CN116660358B - High-resolution time-of-flight mass spectrum detection method - Google Patents
High-resolution time-of-flight mass spectrum detection method Download PDFInfo
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- 238000001196 time-of-flight mass spectrum Methods 0.000 title claims abstract description 18
- 238000001514 detection method Methods 0.000 title abstract description 14
- 238000012360 testing method Methods 0.000 claims abstract description 115
- 238000001819 mass spectrum Methods 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000001269 time-of-flight mass spectrometry Methods 0.000 claims abstract description 21
- 239000000523 sample Substances 0.000 claims description 33
- 238000000605 extraction Methods 0.000 claims description 24
- 239000013074 reference sample Substances 0.000 claims description 5
- 238000013102 re-test Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 32
- 230000008569 process Effects 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 5
- 238000004949 mass spectrometry Methods 0.000 abstract 1
- 238000004364 calculation method Methods 0.000 description 6
- 230000001133 acceleration Effects 0.000 description 5
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002773 nucleotide Substances 0.000 description 2
- 125000003729 nucleotide group Chemical group 0.000 description 2
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- 230000006978 adaptation Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 230000000750 progressive effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
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- G—PHYSICS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a high-resolution time-of-flight mass spectrometry detection method, which relates to the field of mass spectrometry detection, wherein the method comprises the following steps: according to each group of parameters in the time-of-flight mass spectrum system, testing the reference to obtain the optimal parameters of each section of mass range corresponding to the reference; detecting the reference products according to the optimal parameters to obtain conversion functions corresponding to the mass ranges of each section; according to the optimal parameters, testing the sample to be detected, and obtaining mass spectrum data corresponding to each section of mass range by utilizing a conversion function; and splicing the mass spectrum data to obtain a high-resolution mass spectrum. The invention has simple realization process, does not need to change hardware configuration, and can test ions in each mass range interval by adopting more proper parameters after parameter adjustment, thereby avoiding the mass bias, improving the mass resolution of each mass range interval and improving the resolution of a linear flight time mass spectrum system.
Description
Technical Field
The invention relates to the field of mass spectrum detection, in particular to a high-resolution time-of-flight mass spectrum detection method.
Background
Many factors that contribute to mass bias in conventional time-of-flight mass spectrometer designs, with large differences in resolution, sensitivity across different mass intervals. For example, MALDI-TOF (matrix assisted laser Desorption ionization time of flight) mass spectrometers which take nucleotide molecules as objects to be detected in the market at present generally have mass ranges of 4000-10000, and parameters are not changed in calibration and test links after the instruments leave the factory. Since the same setting parameters are used in the full mass range, the minimum value of the mass resolution of the full mass range is generally not more than 1000, molecules with the difference of less than 10Da are difficult to stably distinguish, and errors are easy to cause.
Disclosure of Invention
The invention aims to provide a high-resolution time-of-flight mass spectrum detection method, which has the advantages that the implementation process is simple, the hardware configuration is not required to be changed, after parameter adjustment is carried out, ions in each mass range interval can be tested by adopting more proper parameters, the mass resolution of each mass range interval is improved, and meanwhile, the resolution of a linear time-of-flight mass spectrum system is also improved.
According to one aspect of the present invention, there is provided a method of high resolution time-of-flight mass spectrometry comprising:
according to each group of parameters in the time-of-flight mass spectrum system, testing a reference to obtain optimal parameters of each section of mass range corresponding to the reference;
detecting the reference product according to the optimal parameters to obtain conversion functions corresponding to the mass ranges of the sections;
according to the optimal parameters, testing a sample to be detected, and obtaining mass spectrum data corresponding to each section of mass range by utilizing the conversion function;
and splicing the mass spectrum data to obtain a high-resolution mass spectrum.
Optionally, the testing the reference according to each set of parameters in the time-of-flight mass spectrometry system to obtain the optimal parameters corresponding to each section of mass range of the reference, includes:
according to the parameters of each group, the reference product is tested respectively, and a test result of the reference product in the mass range of each section is obtained; wherein the test result comprises resolution and signal strength, and each segment of mass range comprises at least two mass ranges;
determining whether a value of the test result corresponding to the reference exceeds a preset threshold;
if the preset threshold value is exceeded, determining a parameter corresponding to the resolution of the maximum value in the test result, and setting the parameter as an optimal parameter of a quality range corresponding to the reference;
and if the quality range of the reference object does not exceed the preset threshold, adjusting the parameters of each group, and testing the reference object again to obtain a test result of the reference object in the quality range of each section until the test result exceeds the preset threshold.
Optionally, the testing the reference according to each set of parameters in the time-of-flight mass spectrometry system to obtain optimal parameters corresponding to each section of mass range of the reference, and further includes:
obtaining test parameters corresponding to the reference according to the parameters of the reference;
and testing the reference according to the test parameters to obtain the resolution of the reference in the corresponding quality range, and setting the parameter corresponding to the resolution with the maximum value as the optimal parameter of the quality range corresponding to the reference.
Optionally, the reference is tested according to each set of parameters, so as to obtain a test result of the reference in each section of mass range, wherein each set of parameters comprises a lead-out voltage, a delay time, a focusing voltage, a laser gain and a detector gain.
Optionally, the adjusting the parameters of each group, and testing the reference article again to obtain a test result of the reference article in each section of the mass range, until the test result exceeds the preset threshold value, including:
adjusting the numerical value of the extraction voltage to obtain a new extraction voltage;
according to the new extraction voltage, adjusting the delay time according to a preset interval to obtain each new delay time;
and respectively testing the reference according to the new delay time to obtain a test result of the reference in the mass range of each section until the test result exceeds the preset threshold value.
Optionally, the detecting the reference according to the optimal parameter to obtain a conversion function corresponding to each segment of the mass range includes:
detecting the reference products according to the optimal parameters to obtain flight time data;
and obtaining a conversion function corresponding to each section of mass range according to the flight time data and the mass-to-charge ratio of the reference.
Optionally, the testing the sample to be detected according to the optimal parameter, and obtaining mass spectrum data corresponding to the mass range of each segment by using the conversion function includes:
determining an optimal parameter corresponding to the sample according to the mass-to-charge ratio of the sample to be detected;
testing the sample according to the optimal parameters to obtain flight time data;
and obtaining mass spectrum data corresponding to each section of mass range by utilizing the conversion function according to the flight time data.
Optionally, the testing the reference product to obtain the optimal parameters of the mass ranges of each segment corresponding to the reference product, further includes:
testing the samples to obtain mass-to-charge ratios of each group of samples in the samples;
obtaining optimal parameters corresponding to the groups of samples according to the mass-to-charge ratios of the groups of samples;
correspondingly, according to the optimal parameters, the reference products are detected respectively to obtain conversion functions corresponding to the mass ranges of each section, and the method comprises the following steps:
detecting the reference products according to the optimal parameters corresponding to the groups of samples to obtain corresponding conversion functions;
correspondingly, the testing the sample to be detected according to the optimal parameters, and obtaining mass spectrum data corresponding to the mass range of each section by utilizing the conversion function comprises the following steps:
testing the samples according to the optimal parameters, and obtaining high-resolution mass spectrum data of each group of samples by utilizing the conversion function;
correspondingly, the splicing the mass spectrum data to obtain a high-resolution mass spectrum comprises the following steps:
and splicing the high-resolution mass spectrum data to obtain a mass spectrum.
Optionally, the testing the sample to obtain mass-to-charge ratios of each group of samples in the sample includes:
and testing the samples according to a single parameter method to obtain the mass-to-charge ratios of the groups of samples in the samples.
Optionally, the mass spectrum data are spliced to obtain a high-resolution mass spectrum, wherein an abscissa of the mass spectrum is a mass-to-charge ratio of the sample, and an ordinate of the mass spectrum is a signal intensity corresponding to the mass-to-charge ratio.
Therefore, the invention has simple implementation process, does not need to change hardware configuration, and can test ions in each mass range interval by adopting more proper parameters after parameter adjustment, thereby improving the mass resolution of each mass range interval and improving the resolution of the linear time-of-flight mass spectrum system.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for detecting a high resolution time-of-flight mass spectrum according to an embodiment of the present invention;
FIG. 2 is a flow chart of another method for detecting high resolution time-of-flight mass spectrometry according to an embodiment of the present invention;
FIG. 3 is an exemplary diagram of a specific scaling function provided by an embodiment of the present invention;
fig. 4 is an exemplary diagram of a specific high resolution mass spectrum according to an embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Many factors that contribute to mass bias in conventional time-of-flight mass spectrometer designs, with large differences in resolution, sensitivity across different mass intervals. For example, MALDI-TOF (matrix assisted laser Desorption ionization time of flight) mass spectrometers which take nucleotide molecules as objects to be detected in the market at present generally have mass ranges of 4000-10000, and parameters are not changed in calibration and test links after the instruments leave the factory. Since the same setting parameters are used in the full mass range, the minimum value of the mass resolution of the full mass range is generally not more than 1000, molecules with the difference of less than 10Da are difficult to stably distinguish, and errors are easy to cause.
In view of this, the invention provides a method for detecting high-resolution time-of-flight mass spectrum, which has simple implementation process, does not need to change hardware configuration, and enables ions in each mass range interval to be tested by adopting more proper parameters after parameter adjustment, thereby improving the mass resolution of each mass range interval and improving the resolution of a linear time-of-flight mass spectrum system.
Referring to fig. 1, fig. 1 is a flowchart of a high-resolution time-of-flight mass spectrometry detection method according to an embodiment of the present invention, and the high-resolution time-of-flight mass spectrometry detection method according to the embodiment of the present invention may include:
step S101: and testing the reference according to each group of parameters in the time-of-flight mass spectrum system to obtain the optimal parameters of each section of mass range corresponding to the reference.
In the embodiment of the invention, the flight time mass spectrum system is a classical linear flight time mass spectrum theoretical model, a double-field acceleration technology and a delay extraction technology are applied, the duration time of the ions with different initial speeds being accelerated is changed through delay high-voltage pulse, and finally all the ions almost reach the detector at the same time.
In the embodiment of the present invention, each mass range of each segment includes at least two mass ranges, and each mass range may be obtained by dividing a full mass range, and it should be noted that the dividing manner is not limited in the embodiment of the present invention, and the mass ranges may be uniformly divided according to a preset value, or may be randomly divided, where the full mass range is a range including mass-to-charge ratios of most of actual ions. It should be noted that, in the embodiment of the present invention, the reference sample is a sample containing different mass-to-charge ratios, where the mass-to-charge ratio of the reference sample may be selected according to the mass range of each segment. For example, the full mass range can be set to be a range of 4000 to 10000 mass-to-charge ratios, and then the range is divided according to a value of 2000, so that three mass ranges of 4000 to 6000, 6000 to 8000 and 8000 to 10000 are obtained, and then samples with three mass-to-charge ratios of low, medium and high can be selected from corresponding reference products, and specific mass-to-charge ratios can be 5000, 7000 and 9000.
According to the embodiment of the invention, the reference can be tested according to each group of parameters in the time-of-flight mass spectrometry system to respectively obtain the optimal parameters corresponding to each section of mass range of the reference, the reference can be tested according to each group of parameters to respectively obtain the test result of the reference in each section of mass range, then whether the test result corresponding to the reference exceeds a preset threshold value is determined, if the test result exceeds the preset threshold value, the parameter corresponding to the resolution of the maximum value in the test result is determined, the parameter is set as the optimal parameter corresponding to the mass range of the reference, if the parameter does not exceed the preset threshold value, each group of parameters is adjusted, and the reference is tested again to obtain the test result of the reference in each section of mass range until the test result exceeds the preset threshold value. The test result includes resolution and signal strength, and in the parameter determination process, the resolution may be determined whether the signal strength exceeds a preset threshold value and the resolution is the resolution with the maximum value, which is not limited. The parameters of each group can comprise extraction voltage, delay time, focusing voltage, laser gain, detector gain and the like, wherein the delay time is the time difference between the ion generation time and the time when the extraction voltage is applied, the extraction voltage is the voltage difference of the first accelerating field, and the extraction voltage can be obtained by subtracting the voltage of the first layer of ion network from the initial voltage. For example, the initial voltage (u0) u0=20 kV, the voltage (u1) u1=17.5 kV of the first layer ion network, and the extraction voltage (Ua) ua=u0-u1=2.5 kV. The signal intensity in the test result is the ion quantity corresponding to the mass-to-charge ratio, the value of the signal intensity is influenced by the extraction voltage, the delay time, the focusing voltage, the laser gain and the detector gain parameters, the value of the resolution is influenced by the extraction voltage, the delay time and the focusing voltage parameters, the corresponding relation between the resolution and the delay time can be represented by a peak graph, wherein the resolution of the maximum value is equivalent to the parameter corresponding to the mountain peak in the acquired peak graph and is set as the optimal parameter. The setting of the preset threshold is not limited in the embodiment of the invention, and the preset threshold can be preset for a designer or can be set according to actual use conditions.
It should be noted that in the embodiment of the present invention, the reference may be tested according to each set of parameters, so as to obtain a test result of the reference in each section of quality range, and the delay time may be adjusted only according to a preset interval based on the condition that the extraction voltage and the focusing voltage are unchanged, so as to obtain each new delay time, and then the reference may be tested according to each new delay time, so as to obtain a test result of the reference in each section of quality range. When the test result exceeding the preset threshold value does not exist, each group of parameters can be adjusted, the reference products are tested again, and the test result of the reference products in each section of quality range is obtained until the test result exceeds the preset threshold value. Specifically, the value of the extraction voltage can be adjusted to obtain a new extraction voltage, then the delay time is adjusted according to a preset interval according to the new extraction voltage to obtain each new delay time, and the reference is tested according to each new delay time to obtain the test result of the reference in each section of quality range until the test result exceeds a preset threshold value. For example, the reference may be used to perform a test according to an initial selection of the lead-out voltage (Ua), the delay time (Δt) and the focusing voltage (U3), where the reference includes samples a, b and c with low, medium and high mass-to-charge ratios, the Δt is gradually increased to repeat the test, the test result of each time is recorded, the test result of the sample b with medium mass-to-charge ratio with signal strength exceeding a preset threshold and resolution being the maximum value is selected, the corresponding parameter is used as the reference result, the reference result is set as the optimal parameter of the group, if there is no corresponding reference result, the Ua is increased, the above-mentioned steps of adjusting Δt are repeated until the test result exceeds the preset threshold, the test result with resolution being the maximum value is set as the reference result, the reference result is set as the optimal parameter of the group, the optimal parameters of the mass ranges corresponding to the samples a and c can be obtained according to the same method and recorded as Pa and Pc.
It should be noted that, in the embodiment of the present invention, based on the obtaining of the optimal parameter in a certain quality range by the above manner, the test parameter corresponding to the reference may be obtained according to the parameter of the reference, then the reference is tested according to the test parameter to obtain the resolution of the reference in the corresponding quality range, and the parameter corresponding to the resolution of the maximum value is set as the optimal parameter in the quality range corresponding to the reference. The test parameters may include parameters such as extraction voltage, delay time, focus voltage, laser gain, and detector gain. Wherein, the test parameters corresponding to the reference can be estimated according to a theoretical formula under ideal conditions, and the theoretical formula is as follows:
wherein Deltat is delay time, da is extraction distance, y is partial pressure ratioD is the field-free flight distance,is a coefficient related to the extraction distance, the partial pressure ratio, the secondary acceleration distance, and the field-free flight distance. It should be noted that the calculation formula can be used to obtain the +.>The calculation formula is as follows:
it should be noted that in the above formula,the ion with initial speed of 0, absolute mass of m and charge amount of z is expressed, and the theoretical final speed reached under the action of accelerating voltage (V) is an intermediate variable introduced by a theoretical formula for convenience of expression. Where V is the total acceleration voltage, m is the absolute mass of the ion, and z is the charge of the ion. In the following, a specific example will be described, for example, when the total acceleration voltage is 20kV, the mass number is 7000, and the charge number is 1, the theoretical terminal velocity shown in the following table is obtained, where the absolute mass is the mass number multiplied by the coefficient thereof, and the charge amount is the charge number multiplied by the coefficient thereof:
calculation example table
It should be noted that, the above theoretical formula represents ions with different mass-to-charge ratios, their optimal Δt is approximately proportional to the square root of the mass-to-charge ratio, the optimal delay time corresponding to the reference can be estimated by using the theoretical formula according to the parameters of the reference, then each delay time is obtained based on the optimal delay time, the reference is tested according to each delay time, the resolution of the reference in the corresponding mass range is obtained, and the parameter corresponding to the resolution of the maximum value is set as the optimal parameter corresponding to the mass range of the reference. Specifically, for example, the lead-out voltage (Ua), the delay time (Δt) and the focusing voltage (U3) may be initially selected according to experience, the reference is used to perform a test, where the reference includes samples a, b and c with low, medium and high mass-to-charge ratios, the Δt is gradually increased to repeat the test, each test result is recorded, a test result with the resolution of the sample b with medium mass-to-charge ratio exceeding a preset threshold is selected, the corresponding parameter is used as a parameter adjustment result, if the corresponding parameter adjustment result does not exist, ua is increased, the above-mentioned step of adjusting Δt is repeated until the resolution exceeds the preset threshold, the parameter adjustment result is the set of optimal parameters, and may be denoted as Pb, after Pb is obtained, the optimal delay times corresponding to the samples a and c are calculated by using a theoretical formula, then each delay time is obtained based on the optimal delay time, the samples a and c are tested according to each delay time, the resolution of the corresponding mass range is obtained, and the parameter corresponding to the resolution of the maximum value is set as the optimal parameter corresponding to the mass range of the samples a and c, and Pa is recorded as the optimal parameter corresponding to the mass range of the samples a and Pc.
According to the embodiment of the invention, the reference can be tested according to each group of parameters in the time-of-flight mass spectrum system, so that the optimal parameters of each section of mass range corresponding to the reference are respectively obtained, the ions in each section of mass range can adopt more proper parameters, and the mass resolution of most sections is improved.
Step S102: and detecting the reference products according to the optimal parameters to obtain conversion functions corresponding to the mass ranges of each section.
The conversion function in the embodiment of the invention is a time-mass conversion function, so that the conversion of the flight time into the mass-to-charge ratio can be realized, and the mass spectrogram related to the mass-to-charge ratio can be conveniently obtained later, wherein the mass-to-charge ratio is equal to the mass number under the condition that the charge number is 1.
According to the embodiment of the invention, the reference can be detected according to the optimal parameters to obtain the conversion function corresponding to each section of mass range, the reference can be detected according to the optimal parameters to obtain the flight time data, and the conversion function corresponding to each section of mass range can be obtained according to the flight time data and the mass-to-charge ratio of the reference. Specifically, the flight time data and the mass-to-charge ratio are substituted into a formula to obtain a corresponding conversion function, wherein the formula is as follows:
wherein A, B and C are coefficients to be solved, t is flight time, and m is mass-to-charge ratio. For example, if there are samples a, b and c with low, medium and high mass-to-charge ratios in the reference, the reference may be checked by using three optimal parameters Pa, pb and Pc to obtain time-of-flight data 1, 2 and 3, and then calculated according to the mass-to-charge ratios of a, b and c and the time-of-flight data 1, 2 and 3 by using the above formulas to obtain conversion functions Fa, fb and Fc, respectively.
Step S103: and testing the sample to be detected according to the optimal parameters, and obtaining mass spectrum data corresponding to each section of mass range by utilizing a conversion function.
Step S104: and splicing the mass spectrum data to obtain a high-resolution mass spectrum.
According to the embodiment of the invention, the sample to be detected can be tested according to the optimal parameters, the mass spectrum data corresponding to each section of mass range can be obtained by utilizing the conversion function, the optimal parameters corresponding to the sample can be determined according to the mass-to-charge ratio of the sample to be detected, then the sample is tested according to the optimal parameters to obtain the flight time data, and finally the mass spectrum data corresponding to each section of mass range can be obtained by utilizing the conversion function according to the flight time data. In the embodiment of the invention, each mass spectrum data can be spliced to obtain a high-resolution mass spectrum, wherein the abscissa of the mass spectrum is the mass-to-charge ratio of the sample, and the ordinate is the signal intensity corresponding to the mass-to-charge ratio.
It should be noted that in the embodiment of the present invention, samples may be tested first to obtain mass-to-charge ratios of each group of samples, then according to the mass-to-charge ratios of each group of samples, optimal parameters corresponding to each group of samples are obtained, and according to the optimal parameters corresponding to each group of samples, reference samples are detected respectively to obtain corresponding conversion functions, finally according to the optimal parameters, samples are tested, and high-resolution mass spectrum data of each group of samples are obtained by using the conversion functions, and also high-resolution mass spectrum data may be spliced to obtain a high-resolution mass spectrum. The method for testing is not limited, and the samples can be tested according to a single parameter method to obtain the mass-to-charge ratio of each group of samples, or the samples can be tested according to a multi-parameter method to obtain the mass-to-charge ratio of each group of samples, wherein the samples can be divided to obtain each group of samples.
Compared with a mode of obtaining mass spectrum data by single parameter test, the method and the device for obtaining mass spectrum data in the embodiment of the invention utilize optimal parameters to test the sample to be detected, utilize conversion functions to obtain mass spectrum data corresponding to each section of mass range, splice each mass spectrum data to obtain a mass spectrum, and improve the resolution of a linear flight time mass spectrum system.
Based on the above embodiments, the embodiment of the present invention provides a method for detecting a high-resolution time-of-flight mass spectrum, which has a simple implementation process, does not need to change hardware configuration, and enables ions in each mass range interval to be tested by adopting more appropriate parameters after parameter adjustment, thereby improving the mass resolution of each mass range interval and improving the resolution of a linear time-of-flight mass spectrum system.
Based on the above embodiments, the present invention further provides a flowchart of another high-resolution time-of-flight mass spectrometry detection method, please refer to fig. 2, fig. 2 is a flowchart of another high-resolution time-of-flight mass spectrometry detection method provided by the present invention, which may be that samples are tested first to obtain mass-to-charge ratios of each group of samples in the samples, and then one or more groups of samples of different groups of samples are selected for secondary testing, which may include:
step S201: and testing the samples to obtain the mass-to-charge ratios of the samples in each group.
In the embodiment of the invention, the samples can be tested to obtain the mass-to-charge ratios of the samples in each group, and the samples can be tested according to a single-parameter method or a multi-parameter method to obtain the mass-to-charge ratios and low-resolution mass spectrum data of the samples in each group.
Step S202: and obtaining optimal parameters corresponding to each group of samples according to the mass-to-charge ratio of each group of samples.
According to the embodiment of the invention, the test parameters corresponding to each group of samples can be obtained according to the mass-to-charge ratio of each group of samples, then each group of samples is tested according to the test parameters to obtain the resolution of each group of samples in the corresponding mass range, and the parameters corresponding to the resolution of the maximum value are set as the optimal parameters corresponding to each group of samples.
According to the embodiment of the invention, the test parameters corresponding to each group of samples can be estimated according to a theoretical formula under ideal conditions, wherein the theoretical formula is as follows:
wherein Deltat is delay time, da is extraction distance, y is voltage division ratio, D is field-free flight distance,is a coefficient related to the extraction distance, the partial pressure ratio, the secondary acceleration distance, and the field-free flight distance. It should be noted that the calculation formula can be used to obtain the +.>The calculation formula is as follows:
wherein v is n The theoretical final velocity which can be achieved by the ions with the initial velocity of 0, the mass number of m and the charge number of z under the action of the accelerating voltage (V) is an intermediate variable which is introduced by a theoretical formula for the convenience of expression.
The above theoretical formula represents ions with different mass-to-charge ratios, and their optimal Δt is approximately proportional to the square root of the mass-to-charge ratio, and the optimal delay time corresponding to each group of samples can be calculated according to the parameters of each group of samples by using the formula, then each delay time is obtained based on the optimal delay time, each group of samples is tested according to each delay time, the resolution of each group of samples in the corresponding mass range is obtained, and the parameter corresponding to the resolution of the maximum value is set as the optimal parameter corresponding to each group of samples.
Step S203: and detecting the reference products according to the optimal parameters corresponding to each group of samples, and obtaining corresponding conversion functions.
For the specific content of the step S203, reference may be made to the corresponding content disclosed in the foregoing embodiment, and no detailed description is given here.
Step S204: and testing the samples according to the optimal parameters, and obtaining high-resolution mass spectrum data of each group of samples by utilizing a conversion function.
According to the embodiment of the invention, samples are tested according to the optimal parameters to obtain flight time data, and high-resolution mass spectrum data near each group of samples is obtained by utilizing a conversion function according to the flight time data.
Step S205: and splicing all the high-resolution mass spectrum data to obtain a mass spectrum.
According to the embodiment of the invention, on the basis of obtaining the mass spectrogram, the method for carrying out secondary detection on the ions can obtain high-resolution mass spectrum data near the ions more accurately, so that the mass spectrogram with high resolution is obtained.
The above procedure is described below by way of a specific example in which the full mass range is set to a range of 4000 to 10000 mass-to-charge ratios, and the full mass range is divided into three regions, the first mass range being 4000 to 6000 mass-to-charge ratios, a parameter corresponding to a mass-to-charge ratio of 5000 being adopted as an optimum parameter of the first mass range, the second mass range being 6000 to 8000 mass-to-charge ratios, a parameter corresponding to a mass-to-charge ratio of 7000 being adopted as an optimum parameter of the second mass range, the third mass range being 8000 to 10000 mass-to-charge ratios, a parameter corresponding to a mass-to-charge ratio of 9000 being adopted as an optimum parameter of the third mass range, the procedure being as follows:
1. the reference was tested at mass to charge ratios of 5000, 7000 and 9000 according to the various sets of parameters in the time-of-flight mass spectrometry system.
2. According to the resolution of the reference in each mass range, an optimum parameter Pb of the ion having a mass-to-charge ratio of 7000, for example Pb of ua=3 kV, Δt=2.35 us and u3=4.8 kV, can be obtained, and this optimum parameter is set as the optimum parameter corresponding to the second mass range.
3. According to the formulaThe optimal delay time corresponding to the ions with mass-to-charge ratios of 5000 and 9000 can be obtained, the respective delay times can be obtained based on the optimal delay time, the reference is tested according to the respective delay times to obtain the optimal parameters Pa of the ions with mass-to-charge ratios of 5000, such as Pa being ua=3 kV, Δt=1.99 us and u3=4.8 kV, the parameters Pa are set as the optimal parameters corresponding to the first mass range, the optimal parameters Pc of the ions with mass-to-charge ratios of 9000 are obtained, such as Pc being ua=3 kV, Δt=2.67 us and u3=4.8 kV, and the optimal parameters are set as the optimal parameters corresponding to the third mass range. The following table of optimal parameters is specific (the results in the following table are simulation experiment results of ion simulation software (simion):
optimum parameter table
4. Detecting the reference according to the optimal parameters Pa, pb and Pc of the first mass range, the second mass range and the third mass range respectively, and utilizing a formulaConversion functions Fa, fb and Fc corresponding to the first mass range, the second mass range and the third mass range are obtained respectively, wherein A, B and C are coefficients to be solved, t is flight time, and m is mass-to-charge ratio. Specifically obtained scaling function Fa is shown in FIG. 3, in which the abscissa in FIG. 3 is the time of flight, the ordinate is the signal strength, the leftmost line represents a line table with a mass-to-charge ratio of 5000, and the middleThe mass-to-charge ratio is 7000, the line on the far right side represents the mass-to-charge ratio 9000, and a corresponding conversion function is obtained by calculation according to the optimal parameter of the first mass range, wherein the value of the coefficient a in the formula of the conversion function is 10.48978, the value of the coefficient B is-54.41393, and the value of the coefficient C is 130.13164, wherein the specific conversion functions Fb and Fc are similar to the conversion function Fa, and no description is repeated here.
5. And respectively testing the samples with mass-to-charge ratios of 4046, 5044, 6336, 7516, 8786 and 9977 according to the optimal parameters Pb, pb and Pc, respectively, and converting the time-of-flight data of the first mass range, the second mass range and the third mass range through conversion functions to respectively obtain mass spectrum data corresponding to the mass resolution table as follows:
mass resolution table
It should be noted that, in the mass resolution table, the single parameter-mass resolution is the mass resolution obtained by performing the test by only performing calibration once in the full mass range, and the three-section-mass resolution is the mass resolution obtained by performing the test according to the optimal parameter and the conversion function of each section of the mass range in the embodiment of the invention. As can be seen from the mass resolution table, the mass resolution is significantly improved for target ions having mass to charge ratios of 4046, 5044, 8786 and 9977. Ion resolutions of mass to charge ratios 6336 and 7516 have little variation. After parameter adjustment is carried out on the parameters in the embodiment of the invention, ions in each mass range interval can be tested by adopting more proper parameters, so that the mass bias is avoided, the lowest resolution of the full mass range is obviously improved, and the resolution of the linear flight time mass spectrum system is improved.
6. And splicing the mass spectrum data to obtain a high-resolution mass spectrum of the full mass range as shown in fig. 4. The abscissa of the mass spectrum is the mass-to-charge ratio (m/z) of the sample, and the ordinate is the signal intensity corresponding to the mass-to-charge ratio.
It should be noted that in the embodiment of the present invention, samples may be tested to obtain each group of samples, that is, samples may be tested according to a single parameter method or a multi-parameter method to obtain mass-to-charge ratio and low resolution mass spectrum data of each group of samples, then, one or more groups of samples are selected to perform a secondary test, and parameters with high matching degree are selected to perform a secondary test on each group of samples in different mass ranges, for example, ions with mass-to-charge ratio of 9977 in a third mass range may be used as samples to perform a secondary test, which may include:
1. according to the formulaThe optimum parameters Pd for the ion are calculated, for example Pd is ua=3 kV and Δt=2.81 us.
2. And testing the reference according to the optimal parameter Pd to obtain a corresponding conversion function Fd.
3. Detecting a sample according to the optimal parameter Pd, and converting the sample by using a conversion function Fd to obtain high-resolution mass spectrum data near the sample, wherein the mass resolution data is specifically shown in the following sample mass resolution table:
sample mass resolution table
It should be noted that, the targeting parameter-mass resolution is the mass resolution obtained by testing each sample by adopting the targeted Ua and Δt parameters, and the high-resolution mass spectrum data can be obtained by testing the targeted parameters in the table, wherein in the embodiment of the invention, each group of samples in different mass ranges can be subjected to secondary testing to respectively obtain corresponding different high-resolution mass spectrum data, and each high-resolution mass spectrum data can be spliced to obtain a high-resolution mass spectrum, so that the resolution of the linear flight time mass spectrum system is improved.
The embodiment of the invention provides a high-resolution time-of-flight mass spectrum detection method, which has simple implementation process, does not need to change hardware configuration, and can test ions in each mass range interval by adopting more proper parameters after parameter adjustment, calibration and test, thereby improving the mass resolution of each mass range interval and improving the resolution of a linear time-of-flight mass spectrum system.
In the description, each embodiment is described in a progressive manner, and each embodiment is mainly described by the differences from other embodiments, so that the same similar parts among the embodiments are mutually referred. For the device disclosed in the embodiment, the method is applicable to all devices adopting the principle of linear time-of-flight mass spectrometry, and corresponds to the method disclosed in the embodiment, and relevant points are referred to in the method section.
The high-resolution time-of-flight mass spectrometry detection method provided by the invention is described in detail above. The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present invention and its core ideas. It should be noted that it would be apparent to one of ordinary skill in the art that the present invention does not depart from the invention
The invention is capable of numerous modifications and adaptations, all of which are within the scope of the appended claims, given the principle underlying the invention.
Claims (8)
1. A method for high resolution time-of-flight mass spectrometry comprising:
according to each group of parameters in the time-of-flight mass spectrum system, testing a reference to obtain optimal parameters of each section of mass range corresponding to the reference;
detecting the reference product according to the optimal parameters to obtain conversion functions corresponding to the mass ranges of the sections;
according to the optimal parameters, testing a sample to be detected, and obtaining mass spectrum data corresponding to each section of mass range by utilizing the conversion function;
splicing the mass spectrum data to obtain a high-resolution mass spectrum;
the method for testing the reference according to each group of parameters in the flight time mass spectrum system, respectively obtaining the optimal parameters of each section of mass range corresponding to the reference, comprises the following steps: according to the parameters of each group, the reference product is tested respectively, and a test result of the reference product in the mass range of each section is obtained; wherein the test result comprises resolution and signal strength, and each segment of mass range comprises at least two mass ranges; determining whether a value of the test result corresponding to the reference exceeds a preset threshold; if the preset threshold value is exceeded, determining a parameter corresponding to the resolution of the maximum value in the test result, and setting the parameter as an optimal parameter of a quality range corresponding to the reference; if the quality range of the reference sample does not exceed the preset threshold, adjusting the parameters of each group, and testing the reference sample again to obtain a test result of the reference sample in the quality range of each section until the test result exceeds the preset threshold;
and detecting the reference product according to the optimal parameters to obtain conversion functions corresponding to the mass ranges of each section, wherein the conversion functions comprise: detecting the reference products according to the optimal parameters to obtain flight time data; and obtaining a conversion function corresponding to each section of mass range according to the flight time data and the mass-to-charge ratio of the reference.
2. The method for detecting high-resolution time-of-flight mass spectrometry according to claim 1, wherein the step of testing the reference according to each set of parameters in the time-of-flight mass spectrometry system to obtain the optimal parameters corresponding to each segment of mass range of the reference comprises the steps of:
obtaining test parameters corresponding to the reference according to the parameters of the reference;
and testing the reference according to the test parameters to obtain the resolution of the reference in the corresponding quality range, and setting the parameter corresponding to the resolution with the maximum value as the optimal parameter of the quality range corresponding to the reference.
3. The method of claim 1, wherein the reference is tested according to the respective sets of parameters to obtain a test result of the reference in the respective mass ranges, and wherein the respective sets of parameters include an extraction voltage, a delay time, a focusing voltage, a laser gain, and a detector gain.
4. A method of high resolution time of flight mass spectrometry as claimed in claim 3 wherein said adjusting said sets of parameters to re-test said reference respectively to obtain test results for said reference over said mass ranges of each segment until said test results exceed said predetermined threshold comprises:
adjusting the numerical value of the extraction voltage to obtain a new extraction voltage;
according to the new extraction voltage, adjusting the delay time according to a preset interval to obtain each new delay time;
and respectively testing the reference according to the new delay time to obtain a test result of the reference in the mass range of each section until the test result exceeds the preset threshold value.
5. The method for detecting high-resolution time-of-flight mass spectrometry according to claim 1, wherein the testing the sample to be detected according to the optimal parameter and obtaining mass spectrum data corresponding to the mass ranges of each segment by using the conversion function comprises:
determining an optimal parameter corresponding to the sample according to the mass-to-charge ratio of the sample to be detected;
testing the sample according to the optimal parameters to obtain flight time data;
and obtaining mass spectrum data corresponding to each section of mass range by utilizing the conversion function according to the flight time data.
6. The method for detecting high-resolution time-of-flight mass spectrometry according to claim 1, wherein the step of testing the reference to obtain the optimal parameters of the mass ranges of the respective segments corresponding to the reference comprises the steps of:
testing the samples to obtain mass-to-charge ratios of each group of samples in the samples;
obtaining optimal parameters corresponding to the groups of samples according to the mass-to-charge ratios of the groups of samples;
correspondingly, according to the optimal parameters, the reference products are detected respectively to obtain conversion functions corresponding to the mass ranges of each section, and the method comprises the following steps:
detecting the reference products according to the optimal parameters corresponding to the groups of samples to obtain corresponding conversion functions;
correspondingly, the testing the sample to be detected according to the optimal parameters, and obtaining mass spectrum data corresponding to the mass range of each section by utilizing the conversion function comprises the following steps:
testing the samples according to the optimal parameters, and obtaining high-resolution mass spectrum data of each group of samples by utilizing the conversion function;
correspondingly, the splicing the mass spectrum data to obtain a high-resolution mass spectrum comprises the following steps:
and splicing the high-resolution mass spectrum data to obtain a mass spectrum.
7. The method of high resolution time-of-flight mass spectrometry of claim 5, wherein said testing said samples to obtain mass-to-charge ratios for each set of samples in said samples comprises:
and testing the samples according to a single parameter method to obtain the mass-to-charge ratios of the groups of samples in the samples.
8. The method for detecting high-resolution time-of-flight mass spectrometry according to claim 1, wherein each mass spectrum data is spliced to obtain a high-resolution mass spectrum, and wherein an abscissa of the mass spectrum is a mass-to-charge ratio of the sample and an ordinate is a signal intensity corresponding to the mass-to-charge ratio.
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