Automatic tuning calibration method of quadrupole mass spectrometer
The automatic tuning and calibration method solves the problem of high calibration difficulty of quadrupole mass spectrometers, improves the ease of use and measurement accuracy of the instrument, and simplifies the operation process.
Patent Information
- Application Number
- CN202510902061.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-01
- Publication Date
- 2025-11-21
AI Technical Summary
The calibration of quadrupole mass spectrometers is difficult, which affects the instrument's precision and the accuracy of measurement data. New learners also have a long learning cycle, resulting in poor instrument usability.
An automatic tuning and calibration method is adopted. By introducing calibration standard samples into the mass spectrometer, acquiring ion mass spectrum peaks, optimizing the ion lens voltage and electron multiplier gain, automatically adjusting the parameters of ion mass-to-charge ratio, peak height and full width at half maximum, and outputting a tuning and calibration report.
Automatic calibration of the quadrupole mass spectrometer has been achieved, reducing the difficulty of use and improving the ease of use and measurement accuracy of the instrument.
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Figure CN120998769A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a mass spectrometry technique, in particular to an automatic tuning calibration method of a quadrupole mass spectrometer. BACKGROUND
[0002] The quadrupole mass spectrometer device has many control parameters, mainly including ion transmission lens voltage parameters of an ion source component, control parameters of mass accuracy and half-peak width of a mass analyzer part, and electron multiplier gain of an ion detector part. New students have great difficulty in tuning and calibrating the quadrupole mass spectrometer, and the learning period is long, which is not conducive to the use of the mass spectrometer. Moreover, improper calibration of the mass spectrometer can also cause instrument precision to decrease and measurement data to be inaccurate. SUMMARY
[0003] In order to solve the above problems in the prior art, the present application aims to provide an automatic tuning calibration method of a quadrupole mass spectrometer, which can automatically tune and calibrate the mass spectrometer and improve the ease of use of the mass spectrometer.
[0004] The technical scheme adopted by the present application to solve the technical problem is as follows: an automatic tuning calibration method of a quadrupole mass spectrometer, comprising the following steps,
[0005] calibration standards are introduced into the quadrupole mass spectrometer;
[0006] The control system of the quadrupole mass spectrometer collects ion mass spectrum peak graphs of the calibration standards, and obtains and records actual parameters of ion mass-to-charge ratios, peak heights, and half-peak widths according to the mass spectrum peak graphs;
[0007] The ion lens voltage of the calibration standards is optimized;
[0008] A tuning calibration report is output.
[0009] Optionally, before the calibration standards are introduced into the quadrupole mass spectrometer, the tuning parameters of ion mass-to-charge ratios, peak heights, and half-peak widths of the calibration standards are set.
[0010] Optionally, the ions of the calibration standards are divided into three categories according to the size of the mass-to-charge ratios, namely first characteristic ions, second characteristic ions, and third characteristic ions, and the mass-to-charge ratios of the first characteristic ions, the second characteristic ions, and the third characteristic ions increase in turn.
[0011] When the mass spectrum peak graphs are collected, the three types of characteristic ions are collected respectively.
[0012] Optionally, after the actual parameters of the peak heights are obtained, the tuning parameters of the peak heights are adjusted according to the size of the actual parameters.
[0013] When the maximum value of the peak height actual parameter is less than the lower limit value of the tuning parameter or greater than the upper limit value of the tuning parameter in the mass spectrometry peaks of the first characteristic ion, the second characteristic ion and the third characteristic ion, the electron multiplier is started to increase the gain so that the peak height actual parameter falls between the upper limit value and the lower limit value of the tuning parameter.
[0014] Optionally, after adjusting the tuning parameter of the post-peak height, the actual parameter of the ion mass-to-charge ratio is obtained, and the actual parameter of the ion mass-to-charge ratio is compared with the set tuning parameter of the ion mass-to-charge ratio to obtain the difference between the actual parameter and the tuning parameter of the ion mass-to-charge ratio;
[0015] When the difference is between -0.1 and 0.1, the tuning parameter of the current ion mass-to-charge ratio is saved.
[0016] Optionally, when the difference between the actual parameter and the tuning parameter of the ion mass-to-charge ratio is less than -0.1 or greater than 0.1, the tuning parameter of the peak height is adjusted again, and after the actual parameter of the peak height falls between the upper limit value and the lower limit value of the tuning parameter, the tuning parameter of the ion mass-to-charge ratio is adjusted again until the difference between the actual parameter and the tuning parameter is in the range of -0.1 to 0.1, and the adjusted tuning parameter of the ion mass-to-charge ratio is saved.
[0017] Optionally, after saving the ion mass-to-charge ratio tuning parameter, the actual parameter of the half-peak width is obtained, and the actual parameter of the half-peak width is compared with the set tuning parameter to obtain the difference between the actual parameter and the tuning parameter of the half-peak width;
[0018] When the difference is between -0.6 and 0.6, the tuning parameter of the current half-peak width is saved.
[0019] Optionally, when the difference between the actual parameter and the tuning parameter of the half-peak width is less than -0.6 or greater than 0.6, the tuning parameter of the half-peak width is compensated until the difference between the actual parameter and the tuning parameter of the half-peak width is in the range of -0.6 to 0.6, and the tuning parameter of the half-peak width after compensation is saved.
[0020] Optionally, the step of optimizing the ion lens voltage of the calibration standard sample is,
[0021] The first characteristic ion, the second characteristic ion and the third characteristic ion are selected as target characteristic ions.
[0022] The ion lens voltage of the target characteristic ion is scanned from low to high, the signal intensity of the target characteristic ion is recorded, and a relationship curve of the ion lens voltage and the signal intensity is outputted.
[0023] The voltage at the maximum signal intensity is selected as the optimized ion lens voltage.
[0024] Optionally, the ion lens voltage of the target characteristic ion comprises a repulsion electrode voltage, a focusing electrode voltage and an entrance voltage.
[0025] The repulsion electrode voltage is obtained by scanning the second characteristic ion, the focusing electrode voltage is obtained by scanning the first characteristic ion, and the entrance voltage is obtained by scanning the third characteristic ion.
[0026] By adopting the technical scheme, the quadrupole mass spectrometer can be automatically tuned and calibrated after being started, the use difficulty of the instrument is reduced, and the quadrupole mass spectrometer is conducive to popularization and application. BRIEF DESCRIPTION OF DRAWINGS
[0027] Figure 1 is a flowchart of the present application. DETAILED DESCRIPTION
[0028] The application will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the related application, and not to limit the application. In addition, it should be noted that only the parts related to the application are shown in the drawings for ease of description.
[0029] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict. The present application will be described in detail below with reference to the drawings and embodiments.
[0030] As shown in the drawings, Figure 1 The present application discloses an automatic tuning and calibration method of a quadrupole mass spectrometer, comprising the following steps,
[0031] S1, starting the quadrupole mass spectrometer, opening the standard sample valve, and introducing the calibration standard sample into the quadrupole mass spectrometer.
[0032] In the present application, the calibration standard sample can use a standard sample with multiple mass-to-charge ratios, for example, perfluorotributylamine, which has 17 mass-to-charge ratios. In an embodiment of the present application, the ion with a mass-to-charge ratio of 69 is selected as a low mass characteristic ion, the ion with a mass-to-charge ratio of 219 is selected as a medium mass characteristic ion, and the ion with a mass-to-charge ratio of 502 is selected as a high mass characteristic ion.
[0033] S2, the control system of the quadrupole mass spectrometer collects the ion mass spectrum peak graph of the calibration standard sample, and obtains and records the actual parameters of ion mass-to-charge ratio, peak height and half-peak width according to the mass spectrum peak graph. Wherein, before collecting the mass spectrum peak graph of the target characteristic ion, the tuning parameters to be calibrated are set in the control system.
[0034] First, the mass spectrum peak graphs of the three characteristic ions of the calibration standard sample are collected respectively;
[0035] Secondly, the actual parameters of the three characteristic ions are obtained by scanning the mass spectrum peak data, and the actual parameters are compared with the calibrated tuning parameters, and finally the calibrated tuning parameters are obtained.
[0036] In specific embodiments of the application, the low mass characteristic ion is defined as the first characteristic ion, the medium mass characteristic ion is defined as the second characteristic ion, and the high mass characteristic ion is defined as the third characteristic ion. When calibrating the tuning parameters, the first characteristic ion, the second characteristic ion and the third characteristic ion are calibrated in turn, respectively, and after all three characteristic ions are calibrated and qualified, the next step is entered.
[0037] Specifically, when calibrating the tuning parameters, each tuning parameter needs to be calibrated in turn according to the order.
[0038] S21, first calibrate the tuning parameter of peak height.
[0039] When calibrating the tuning parameter of peak height, the first characteristic ion and the one with the largest peak height actual parameter among the second characteristic ion and the third characteristic ion are selected as the calibration reference, for example, by judging the mass spectrum peak map that the peak height of the first characteristic ion is the largest, and the peak height actual parameter of the first characteristic ion is used to calibrate the peak height tuning parameters of the three characteristic ions. When the maximum value of the peak height actual parameter is less than the lower limit value of the tuning parameter or greater than the upper limit value of the tuning parameter, the electron multiplier is started to increase the gain, so that the peak height actual parameter falls between the upper limit value and the lower limit value of the tuning parameter, for example, the lower limit value of the peak height tuning parameter is 900000, and the upper limit value is 1000000, when the peak height actual parameter does not fall between 900000~1000000, the upper limit value or the lower limit value of the peak height tuning parameter is adjusted by starting the electron multiplier, so that the peak height actual parameter falls between the upper limit value and the lower limit value.
[0040] S22, after calibrating the peak height tuning parameter, the mass-to-charge ratios of the three characteristic ions are calibrated in turn. The control system obtains the actual parameters of the ion mass-to-charge ratio, and compares the actual parameters of the ion mass-to-charge ratio with the set ion mass-to-charge ratio tuning parameters, to obtain the difference between the actual parameters and the tuning parameters of the ion mass-to-charge ratio. When the difference is between -0.1 and 0.1, save the tuning parameters of the current ion mass, and when the difference does not fall between -0.1 and 0.1, the tuning parameter m_b needs to be compensated, and the compensation is △m_b,
[0041] Wherein, △m_b=(m0-m1) / K m .
[0042] In the above formula, m1 is the tuning parameter of the current mass-to-charge ratio, m0 is the actual parameter of the mass-to-charge ratio, K m is the sensitivity coefficient of the mass-to-charge ratio tuning parameter to the mass axis, which is obtained by the following formula.
[0043] K m = mass axis change amount ÷ mass-to-charge ratio tuning parameter change amount.
[0044] When the K m coefficient and the actual deviation are large, the compensated tuning parameter still does not meet the requirements, and the above steps need to be repeated multiple times until the difference between the actual parameter and the tuning parameter is between -0.1 and 0.1.
[0045] S23, after the peak height and ion mass-to-charge ratio tuning parameters are calibrated, the tuning parameter of the half-peak width is calibrated.
[0046] The control system obtains the actual parameter of the half-peak width, and compares the actual parameter of the half-peak width with the set tuning parameter to obtain the difference between the actual parameter of the half-peak width and the tuning parameter. When the difference is between -0.6 and 0.6, the current tuning parameter of the half-peak width is saved, and when the difference between the actual parameter of the half-peak width and the tuning parameter is less than -0.6 or greater than 0.6, the tuning parameter pw_b of the half-peak width is compensated, and the compensation amount is △pw_b,
[0047] wherein, △pw_b= (pw0-pw1) / Kpw m .
[0048] In the above formula, pw1 is the current tuning parameter of the half-peak width, pw0 is the actual parameter of the half-peak width, Kpw m is the sensitivity coefficient of the tuning parameter of the half-peak width to the mass axis, which is obtained by the following formula.
[0049] Kpw m = mass axis change amount ÷ half-peak width tuning parameter change amount.
[0050] When the Kpw m coefficient and the actual deviation are large, the compensated tuning parameter still does not meet the requirements, and the above steps need to be repeated multiple times until the difference between the actual parameter and the tuning parameter is between -0.6 and 0.6.
[0051] S3, optimizing the ion lens voltage of the target characteristic ion.
[0052] The steps of optimizing the ion lens voltage of the target characteristic ion are,
[0053] S31, selecting a target characteristic ion.
[0054] When optimizing the ion lens voltage, only one ion can be selected for optimization each time, and after the ion is optimized, the remaining ions are optimized in turn.
[0055] S32, scan the ion lens voltage of the target characteristic ion from low to high, record the signal intensity of the target characteristic ion, and output the relationship curve between the ion lens voltage and the signal intensity of the target characteristic ion.
[0056] S33, select the voltage at the maximum signal intensity as the optimized lens voltage.
[0057] The ion lens voltage of the target characteristic ion includes a repelling electrode voltage, a focusing electrode voltage, and an entrance voltage, wherein the repelling electrode voltage is obtained by scanning the second characteristic ion, the focusing electrode voltage is obtained by scanning the first characteristic ion, and the entrance voltage is obtained by scanning the third characteristic ion.
[0058] S4, output a tuning calibration report.
[0059] After the calibration is completed, the adjusted tuning parameters and ion lens voltage parameters are saved, and a tuning report is output, and the tuning report content includes tuning parameter values, characteristic ion mass spectrum profile graphs, and calibration standard sample full spectrum graphs.
[0060] The automatic tuning is completed after the tuning report is output.
[0061] The above description is only the preferred embodiment of the present application and the explanation of the applied technical principles. Those skilled in the art should understand that the scope of the invention involved in the present application is not limited to the technical solutions formed by the specific combination of the above technical features, and should also cover other technical solutions formed by any combination of the above technical features or their equivalent features without departing from the inventive concept. For example, the above features can be replaced with the technical features disclosed in the present application (but not limited to) having similar functions to form technical solutions.
[0062] In addition to the technical features described in the specification, the remaining technical features are known to those skilled in the art, and in order to highlight the innovative features of the present application, the remaining technical features will not be described here.
Claims
1. A method of automatic tuning calibration of a quadrupole mass spectrometer, characterized by, The method comprises the following steps, a calibration sample is introduced into a quadrupole mass spectrometer; a control system of the quadrupole mass spectrometer collects an ion mass spectrum peak diagram of the calibration sample, and obtains and records actual parameters of ion mass-to-charge ratio, peak height and half-height peak width according to the mass spectrum peak diagram; ion lens voltage of the calibration sample is optimized; a tuning calibration report is output.
2. The method of automatic tuning calibration of a quadrupole mass spectrometer of claim 1, wherein, Before the calibration sample is introduced into the quadrupole mass spectrometer, tuning parameters of ion mass-to-charge ratio, peak height and half-height peak width of the calibration sample are set.
3. The method of automatic tuning calibration of a quadrupole mass spectrometer of claim 2, wherein, The ions of the calibration sample are divided into three categories according to the size of the mass-to-charge ratio, namely first characteristic ions, second characteristic ions and third characteristic ions, and the mass-to-charge ratios of the first characteristic ions, the second characteristic ions and the third characteristic ions increase in turn; When the mass spectrum peak diagram is collected, the three types of characteristic ions are collected respectively.
4. The method of automatic tuning calibration of a quadrupole mass spectrometer of claim 3, wherein, After the actual parameters of the peak height are obtained, the tuning parameters of the peak height are adjusted according to the size of the actual parameters; When the maximum value of the actual parameters of the peak height is less than the lower limit value of the tuning parameters or greater than the upper limit value of the tuning parameters in the mass spectrum peaks of the first characteristic ions, the second characteristic ions and the third characteristic ions, the electron multiplier is started to increase the gain, so that the actual parameters of the peak height fall between the upper limit value and the lower limit value of the tuning parameters.
5. The method of automatic tuning calibration of a quadrupole mass spectrometer of claim 4, wherein, After the tuning parameters of the peak height are adjusted, the actual parameters of the ion mass-to-charge ratio are obtained, and the actual parameters of the ion mass-to-charge ratio are compared with the set tuning parameters of the ion mass-to-charge ratio to obtain the difference between the actual parameters and the tuning parameters of the ion mass-to-charge ratio; When the difference is between -0.1 and 0.1, the tuning parameters of the current ion mass-to-charge ratio are saved.
6. The method of automatic tuning calibration of a quadrupole mass spectrometer of claim 5, wherein, When the difference between the actual parameters and the tuning parameters of the ion mass-to-charge ratio is less than -0.1 or greater than 0.1, the tuning parameters of the peak height are adjusted again, and after the actual parameters of the peak height fall between the upper limit value and the lower limit value of the tuning parameters, the tuning parameters of the ion mass-to-charge ratio are adjusted again until the difference between the actual parameters and the tuning parameters is in the range of -0.1 to 0.1, and the tuning parameters of the ion mass-to-charge ratio after adjustment are saved.
7. The method of automatic tuning calibration of a quadrupole mass spectrometer of claim 6, wherein, After the tuning parameters of the ion mass-to-charge ratio are saved, the actual parameters of the half-height peak width are obtained, and the actual parameters of the half-height peak width are compared with the set tuning parameters to obtain the difference between the actual parameters and the tuning parameters of the half-height peak width; When the difference is between -0.6 and 0.6, the tuning parameters of the current half-height peak width are saved.
8. The method of automatic tuning calibration of a quadrupole mass spectrometer of claim 7, wherein, When the difference between the actual parameters and the tuning parameters of the half-height peak width is less than -0.6 or greater than 0.6, the tuning parameters of the half-height peak width are compensated until the difference between the actual parameters and the tuning parameters of the half-height peak width is in the range of -0.6 to 0.6, and the tuning parameters of the half-height peak width after compensation are saved.
9. The method of automatic tuning calibration of a quadrupole mass spectrometer of claim 8, wherein, The steps for optimizing the ion lens voltage of the calibration sample are as follows, a target characteristic ion is selected from the first characteristic ion, the second characteristic ion and the third characteristic ion; the ion lens voltage of the target characteristic ion is scanned from low to high, the signal intensity of the target characteristic ion is recorded, and a relationship curve of the ion lens voltage and the signal intensity is output; the voltage at the maximum signal intensity is selected as the optimized ion lens voltage.
10. The method of automatic tuning calibration of a quadrupole mass spectrometer of claim 9, wherein, The ion lens voltage of the target characteristic ion includes repulsion electrode voltage, focusing electrode voltage and inlet voltage; Wherein the repeller voltage is obtained by scanning the second characteristic ion, the focusing voltage is obtained by scanning the first characteristic ion, and the entrance voltage is obtained by scanning the third characteristic ion.