the target voltage value to a control circuit of the flight time mass spectrum, so that the control circuit regulates the working voltage applied to the ion detector according to the target voltage value, wherein the working voltage applied to the ion detector is used for improving the sensitivity of a mass spectrometer.
A device for improving sensitivity of mass spectrum comprises
The ion detector comprises an information acquisition module, a data acquisition module and a data processing module, wherein the information acquisition module is used for acquiring an initial time value of an th ion reaching the ion detector, a reference voltage value of the ion detector and a voltage regulation function of the ion detector, and the voltage regulation function is used for recording the corresponding relation of working voltage applied to the ion detector along with the change of ion flight time;
the target voltage value calculating module is used for calculating a target voltage value which continuously changes within a preset ion flight time range according to the initial time value, the reference voltage value and the voltage regulating function;
and the target voltage value sending module is used for sending the target voltage value to a control circuit of the time-of-flight mass spectrum so as to enable the control circuit to adjust the working voltage applied to the ion detector according to the target voltage value, wherein the working voltage applied to the ion detector is used for improving the sensitivity of a mass spectrometer.
A computer device comprising a memory, a processor and a computer program stored on the memory and executable on the processor, the processor when executing the program implementing the steps of:
acquiring an th ion arrival time value at an ion detector, a reference voltage value of the ion detector and a voltage adjusting function of the ion detector, wherein the voltage adjusting function is used for recording the corresponding relation of working voltage applied to the ion detector along with the change of ion flight time;
and calculating a target voltage value which continuously changes in a preset ion flight time range according to the initial time value, the reference voltage value and the voltage regulation function, and sending the target voltage value to a control circuit of the flight time mass spectrum, so that the control circuit regulates the working voltage applied to the ion detector according to the target voltage value, wherein the working voltage applied to the ion detector is used for improving the sensitivity of a mass spectrometer.
computer storage medium having stored thereon a computer program which, when executed by a processor, performs the steps of:
acquiring an th ion arrival time value at an ion detector, a reference voltage value of the ion detector and a voltage adjusting function of the ion detector, wherein the voltage adjusting function is used for recording the corresponding relation of working voltage applied to the ion detector along with the change of ion flight time;
and calculating a target voltage value which continuously changes in a preset ion flight time range according to the initial time value, the reference voltage value and the voltage regulation function, and sending the target voltage value to a control circuit of the flight time mass spectrum, so that the control circuit regulates the working voltage applied to the ion detector according to the target voltage value, wherein the working voltage applied to the ion detector is used for improving the sensitivity of a mass spectrometer.
The method and the device for improving the sensitivity of the mass spectrum are characterized in that firstly, an initial time value of an th ion reaching the ion detector, a reference voltage value of the ion detector and a voltage regulation function are obtained, wherein the voltage regulation function is mainly a function of the working voltage of the ion detector depending on the flight time of the ion, then a target voltage value in the preset flight time of the ion is calculated according to the initial time value, the reference voltage value and the voltage regulation function (namely, the target voltage value is determined along with the change of the flight time of the ion), the calculated target voltage value is sent to a control circuit of the flight time mass spectrum, and the control circuit adjusts the working voltage applied to the ion detector according to the received target voltage value.
Drawings
FIG. 1 is a schematic flow chart of the method for improving sensitivity of mass spectrometry according to the present invention in embodiments;
FIG. 2 is a schematic diagram of the operating principle of the microchannel plate detector of the present invention;
FIG. 3 is a schematic flow chart of the method for improving sensitivity of mass spectrometry according to the present invention in embodiments;
FIG. 4 is a block diagram of the operating voltage of the ion detector of the present invention as a function of linear ion time of flight at embodiments;
FIG. 5 is a schematic flow chart of the method for improving sensitivity of mass spectrometry according to the present invention in embodiments;
FIG. 6 is a block diagram of the operating voltage of the ion detector of the present invention as a function of linear ion time of flight at embodiments;
FIG. 7 is a block diagram of the operating voltage of the ion detector of the present invention as a function of linear ion time of flight at embodiments;
FIG. 8 is a schematic flow chart of an apparatus for increasing sensitivity of mass spectrometry according to the present invention in embodiments;
fig. 9 is a schematic structural diagram of embodiments of the computer device of the present invention.
Detailed Description
The present invention will now be described in detail with reference to preferred embodiments illustrated in the accompanying drawings, it is to be understood that the embodiments are merely illustrative of the present invention and not restrictive, and that all other embodiments, which may be made by those skilled in the art without any inventive faculty, based on the embodiments of the present invention, are encompassed by the present invention.
Fig. 1 is a schematic flow chart of embodiments of the method for improving mass spectrometry sensitivity of the present invention, as shown in fig. 1, the method for improving mass spectrometry sensitivity of the embodiment of the present invention includes the following steps:
step S110, obtaining an initial time value of the th ion reaching the ion detector, a reference voltage value of the ion detector and a voltage adjusting function of the ion detector, wherein the voltage adjusting function is used for recording the corresponding relation of the working voltage applied to the ion detector along with the change of the ion flight time.
And step S120, calculating a target voltage value continuously changing in a preset ion flight time range according to the initial time value, the reference voltage value and the voltage regulation function, and sending the target voltage value to a control circuit of the flight time mass spectrum so that the control circuit regulates the working voltage applied to the ion detector according to the target voltage value, wherein the working voltage applied to the ion detector is used for improving the sensitivity of the mass spectrometer.
The time-of-flight mass spectrometer distinguishes ions according to their flight time, with small mass ions arriving at the detector quickly, large mass ions arriving at the detector slowly, and small mass ions arriving at the detector in large quantities. In addition, the mass-to-charge ratio of ions in time-of-flight mass spectrometry is proportional to the square of time, and the mass-to-charge ratio can be calculated by measuring the time of flight of the ions. During detection, the ions with small mass-to-charge ratio arrive at the ion detector first, and the ions with large mass-to-charge ratio arrive at the ion detector later. The ion detector requires a relatively small operating voltage (i.e., a small voltage to be applied to the ion detector) when detecting ions having a small mass-to-charge ratio, and requires a relatively large operating voltage (i.e., a large voltage to be applied to the ion detector) when detecting ions having a large mass-to-charge ratio.
A Micro-Channel Plate (MCP) detector is an ion detector commonly used in time-of-flight mass spectrometry, and as shown in fig. 2, the MCP detector includes an MCP Plate (2 blocks), three resistors R1-R3, an anode tube, a capacitor C1, a signal output terminal, and an MCP charging terminal, where ions impact (reach) the MCP to generate electrons, the electrons fly from the MCP output to the anode tube, and a current signal is generated and output from the signal output terminal. The higher the voltage applied by the MCP household appliance terminal is, the more secondary electrons generated by the MCP are, and the higher the sensitivity is. When the MCP detector is used for detecting ions, the ion quantity of ions with small mass number is large, the ions can be easily detected by the MCP detector, the supersaturation phenomenon is easy to occur, and the phenomenon can be solved by reducing the voltage of the MCP detector; however, the ion amount of the ion having a large mass number is small, and the voltage of the MCP detector needs to be increased to improve the sensitivity. Since the ion mass of the ions is time-of-flight dependent, the voltage of the MCP detector can be determined from the time-of-flight.
The voltage of the MCP detector is maintained unchanged until the th ion reaches the MCP detector, and the voltage at this time is recorded as the reference voltage value, and then the MCP detector voltage should also be changed when the ion (i.e., when the th ion) reaches the MCP detector.
An initial time value for the ion detector to arrive at the th ion, a reference voltage value for the ion detector, and a voltage adjustment function for the ion detector are obtained, wherein the voltage adjustment function is used to record a correspondence relationship between an operating voltage applied to the ion detector as a function of ion flight time, then an MCP detector voltage value (i.e., a target voltage value) as a function of ion flight time is calculated from the initial time value, the reference voltage value, and the voltage adjustment function, and then a voltage applied to the MCP detector is adjusted based on the calculated MCP detector voltage value.
The preset ion flight time range refers to any value less than the maximum ion flight time.
It should be understood that the ion detector may include not only an MCP detector, but also an electron multiplier detector, a photomultiplier detector, a scintillation detector, etc. and other ion detectors that may be used in time-of-flight mass spectrometry for ion detection, and those skilled in the art may select a suitable ion detector according to their own needs.
The method for improving the sensitivity of the mass spectrometer comprises the steps of firstly obtaining an initial time value of an th ion reaching the ion detector, a reference voltage value of the ion detector and a voltage regulation function, wherein the voltage regulation function is mainly a function of the working voltage of the ion detector depending on the flight time of the ion, then calculating a target voltage value in the preset flight time of the ion according to the initial time value, the reference voltage value and the voltage regulation function (namely, the target voltage value is determined along with the change of the flight time of the ion), sending the calculated target voltage value to a control circuit of the flight time mass spectrometer, and adjusting the working voltage applied to the ion detector by the control circuit according to the received target voltage value.
In embodiments, as shown in fig. 3, the step of calculating the target voltage value continuously changing in the preset ion flight time range includes:
step S121, calculating a target voltage value that continuously changes within a preset ion flight time range by using an incremental voltage adjustment function, where the incremental voltage adjustment function is a function in which the operating voltage of the ion detector depends on the ion flight time, and the operating voltage of the ion detector increases as the ion flight time increases.
Specifically, the incremental voltage adjustment function is a function in which the operating voltage of the ion detector depends on the ion flight time, that is, the incremental voltage adjustment function represents the correspondence between the operating voltage of the ion detector and the ion flight time, where the operating voltage of the ion detector is a dependent variable and the ion flight time is an independent variable.
According to the principle of time-of-flight mass spectrometry, ions with small mass-to-charge ratio (namely, ions with large quantity) have small time-of-flight and reach an ion detector first; the ions with large mass-to-charge ratio (i.e. small ion amount) have large flight time and then arrive at the ion detector, and the ion detector needs a smaller voltage when detecting the ions with small mass-to-charge ratio (i.e. large ion amount) and needs a larger voltage when detecting the ions with small mass-to-charge ratio (i.e. large ion amount), so that the voltage adjustment function should be increased, that is, the voltage adjustment function in which the operating voltage of the ion detector increases with the increase of the ion flight time is used to calculate the target voltage value, that is, the longer the ion flight time, the larger the operating voltage of the ion detector. In the above-described target voltage value calculation method, a varying voltage is applied to the ion detector according to the characteristics of the ions themselves, and the sensitivity of the mass spectrometer can be improved to the maximum extent.
In embodiments, the step of calculating the target voltage value that continuously changes within the preset ion flight time range by using the incremental voltage adjustment function comprises:
a linear incremental voltage adjustment function is employed to calculate a target voltage value that varies continuously over a preset ion flight time range, the linear incremental voltage adjustment function being a function of the operating voltage of the ion detector as a function of ion flight time, wherein the operating voltage of the ion detector increases linearly with increasing ion flight time.
The incremental linear voltage adjustment function is a function that the operating voltage of the ion detector depends on the ion flight time, that is, the linear incremental voltage adjustment function represents the corresponding relationship between the operating voltage of the ion detector and the ion flight time, wherein the operating voltage of the ion detector is a dependent variable, and the ion flight time is an independent variable.
The linear relation means that times function relation exists between the two variables, the voltage regulation function that the working voltage of the ion detector linearly increases along with the increase of the ion flight time means that the working voltage value of the ion detector linearly increases along with the increase of the ion flight time, and a linear calculation mode is adopted, so that the data processing in the calculation process is simple, and the working voltage of the ion detector can be quickly calculated.
In of these examples, the following linear incremental voltage adjustment functions were used to calculate a continuously varying target voltage value over a preset ion time-of-flight range;
Figure BDA0001513043190000071
wherein V represents a target voltage value, U represents a reference voltage value, W represents an operating voltage applied to the ion detector when the last ions arrive at the ion detector, t represents a variable of ion flight time, t represents a time of flight of the ions, andLrepresenting an initial time value, twRepresenting the time of arrival of the last ions at the ion detector.
Specifically, as shown in fig. 4, V represents the operating voltage of the ion detector (i.e., the target voltage at time t) when the ion flight time is t, the operating voltage of the ion detector is maintained at U, which is recorded as the reference voltage value, when the ions are generated, and the th ion has a flight time tLArriving at the ion detector, starting with the reference voltage value U, and generating the final ion arrival time (t) of ion packets with the ion flight time t as the variableL+tW) The operating voltage of the ion detector reaches a maximum value W. By adopting the calculation formula, the data processing in the calculation process is simple, and the working voltage of the ion detector can be quickly calculated.
In embodiments, as shown in fig. 5, in the step of calculating the target voltage value that continuously changes within the preset ion flight time range, the method further includes:
step S122, a nonlinear incremental voltage adjustment function is used to calculate a target voltage value that continuously changes within a preset ion flight time range, where the nonlinear incremental voltage adjustment function is a function of the operating voltage of the ion detector depending on the ion flight time, and the operating voltage of the ion detector increases nonlinearly with the increase of the ion flight time.
The nonlinear incremental voltage adjustment function is a function that the operating voltage of the ion detector depends on the ion flight time, namely the nonlinear incremental voltage adjustment function represents the corresponding relation between the operating voltage of the ion detector and the ion flight time, wherein the operating voltage of the ion detector is a dependent variable, and the ion flight time is an independent variable.
When the ions are detected by the mass spectrometer, the parameters of the mass spectrometer are more, the influence of test conditions and the like is less, and the possibility that the working voltage of the ion detector and the flight time of the ions change linearly is lower, so that in practical application, a nonlinear incremental voltage regulating function is adopted, namely a voltage regulating function that the working voltage of the ion detector increases nonlinearly along with the increase of the flight time of the ions is adopted to calculate a target voltage value (namely the working voltage of the ion detector) which continuously changes in a preset ion flight time range, namely the working voltage of the ion detector increases nonlinearly along with the increase of the flight time of the ions.
In embodiments, the step of calculating the target voltage value that continuously changes within the preset ion flight time range using the non-linear incremental voltage adjustment function comprises:
an th nonlinear incremental voltage adjustment function is used to calculate a continuously varying target voltage value over a preset ion time-of-flight range, the th nonlinear incremental voltage adjustment function being a function of the ion detector's operating voltage as a function of ion time-of-flight, wherein the ion detector's operating voltage increases in a curve with increasing ion time-of-flight.
Specifically, as shown in fig. 6, V represents the operating voltage of the ion detector (i.e., the target voltage at time t) when the ion flight time is t, the operating voltage of the ion detector is maintained at U, which is recorded as the reference voltage value, when ions are generated, and the th ion has a flight time tLArrive atAn ion detector, wherein the working voltage of the ion detector starts from a reference voltage value U, and reaches the final ion arrival time (t) generated by ion packets under the condition that the ion flight time t is taken as a variableL+tW) The operating voltage of the ion detector reaches a maximum value W. By adopting the calculation mode, the actual use condition of the mass spectrometer is comprehensively considered when the working voltage of the ion detector is calculated, the obtained result is more accurate, and the sensitivity of the ion detector can be improved to the greatest extent.
The user can obtain the corresponding relation between the sub-flight time and the working voltage of the ion detector, namely the voltage regulating function, by taking historical ion flight times and the working voltage value of the ion detector as training models.
In embodiments, the step of calculating the target voltage value continuously changing within the preset ion flight time range by using the non-linear incremental voltage adjustment function further comprises:
a second non-linear incremental voltage adjustment function is employed to calculate a target voltage value that varies continuously over a preset ion time-of-flight range, the second non-linear incremental voltage adjustment function being a function of the operating voltage of the ion detector in dependence on the ion time-of-flight, wherein the operating voltage of the ion detector increases exponentially or in steps with increasing ion time-of-flight.
Specifically, as shown in fig. 7, V represents the operating voltage of the ion detector (i.e., the target voltage at time t) when the ion flight time is t, and when the ions are generated, the operating voltage of the ion detector is maintained at U, which is recorded as the reference voltage value, and the th ion has elapsed flight time tLArriving at the ion detector, starting with the reference voltage value U, and generating the final ion arrival time (t) of ion packets with the ion flight time t as the variableL+tW) The operating voltage of the ion detector reaches a maximum value W. By adopting the calculation mode, the working electricity of the ion detector is calculatedThe actual use conditions of the mass spectrometer are comprehensively considered during pressing, the obtained result is more accurate, and the sensitivity of the ion detector can be improved to the greatest extent.
In addition, a voltage regulation function that the working voltage of the ion detector exponentially increases along with the increase of the ion flight time can be adopted to calculate the target voltage value which continuously changes in the preset ion flight time range
Fig. 8 is a schematic structural diagram of an embodiments of the apparatus for increasing mass sensitivity of the present invention, as shown in fig. 8, the apparatus for increasing mass sensitivity of the present invention includes:
the information acquisition module 10 is used for acquiring an initial time value of an th ion reaching the ion detector, a reference voltage value of the ion detector and a voltage adjusting function of the ion detector, wherein the voltage adjusting function is used for recording the corresponding relation of working voltage applied to the ion detector along with the change of ion flight time;
a target voltage value calculation module 20, configured to calculate a target voltage value that continuously changes within a preset ion flight time range according to the initial time value, the reference voltage value, and the voltage adjustment function;
and a target voltage value sending module 30, configured to send the target voltage value to a control circuit of the time-of-flight mass spectrometer, so that the control circuit adjusts an operating voltage applied to the ion detector according to the target voltage value, where the operating voltage applied to the ion detector is used to improve sensitivity of the mass spectrometer.
In embodiments, the method further comprises:
the target voltage value calculating module 20 is further configured to calculate a target voltage value that continuously changes within a preset ion flight time range using an incremental voltage adjustment function, where the incremental voltage adjustment function is a function of the operating voltage of the ion detector depending on the ion flight time, and the operating voltage of the ion detector increases with the increase of the ion flight time.
In embodiments, the apparatus for improving sensitivity of mass spectrometry further comprises:
the target voltage value calculating module 20 is further configured to calculate a target voltage value that continuously changes within a preset ion flight time range by using a linear incremental voltage adjustment function, where the linear incremental voltage adjustment function is a function of the operating voltage of the ion detector depending on the ion flight time, and the operating voltage of the ion detector linearly increases with the increase of the ion flight time.
In embodiments, the apparatus for improving sensitivity of mass spectrometry further comprises:
the target voltage value calculating module 20 is further configured to calculate a target voltage value that continuously changes within a preset ion flight time range by using the following linear incremental voltage adjustment function;
Figure BDA0001513043190000101
wherein V represents a target voltage value, U represents a reference voltage value, W represents an operating voltage applied to the ion detector when the last ions arrive at the ion detector, t represents a variable of ion flight time, t represents a time of flight of the ions, andLrepresenting an initial time value, twRepresenting the time of arrival of the last ions at the ion detector.
In embodiments, the apparatus for improving sensitivity of mass spectrometry further comprises:
the target voltage value calculating module 20 is further configured to calculate a target voltage value that continuously changes within a preset ion flight time range by using a nonlinear incremental voltage adjustment function, where the nonlinear incremental voltage adjustment function is a function of the ion detector operating voltage depending on the ion flight time, and the ion detector operating voltage nonlinearly increases with the increase of the ion flight time.
In embodiments, the apparatus for improving sensitivity of mass spectrometry further comprises:
the target voltage value calculating module 20 is further configured to calculate a target voltage value continuously varying within a preset ion flight time range using an th nonlinear incremental voltage adjustment function, wherein the th nonlinear incremental voltage adjustment function is a function of the operating voltage of the ion detector depending on the ion flight time, and the operating voltage of the ion detector increases in a curve with the increase of the ion flight time.
In embodiments, the method further comprises:
the target voltage value calculating module 20 is further configured to calculate a target voltage value that continuously changes within a preset ion flight time range by using a second nonlinear incremental voltage adjusting function, where the second nonlinear incremental voltage adjusting function is a function of the operating voltage of the ion detector depending on the ion flight time, and the operating voltage of the ion detector increases exponentially or in steps with the increase of the ion flight time.
The device for improving the sensitivity of the mass spectrum can execute the method for improving the sensitivity of the mass spectrum provided by the embodiment of the invention, and has corresponding functional modules and beneficial effects of the execution method. As for the processing methods executed by the functional modules, for example, the information obtaining module 10, the target voltage value calculating module 20, and the target voltage value sending module 30, reference may be made to the description in the foregoing method embodiments, and details are not repeated here.
According to the method and apparatus for improving sensitivity of mass spectrometry of the present invention, the present invention further provides computer devices, which are described in detail below with reference to the accompanying drawings and preferred embodiments.
Fig. 9 is a schematic structural diagram of embodiments of the computer device of the present invention, as shown in fig. 9, the computer device 900 in this embodiment includes a memory 901, a processor 902, and a computer program stored in the memory and running on the processor, wherein the processor executes the computer program to implement all the method steps in the method embodiment of the present invention.
The processor 902 in the computer device 900 can execute the method for improving the sensitivity of the mass spectrum provided by the embodiment of the invention, and has corresponding beneficial effects of the execution method. Reference may be made to the description of the above method embodiments, which are not repeated herein.
According to the method, the apparatus and the computer device for improving the sensitivity of mass spectrometry of the present invention, computer readable storage media are further provided, and the computer readable storage media of the present invention will be described in detail with reference to the accompanying drawings and the preferred embodiments.
A computer-readable storage medium in an embodiment of the invention, on which a computer program is stored which, when being executed by a processor, is able to carry out all the method steps in a method embodiment of the invention.
It will be understood by those skilled in the art that all or part of the processes of the methods of the embodiments described above may be implemented by hardware instructed by a computer program, which may be stored in computer readable storage medium, and when executed, the processes of the embodiments of the methods described above may be included.
The computer-readable storage medium is used for storing a program (instruction) of the method for improving the sensitivity of the mass spectrum provided by the embodiment of the invention, wherein the method for improving the sensitivity of the mass spectrum provided by the embodiment of the invention can be executed by executing the program, and the method has corresponding advantages. Reference may be made to the description of the above method embodiments, which are not repeated herein.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

  1. A method for improving sensitivity of mass spectrometry used for time-of-flight mass spectrometry, comprising the steps of:
    acquiring an th ion arrival time value at an ion detector, a reference voltage value of the ion detector and a voltage adjusting function of the ion detector, wherein the voltage adjusting function is used for recording the corresponding relation of working voltage applied to the ion detector along with the change of ion flight time;
    calculating a target voltage value which continuously changes in a preset ion flight time range according to the initial time value, the reference voltage value and the voltage regulation function, and sending the target voltage value to a control circuit of the flight time mass spectrum, so that the control circuit regulates working voltage applied to the ion detector according to the target voltage value, wherein the working voltage applied to the ion detector is used for improving the sensitivity of a mass spectrometer;
    the reference voltage value is the voltage applied to the ion detector before the th ion reaches the ion detector, and the ion detector is an MCP detector, an electron multiplication detector, a photomultiplier detector or a scintillation detector.
  2. 2. The method of claim 1, wherein the step of calculating the target voltage value that continuously varies within a predetermined ion time-of-flight range comprises:
    calculating a target voltage value that varies continuously over a preset ion time-of-flight range using an incremental voltage adjustment function that is a function of the operating voltage of the ion detector as a function of the ion time-of-flight, wherein the operating voltage of the ion detector increases as the ion time-of-flight increases.
  3. 3. The method of claim 2, wherein the step of using the incremental voltage adjustment function to calculate the target voltage value that varies continuously over the predetermined ion time of flight range comprises:
    calculating a continuously varying target voltage value over a preset ion time-of-flight range using a linear incremental voltage adjustment function that is a function of the operating voltage of the ion detector as a function of the ion time-of-flight, wherein the operating voltage of the ion detector increases linearly with increasing ion time-of-flight.
  4. 4. The method of improving sensitivity of mass spectrometry of claim 3, wherein the linear incremental voltage adjustment function is used to calculate a target voltage value that varies continuously over a preset ion time-of-flight range;
    Figure FDA0002128184340000021
    wherein V represents the target voltage value, U is the reference voltage value, W represents the operating voltage applied to the ion detector when the last ions arrive at the ion detector, t represents a variable of ion flight time, t represents a time of flight variable, andLrepresenting said initial time value, twRepresenting the time of arrival of the last ions at the ion detector.
  5. 5. The method of claim 2, wherein in the step of calculating the target voltage value that varies continuously over a predetermined ion time-of-flight range, the method further comprises:
    calculating a target voltage value that varies continuously over a preset ion time-of-flight range using a non-linear incremental voltage adjustment function that is a function of the operating voltage of the ion detector as a function of the ion time-of-flight, wherein the operating voltage of the ion detector increases non-linearly with increasing ion time-of-flight.
  6. 6. The method of claim 5, wherein the step of using the non-linear incremental voltage adjustment function to calculate the target voltage value that varies continuously over the predetermined ion time of flight comprises:
    calculating a continuously varying target voltage value over a preset ion time-of-flight range using an th non-linear incremental voltage adjustment function, the th non-linear incremental voltage adjustment function being a function of the ion detector's operating voltage as a function of the ion time-of-flight, wherein the ion detector's operating voltage increases in a curve as the ion time-of-flight increases.
  7. 7. The method of claim 5 or 6, wherein the step of calculating the target voltage value that continuously changes within the predetermined ion time-of-flight range using a non-linear incremental voltage adjustment function further comprises:
    calculating a continuously varying target voltage value over a preset ion time-of-flight range using a second non-linear incremental voltage adjustment function that is a function of the operating voltage of the ion detector in dependence on the ion time-of-flight, wherein the operating voltage of the ion detector increases exponentially or in steps as the ion time-of-flight increases.
  8. An apparatus for increasing sensitivity of mass spectrometry of the type 8, , comprising:
    the ion detector comprises an information acquisition module, a data acquisition module and a data processing module, wherein the information acquisition module is used for acquiring an initial time value of an th ion reaching the ion detector, a reference voltage value of the ion detector and a voltage regulation function of the ion detector, and the voltage regulation function is used for recording the corresponding relation of working voltage applied to the ion detector along with the change of ion flight time;
    the target voltage value calculating module is used for calculating a target voltage value which continuously changes within a preset ion flight time range according to the initial time value, the reference voltage value and the voltage regulating function;
    a target voltage value sending module, configured to send the target voltage value to a control circuit of the time-of-flight mass spectrometer, so that the control circuit adjusts an operating voltage applied to the ion detector according to the target voltage value, where the operating voltage applied to the ion detector is used to improve sensitivity of the mass spectrometer;
    the reference voltage value is the voltage applied to the ion detector before the th ion reaches the ion detector, and the ion detector is an MCP detector, an electron multiplication detector, a photomultiplier detector or a scintillation detector.
  9. Computer device of the kind 9, , comprising a memory, a processor and a computer program stored on the memory and executable on the processor, characterized in that the steps of the method of claims 1-7 are implemented when the processor executes the program.
  10. A computer storage medium , having a computer program stored thereon, characterized in that the program, when being executed by a processor, is adapted to carry out the steps of the method of claims 1-7.
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