Method for evaluating wear level of consumable for gas chromatograph and mass spectrometer

Abstract

To evaluate a wear level of consumables provided at a position of contacting a sample in a gas chromatograph and a mass spectrometer.SOLUTION: The present method has: an analysis step of passing an evaluation sample containing an indicator substance through a gas chromatograph equipped with a consumable that contacts the sample and mass-analyzing the evaluation sample having passed through using a mass spectrometer, or an analysis step of mass-analyzing the evaluation sample containing an indicator substance using the mass spectrometer equipped with the consumable that contacts the sample; a signal intensity acquisition step of acquiring a signal intensity of the indicator substance from the result of the mass analysis in the analysis step; and an evaluation step of evaluating a consumption degree of the consumable by comparing the signal intensity acquired in the signal intensity acquisition step with a preset reference signal intensity.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a method for assessing the degree of wear of consumables used in gas chromatographs and mass spectrometers. [Background technology]

[0002] Analytical instruments such as chromatographs and mass spectrometers contain consumables among their components, which become deteriorated or contaminated with use and require replacement. If consumables are not replaced properly, it may affect the accuracy of measurements. For this reason, many analytical instruments and analytical instrument control systems are equipped with a function to notify the user of the usage status of consumables and the estimated replacement time.

[0003] For example, Patent Document 1 describes an analytical device control system that monitors the usage of consumables (time of use, number of uses, amount of use) and calculates the planned replacement date for the consumables based on the usage and an upper limit value of the usage that is preset for each consumable. In this system, the calculated planned replacement date is shown on a display for each consumable, and an alert saying "replacement required" is also shown for consumables whose planned replacement date has passed. Users can maintain the analytical device in an appropriate condition by checking these displays and replacing consumables. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2014-032022 A Summary of the Invention [Problem to be solved by the invention]

[0005] Consumables such as septa and inserts in the sample vaporization chamber of a gas chromatograph, separation columns, and the ionization chamber of a mass spectrometer, as well as filaments in the ionization chamber's ion source, are exposed to vaporized or ionized samples during measurement. The degree of deterioration or contamination of such consumables (hereinafter referred to as "consumption degree") varies depending not only on the usage of the analytical device but also on the properties of the sample being measured. The method of Patent Document 1 does not take such factors into consideration, and there is a problem in that the actual consumption degree of the consumables cannot be evaluated.

[0006] An object of the present invention is to appropriately evaluate the degree of consumption of a consumable provided at a position where it comes into contact with a sample in a gas chromatograph or mass spectrometer. [Means for solving the problem]

[0007] In order to solve the above problems, the present invention provides a method for evaluating the degree of consumption of consumables for a gas chromatograph, comprising the steps of: an analysis step of passing an evaluation sample containing an indicator substance through a gas chromatograph having a consumable that comes into contact with the sample, and subjecting the passed evaluation sample to mass analysis by a mass spectrometer; a signal intensity acquiring step of acquiring a signal intensity of the indicator substance from a result of the mass spectrometry in the analyzing step; an evaluation step of evaluating a degree of consumption of the consumable by comparing the signal strength acquired in the signal strength acquisition step with a preset reference signal strength; has.

[0008] In order to solve the above problems, a method for evaluating the degree of consumption of a consumable for a mass spectrometer according to the present invention comprises the steps of: an analysis step of performing mass analysis of an evaluation sample containing an indicator substance using a mass spectrometer having a consumable item that contacts the sample; a signal intensity acquiring step of acquiring a signal intensity of the indicator substance from a result of the mass spectrometry in the analyzing step; an evaluation step of evaluating a degree of consumption of the consumable by comparing the signal strength acquired in the signal strength acquisition step with a preset reference signal strength; has. Effect of the Invention

[0009] According to the present invention, it is possible to appropriately evaluate the degree of consumption of a consumable provided at a position where it comes into contact with a sample in a gas chromatograph or mass spectrometer. [Brief description of the drawings]

[0010] [Figure 1] 1 is a schematic diagram of a gas chromatograph mass spectrometer for performing evaluation according to an embodiment of a method for evaluating the degree of consumption of a consumable item according to the present invention; [Diagram 2] 4 is a flowchart showing an evaluation procedure according to the embodiment. [Diagram 3] FIG. 13 is a diagram showing the results of a primary analysis of a cluster analysis carried out to select an index substance for evaluating the wear degree of a glass insert. [Figure 4A] FIG. 4 shows the results of secondary analysis of cluster G1 in FIG. 3 . [Figure 4B] A diagram showing the results of secondary analysis of clusters G2 and G3 in Figure 3. [Diagram 5] FIG. 1 shows the results of a primary analysis of a cluster analysis carried out to select an index substance for evaluating the degree of column consumption. [Figure 6] FIG. 6 shows the results of secondary analysis of cluster C5 in FIG. 5 . [Figure 7] FIG. 13 shows the results of a primary analysis of a cluster analysis carried out to select an index substance for evaluating the degree of consumption of an ionization chamber. [Figure 8A] FIG. 8 shows the results of secondary analysis of cluster M1 in FIG. 7. [Figure 8B] FIG. 8 shows the results of secondary analysis of cluster M3 in FIG. 7. [Figure 9] A diagram showing the results of tertiary analysis of cluster M11 in Figure 8A. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, an embodiment of a method for evaluating the degree of consumption of a consumable according to the present invention will be described with reference to the drawings. In this embodiment, a method for evaluating the degree of consumption of a consumable for a gas chromatograph mass spectrometer (GC-MS) will be described. Note that the "gas chromatograph" and "mass spectrometer" in the present invention respectively include a gas chromatograph and a mass spectrometer that constitute a part of the gas chromatograph mass spectrometer.

[0012] 1 is a schematic diagram of a GC-MS for evaluating the degree of consumption of a consumable in this embodiment. The GC-MS includes a gas chromatograph 1, a mass spectrometer 2, a data processing unit 3, and a storage unit 4.

[0013] Gas chromatograph 1 comprises a sample vaporization chamber 10 for vaporizing a minute amount of liquid sample, a microsyringe 11 for injecting the liquid sample into sample vaporization chamber 10, a column 12 for separating sample components in the time direction, and a column oven 13 for controlling the temperature of column 12. A glass insert 101 is housed inside sample vaporization chamber 10, and its top is sealed with a septum 102.

[0014] The mass spectrometer 2 is, for example, a triple quadrupole mass spectrometer, and is provided with an ionization chamber 21 in which a compound to be measured is ionized, an ion lens 22 for converging and transporting ions, a front-stage quadrupole mass filter 23 consisting of four rod electrodes, a collision cell 25 in which a multipole ion guide 24 is arranged, a rear-stage quadrupole mass filter 26, and a detector 27 for outputting an ion intensity signal corresponding to the amount of ions incident thereon as a detection signal. A collision gas, which is an inert gas such as argon or nitrogen, is continuously or intermittently supplied into the collision cell 25. The ionization chamber 21 is provided with an ion source (not shown) for ionizing a compound to be measured by electron ionization, and the ion source is provided with a filament 211 for generating thermal electrons.

[0015] In gas chromatograph 1, a carrier gas such as helium is supplied at a constant flow rate to column 12 via sample vaporization chamber 10. When a minute amount of liquid sample is injected from microsyringe 11 into sample vaporization chamber 10, the liquid sample is instantly vaporized in sample vaporization chamber 10 and carried by the carrier gas flow into column 12. Then, while passing through column 12, the temperature of which is controlled by column oven 13, various components contained in the sample are separated and flow out from the outlet of column 12 with a time lag.

[0016] The sample gas flowing out from the column 12 is introduced into the ionization chamber 21 of the mass spectrometer 2. The component molecules contained in the sample gas are successively ionized by collision with thermal electrons generated from the filament 211. The ionized component molecules are subjected to mass analysis by various monitoring modes and scan modes, such as SIM (selected ion monitoring) measurement, product ion scan measurement, and MRM (multiple reaction monitoring) measurement.

[0017] For example, in SIM measurement, the front quadrupole mass filter 23 does not select ions (does not function as a mass filter), and detects ions by fixing the mass-to-charge ratio of ions passing through the rear quadrupole mass filter 26. On the other hand, in product ion scan measurement and MRM measurement, both the front quadrupole mass filter 23 and the rear quadrupole mass filter 26 function as mass filters. The front quadrupole mass filter 23 passes only ions set as precursor ions. In addition, a collision gas is supplied to the inside of the collision cell 25 to dissociate the precursor ions and generate product ions. In MS / MS scan measurement, the mass-to-charge ratio of ions passing through the rear quadrupole mass filter 26 is scanned, and in MRM measurement, the mass-to-charge ratio of ions passing through the rear quadrupole mass filter 26 is fixed. The ions passing through the rear quadrupole mass filter 26 are detected by the detector 27.

[0018] The data processing unit 3 includes, as functional blocks, a data storage unit 30, a chromatogram creation unit 31, a peak detection unit 32, a peak area ratio calculation unit 33, and an evaluation processing unit 34. The data processing unit 3 is also connected to a memory unit 4. The details of each of these units will be described later.

[0019] The data processing unit 3 and the memory unit 4 are actually implemented, for example, by a personal computer, and each function can be realized by running dedicated control and processing software pre-installed on the computer.

[0020] The glass insert 101, septum 102, and column 12 of the gas chromatograph 1, as well as the ionization chamber 21 and filament 211 of the mass spectrometer 2, are consumables that come into contact with a sample during analysis, and are the objects of evaluation by the consumption evaluation method according to this embodiment. The evaluation procedure of the consumption evaluation method according to this embodiment will be described below with reference to the flowchart of Fig. 2. In the following description, the consumption of the consumables is evaluated using two types of indicator substances, but the indicator substances used to evaluate the consumption may be one type, or three or more types.

[0021] In step S1, an evaluation sample containing two types of indicator substances corresponding to a certain consumable is prepared. If there are multiple consumables to be evaluated, an evaluation sample containing two types of indicator substances corresponding to each consumable is prepared. Details of the indicator substances will be described later. In step S2, mass analysis of the evaluation sample is performed using a GC-MS equipped with the consumable to be evaluated. In step S3, signal intensities of the two types of indicator substances are obtained from the results of mass analysis obtained in step S2. In step S4, a ratio of the signal intensities of the two types of indicator substances obtained is calculated. In step S5, the calculated signal intensity ratio is compared with a reference signal intensity ratio that is preset as a guide for replacing the consumable to be evaluated, thereby evaluating the degree of consumption of the consumable. If there are multiple consumables to be evaluated, each process from step S3 to step S5 is performed for each consumable.

[0022] In the above-mentioned GC-MS, steps S3 to S5 are performed by the peak detection unit 32, the peak area ratio calculation unit 33, and the evaluation processing unit 34 of the data processing unit 3. It is also assumed that information on the indicator substance corresponding to each consumable item (type of indicator substance, mass-to-charge ratio value of ions derived from the indicator substance, retention time) and the reference signal intensity ratio are stored in the storage unit 4.

[0023] Specifically, the detection signal data output from the detector 27 of the mass spectrometer 2 is temporarily stored in the data storage unit 30 of the data processing unit 3. When the analysis is completed, the chromatogram creation unit 31 reads out the data of the evaluation sample from the data storage unit 30, and creates mass chromatograms for each of the two types of indicator substances at a specific mass-to-charge ratio characteristic of the indicator substances based on the data. The peak detection unit 32 detects peaks near preset retention times in the mass chromatograms, and calculates the peak areas of the detected peaks as the signal intensities of the two types of indicator substances. The peak area ratio calculation unit 33 calculates the ratio of the peak areas of the two types of indicator substances calculated by the peak detection unit 32. The evaluation processing unit 34 reads out the reference peak area ratio (reference signal intensity ratio) preset for these two types of indicator substances from the storage unit 4, and compares the peak area ratio calculated by the peak area ratio calculation unit 33 with the reference peak area ratio.

[0024] The indicator substance can be a substance that has been confirmed in advance to have a signal intensity that changes (increases, decreases) or does not change depending on the degree of deterioration or contamination of the consumables. For example, the indicator substance is selected from metabolic components in plasma. Specifically, a GC-MS connected to a gas chromatograph and a triple quadrupole mass spectrometer is used to measure a plasma sample using unused consumables. Then, a normal measurement is performed to measure the plasma sample under conditions in which the number of times the corresponding consumables have been used is changed. At this time, the consumables other than the corresponding consumables are replaced with new ones each time, and measurements are performed to keep the other conditions the same except for the number of times the corresponding consumables have been used. From the measurement results obtained in this way, changes in the signal intensity (peak area) value of the mass chromatogram peak derived from the metabolic components in the plasma sample are confirmed.

[0025] As an example, the above-mentioned measurement was performed by changing the number of times the glass insert 101 was used, and the change rate of the signal intensity when the number of times the glass insert 101 was changed relative to the initial signal intensity was obtained. The results of grouping by cluster analysis based on the change rate are shown in Figures 3, 4A, and 4B. Figure 3 shows the results of the primary analysis, with G1 to G10 representing each primary cluster. Figure 4A shows the results of the secondary analysis in cluster G1 in Figure 3, with G11 to G15 representing each secondary cluster. Figure 4B shows the results of the secondary analysis in clusters G2 and G3 in Figure 3, with G21 to G24 representing each secondary cluster. Table 1 also shows a table summarizing the change rate of the signal intensity (peak area) when the number of times the glass insert 101 was used in clusters G13 to G15, G6, and G22 to 24 is changed. The change rate is the average value obtained by adding up the change rates of the components contained in each cluster and dividing the sum by the number of components. The same applies below.

[0026] [Table 1]

[0027] For the compounds contained in clusters G13 to G15 and cluster G6, the signal intensity tended to increase with an increase in the number of times the glass insert 101 was used. On the other hand, for the compounds contained in clusters G22 to G24, the detection intensity tended to decrease with an increase in the number of times the glass insert 101 was used.

[0028] Similarly, the number of times column 12 was used was changed, and grouping was performed by cluster analysis based on the rate of change in signal intensity. The results are shown in Figures 5 and 6. Figure 5 shows the results of the primary analysis, with C1 to C10 representing each primary cluster. Figure 6 shows the results of the secondary analysis for cluster C5 in Figure 5, with C51 to C53 representing each secondary cluster. Table 2 shows a summary of the rate of change in signal intensity when the number of times column 12 was used was changed in clusters C2 to C4, C53, C9, and C10.

[0029] [Table 2]

[0030] The analysis showed that in clusters C2, C3, and C53, the signal intensity did not change significantly even if the number of times column 12 was used increased, whereas in clusters C4, C9, and C10, the signal intensity tended to increase as the number of times it was used increased.

[0031] Similarly, the results of grouping by cluster analysis based on the rate of change in signal intensity when the number of times the ionization chamber 21 is used is changed are shown in Figs. 7, 8A, 8B, and 9. Fig. 7 shows the results of the primary analysis, with M1 to M10 representing the primary clusters. Fig. 8A shows the results of the secondary analysis in the cluster M1 in Fig. 7, with M11 to M14 representing the secondary clusters. Fig. 8B shows the results of the secondary analysis in the cluster M3 in Fig. 7, with M31 to M33 representing the secondary clusters. Fig. 9 shows the results of the tertiary analysis in the cluster M11 in Fig. 8A, with M111 to M116 representing the tertiary clusters. Table 3 shows the rates of change in detection intensity when the number of times the ionization chamber 21 is used is changed in the clusters M111 to M113, M32, M33, and M4.

[0032] [Table 3]

[0033] As a result of the analysis, in clusters M111 to M113, the signal intensity did not change much even if the number of times of use of the ionization chamber 21 increased. On the other hand, in clusters M32, M33, and M4, the signal intensity tended to decrease as the number of times of use increased.

[0034] From the above analysis results, it is believed that by using two types of indicator substances that have different trends in signal intensity changes when the number of times a consumable is used is changed, and calculating the ratio of the signal intensities of the peaks derived from them, it is possible to evaluate the degree of consumption of each consumable based on the signal intensity ratio.

[0035] Therefore, from Figures 3, 4A, and 4B, it was confirmed that the evaluation samples used to evaluate the glass insert 101 tended to have an increasing detection intensity. (Cluster G13): Lactic acid-2TMS, 2-Hydroxybutyric acid-2TMS, 3-Hydroxybutyric acid-2TMS, 2-Hydroxyisovaleric acid-2TMS, 3-Hydroxyisobutyric acid-2TMS, Pyruvic acid-meto-TMS, Elaidic acid-TMS, Uric acid-4TMS, 1,5-Anhydro-glucitol-4TMS, Benzoic acid-TMS, 2-Hydroxyisobutyric acid-2TMS, (Cluster G14): Margaric acid-TMS, (Cluster G15): Glycerol-3TMS, Hippuric acid-TMS, 3-Hydroxyisovaleric acid-2TMS, Myristic It is preferable that the indicator substance contains at least one compound selected from a first group consisting of (Cluster G6): Urea-2TMS, Octanoic acid-TMS, Stearic acid-TMS, Palmitic acid-TMS, and at least one compound selected from a second group consisting of (Cluster G22): Glutamine-3TMS, Histidine-3TMS, Threitol-4TMS, Glutamic acid-3TMS, Phenylalanine-2TMS, 3-Aminoglutaric acid-2TMS, Asparagine-3TMS, (Cluster G23): Cysteine-3TMS, Methionine-2TMS, 4-Hydroxyproline-3TMS, and (Cluster G24): N-Acetyl-Ornithine-4TMS, Alanine-2TMS, in which a decreasing tendency of detection intensity has been confirmed. In addition, TMS and meto stand for trimethylsilyl and methoxim, respectively. The same applies below.

[0036] 5 and 6, it was confirmed that the evaluation samples used in the evaluation of column 12 showed no change in detection intensity (Cluster C2): 2-Hydroxyisobutyric acid-2TMS, Uric acid-4TMS, 3-Aminopropanoic acid-3TMS, Malic acid-3TMS, Gluconic acid-methyloxime-5TMS, (Cluster C3): Glucosamine-5TMS, Hippuric acid-TMS, and (Cluster C53): at least one compound selected from the third group consisting of Fructose-meto-5TMS, Sorbose-meto-5TMS, and 2-Aminoadipic acid-3TMS, and that the detection intensity tended to increase (Cluster C4): 2-Deoxy-glucose-4TMS, Ornithine-4TMS, Tyramine-3TMS, Succinic acid-2TMS, Isocitric acid-4TMS, Valine-2TMS, Citric It is preferable that the indicator substance comprises at least one compound selected from the fourth group consisting of: (Cluster C9): Cystine-4TMS, Glutamic acid-3TMS, Phenylalanine-2TMS, Glutamine-3TMS, and (Cluster C10): Alanine-2TMS.

[0037] 7, 8A, 8B, and 9, it was confirmed that the evaluation samples used to evaluate the ionization chamber 21 did not change in detection intensity. (Cluster M111): 2-Aminoethanol-3TMS, 2-Aminopimelic acid-3TMS, Sorbose-meto-5TMS, myo-Inositol-6TMS, Psicose-meto-5TMS, 3-Aminopropanoic acid-3TMS, Isocitric acid-4TMS, (Cluster M112): Glycerol-3TMS, 3-Hydroxybutyric acid-2TMS, Inositol-6TMS, 2-Isopropylmalic acid-3TMS, Citric acid-4TMS, and (Cluster M113): Uric acid-4TMS, Fructose-meto-5TMS, Glucuronic acid-4TMS. It is preferable that the indicator substance contains at least one compound selected from a fifth group consisting of 2-aminobutyric acid-2TMS, Alanine-2TMS, Phenylalanine-2TMS, Glutamic acid-3TMS, Isoleucine-2TMS, Leucine-2TMS, Arginine-3TMS, (Cluster M33): Threonine-3TMS, Serine-3TMS, 4-Hydroxyproline-3TM, 3-Aminoglutaric acid-2TMS, Glucosamine-5TMS(1), and (Cluster M4): Cysteine-3TMS, Cystine-4TMS, Octanoic acid-TMS, in which a decreasing tendency of detection intensity has been confirmed.

[0038] The indicator substances can be selected in the same manner as described above for the septum 102 and the filament 211. The evaluation sample may contain all of the indicator substances for evaluation of the glass insert 101, the indicator substances for evaluation of the septum 102, the indicator substances for evaluation of the column 12, the indicator substances for evaluation of the ionization chamber 21, and the indicator substances for evaluation of the filament 211, or may contain any combination of indicator substances for evaluation of the consumables.

[0039] According to the method for evaluating the degree of consumption of consumables according to the present embodiment, the deterioration or contamination state of the consumables can be appropriately evaluated. In addition, when the evaluation sample contains index substances for evaluating a plurality of consumables, the degree of consumption of the plurality of consumables can be evaluated by a single measurement. For example, when the measurement sensitivity of a gas chromatograph or mass spectrometer decreases, by performing mass spectrometry on the evaluation sample containing the index substances for evaluating the plurality of consumables, it is possible to evaluate at once which consumable has a large degree of consumption, and to easily identify the cause of the decrease in sensitivity.

[0040] (Modification) The present invention is not limited to the above-described embodiment, and can be modified as appropriate.

[0041] For example, in the above embodiment, the degree of consumption of the consumables is evaluated based on the ratio of the area values ​​of the peaks corresponding to the two indicator substances, each of which has a different tendency of changing in signal intensity due to use of the consumables, by measuring the evaluation sample containing the two indicator substances. However, the degree of consumption may be evaluated by mass spectrometry of the evaluation sample containing one indicator substance whose signal intensity has been confirmed to change. Specifically, for an indicator substance whose signal intensity has been confirmed to change due to use of the consumables, a peak is detected from the created mass chromatogram, and the area value of the peak is compared with a preset reference area value to evaluate the degree of consumption.

[0042] The indicator substance may be labeled with a stable isotope (such as deuterium or carbon-13). If such an indicator substance is used, even if the indicator substance is mixed with a normal measurement sample and then measured, the indicator substance contained in the measurement sample and the labeled indicator substance can be distinguished by mass spectrometry.

[0043] [Aspects] It will be apparent to those skilled in the art that the above-described exemplary embodiments are illustrative of the following aspects.

[0044] (Item 1) A method for evaluating the degree of consumption of a consumable for a gas chromatograph according to one aspect of the present invention includes: an analysis step of passing an evaluation sample containing an indicator substance through a gas chromatograph having a consumable that comes into contact with the sample, and subjecting the passed evaluation sample to mass analysis by a mass spectrometer; a signal intensity acquiring step of acquiring a signal intensity of the indicator substance from a result of the mass spectrometry in the analyzing step; an evaluation step of evaluating a degree of consumption of the consumable by comparing the signal strength acquired in the signal strength acquisition step with a preset reference signal strength; has.

[0045] (2) In the method for evaluating the degree of wear of a consumable for a gas chromatograph according to the first aspect of the present invention, The consumable may be a septum, a glass insert, or a column.

[0046] According to the method for evaluating the degree of consumption of a consumable for a gas chromatograph according to the first or second aspect, the degree of consumption of a consumable that comes into contact with a sample in a gas chromatograph can be appropriately evaluated.

[0047] (3) In the method for evaluating the wear level of a gas chromatograph consumable according to paragraph 1 or 2, The evaluation sample contains at least two types of the indicator substances, In the signal intensity acquiring step, signal intensities of two types of the indicator substances are acquired; In the evaluation process, the degree of consumption of the consumable may be evaluated by comparing the ratio of the signal intensities of the two types of indicator substances acquired in the signal intensity acquisition process with a predetermined reference signal intensity ratio.

[0048] (4) In the method for evaluating the degree of wear of consumables for a gas chromatograph according to paragraph 3, the consumable is a glass insert; In the signal intensity acquisition step, Lactic acid-2TMS, Benzoic acid-TMS, 3-Hydroxybutyric acid-2TMS, Pyruvic acid-meto-TMS, 2-Hydroxybutyric acid-2TMS, 2-Hydroxyisovaleric acid-2TMS, 3-Hydroxyisobutyric acid-2TMS, Elaidic acid-TMS, 2-Hydroxyisobutyric acid-2TMS, Uric acid-4TMS, 1,5-Anhydro-glucitol-4TMS, Margaric acid-TMS, Glycerol-3TMS, Hippuric acid-TMS, 3-Hydroxyisovaleric acid-2TMS, Myristic acid-TMS, Urea-2TMS, Stearic acid-TMS, Palmitic acid-TMS acid-TMS, and Octanoic The signal intensity of one indicator substance selected from a first group consisting of Glutamine-3TMS, Glutamic acid-3TMS, Phenylalanine-2TMS, Histidine-3TMS, Asparagine-3TMS, Threitol-4TMS, 3-Aminoglutaric acid-2TMS, N-Acetyl-Ornithine-4TMS, Cysteine-3TMS, Alanine-2TMS, 4-Hydroxyproline-3TMS, and Methionine-2TMS may be obtained.

[0049] (5) In the method for evaluating the wear level of a gas chromatograph consumable according to the third aspect of the present invention, the consumable is a column; In the signal intensity acquisition step, the signal intensity of one indicator substance selected from a third group consisting of 2-Hydroxyisobutyric acid-2TMS, Malic acid-3TMS, 3-Aminopropanoic acid-3TMS, Gluconic acid-methyloxime-5TMS, Uric acid-4TMS, Glucosamine-5TMS, Hippuric acid-TMS, Fructose-meto-5TMS, Sorbose-meto-5TMS, and 2-Aminoadipic acid-3TMS, and 2-Deoxy-glucose-4TMS, Succinic acid-2TMS, Isocitric acid-4TMS, Ornithine-4TMS, Tyramine-3TMS, Ascorbic acid-4TMS, Citric The signal intensity of one indicator substance selected from a fourth group consisting of Glutamic acid-4TMS, Glucose-meto-5TMS, Kynurenine-3TMS, Rhamnose-meto-4TMS, Xylulose-meto-4TMS, Valine-2TMS, Cystine-4TMS, Glutamic acid-3TMS, Phenylalanine-2TMS, Glutamine-3TMS, and Alanine-2TMS may be obtained.

[0050] According to the method for evaluating the degree of consumption of a gas chromatograph consumable product of any one of items 3 to 5, the degree of consumption is evaluated based on the ratio of the signal intensities of two types of indicator substances, making it easier to see changes in signal intensity and enabling a more appropriate evaluation of the degree of consumption of the consumable product.

[0051] (6) In the method for evaluating the degree of wear of a gas chromatograph consumable according to paragraph 4 or 5, The indicator substance may be labeled with a stable isotope.

[0052] According to the method for evaluating the degree of consumption of consumables for a gas chromatograph in accordance with paragraph 6, the degree of consumption of the consumables can be appropriately evaluated even when an indicator substance is mixed into a normal measurement sample and then measured.

[0053] (Item 7) A sample for evaluating the degree of consumption of a consumable for a gas chromatograph according to one aspect of the present invention is an evaluation sample for use in the method for evaluating the degree of consumption of a consumable for a gas chromatograph according to item 4, The sample contains at least one indicator substance selected from the first group and at least one indicator substance selected from the second group.

[0054] (Item 8) A sample for evaluating the degree of consumption of a consumable for a gas chromatograph according to one aspect of the present invention is an evaluation sample for use in the method for evaluating the degree of consumption of a consumable for a gas chromatograph according to item 5, It contains at least one indicator substance selected from the third group and at least one indicator substance selected from the fourth group.

[0055] According to the sample for evaluating the degree of consumption of a consumable for a gas chromatograph according to the seventh or eighth aspect, the degree of consumption of the consumable that comes into contact with the sample in the gas chromatograph can be appropriately evaluated.

[0056] (Item 9) A method for evaluating the degree of consumption of a consumable for a mass spectrometer according to one aspect of the present invention includes: an analysis step of performing mass analysis of an evaluation sample containing an indicator substance using a mass spectrometer having a consumable item that contacts the sample; a signal intensity acquiring step of acquiring a signal intensity of the indicator substance from a result of the mass spectrometry in the analyzing step; an evaluation step of evaluating a degree of consumption of the consumable by comparing the signal strength acquired in the signal strength acquisition step with a preset reference signal strength; has.

[0057] (10) In the method for evaluating the degree of consumption of consumables of a mass spectrometer according to paragraph 9, The consumable may be an ionization chamber or a filament.

[0058] According to the method for evaluating the degree of consumption of a consumable for a mass spectrometer according to the ninth or tenth aspect, the degree of consumption of a consumable that comes into contact with a sample in a mass spectrometer can be appropriately evaluated.

[0059] (11) In the method for evaluating the degree of consumption of a consumable for a mass spectrometer according to paragraph 9 or 10, The evaluation sample contains at least two types of the indicator substances, In the signal intensity acquiring step, signal intensities of two types of the indicator substances are acquired; In the evaluation process, the degree of consumption of the consumable may be evaluated by comparing the ratio of the signal intensities of the two types of indicator substances acquired in the signal intensity acquisition process with a predetermined reference signal intensity ratio.

[0060] (12) In the method for evaluating the degree of consumption of a consumable for a mass spectrometer according to the paragraph 11, the consumable is an ionization chamber; In the signal intensity acquiring step, a signal intensity of one indicator substance selected from a fifth group consisting of 2-Aminoethanol-3TMS, myo-Inositol-6TMS, 2-Aminopimelic acid-3TMS, Sorbose-meto-5TMS, 3-Aminopropanoic acid-3TMS, Isocitric acid-4TMS, Psicose-meto-5TMS, Glycerol-3TMS, 2-Isopropylmalic acid-3TMS, 3-Hydroxybutyric acid-2TMS, Inositol-6TMS, Citric acid-4TMS, Uric acid-4TMS, Fructose-meto-5TMS, Glucuronic acid-meto-5TMS, and Arabinose-meto-4TMS is acquired, and 2-Aminobutyric acid-2TMS, Phenylalanine-2TMS, Glutamic The signal intensity of one indicator substance selected from a sixth group consisting of 3-aminoglutaric acid-3TMS, Alanine-2TMS, Isoleucine-2TMS, Leucine-2TMS, Arginine-3TMS, Threonine-3TMS, Glucosamine-5TMS, Serine-3TMS, 3-Aminoglutaric acid-2TMS, 4-Hydroxyproline-3TM, Cysteine-3TMS, Octanoic acid-TMS, and Cystine-4TMS may be obtained.

[0061] According to the method for evaluating the degree of consumption of consumables for a mass spectrometer relating to paragraph 11 or 12, the degree of consumption is evaluated based on the ratio of the signal intensities of two types of indicator substances, making it easier to see changes in signal intensity and enabling a more appropriate evaluation of the degree of consumption of the consumables.

[0062] (13) In the method for evaluating the degree of consumption of a consumable for a mass spectrometer according to the paragraph 12, The indicator substance may be labeled with a stable isotope.

[0063] According to the method for evaluating the degree of consumption of consumables for a mass spectrometer according to paragraph 13, even when an indicator substance is mixed into a normal measurement sample and then measured, the degree of consumption of the consumables can be appropriately evaluated.

[0064] (Item 14) A sample for evaluating the degree of consumption of a consumable of a mass spectrometer according to one aspect of the present invention comprises: An evaluation sample used in the method for evaluating the degree of consumption of a consumable for a mass spectrometer according to claim 12 may contain at least one indicator substance selected from the fifth group and at least one indicator substance selected from the sixth group.

[0065] According to the sample for evaluating the degree of consumption of a consumable for a mass spectrometer according to the fourteenth aspect, the degree of consumption of the consumable that comes into contact with the sample in the mass spectrometer can be appropriately evaluated. [Explanation of symbols]

[0066] 1. Gas chromatograph 10...Sample vaporizer 101…Glass insert 102…Septum 11. Micro syringe 12…Column 13…Column oven 2...Mass spectrometer 20…Analysis room 21…Ionization chamber 211…Filament 22…Ion lens 23...Pre-quadrupole mass filter 24...Multipole ion guide 25…Collision cell 26...Post-quadrupole mass filter 27…Detector 3. Data processing section 30…Data storage section 31... Chromatogram creation section 32...Peak detector 33...Peak area ratio calculation section 34...Evaluation processing unit 4...Storage section

Claims

1. An analytical process comprising passing an evaluation sample containing an indicator substance through a gas chromatograph equipped with consumables that come into contact with the sample, and then performing mass analysis on the evaluation sample that has passed through the gas chromatograph using a mass spectrometer, A signal intensity acquisition step is performed to obtain the signal intensity of the indicator substance from the results of mass spectrometry in the analysis step, An evaluation step in which the degree of wear of the consumable is evaluated by comparing the signal strength obtained in the signal strength acquisition step with a preset reference signal strength, A method for evaluating the wear and tear of consumables for a gas chromatograph having [a specific feature / feature].

2. The method for evaluating the wear and tear of consumables for a gas chromatograph according to claim 1, wherein the consumables are a septum, a glass insert, or a column.

3. The evaluation sample comprises at least two types of the indicator substances, In the signal intensity acquisition step, the signal intensity of two types of indicator substances is acquired. A method for evaluating the degree of wear of consumables for a gas chromatograph according to claim 1, wherein in the evaluation step, the degree of wear of the consumables is evaluated by comparing the ratio of the signal intensities of two types of indicator substances obtained in the signal intensity acquisition step with a preset reference signal intensity ratio.

4. The aforementioned consumable is a glass insert. In the signal intensity acquisition step, Lactic acid-2TMS, Benzoic acid-TMS, 3-Hydroxybutyric acid-2TMS, Pyruvic acid-meto-TMS, 2-Hydroxybutyric acid-2TMS, 2-Hydroxyisovaleric acid-2TMS, 3-Hydroxyisobutyric acid-2TMS, Elaidic acid-TMS, 2-Hydroxyisobutyric acid-2TMS, Uric acid-4TMS, 1,5-Anhydro-glucitol-4TMS, Margaric acid-TMS, Glycerol-3TMS, Hippuric acid-TMS, 3-Hydroxyisovaleric acid-2TMS, Myristic acid-TMS, Urea-2TMS, Stearic acid-TMS, Palmitic acid-TMS acid-TMS, and Octanoic A method for evaluating the wear and tear of consumables for a gas chromatograph according to claim 3, comprising obtaining the signal intensity of one indicator substance selected from a first group consisting of acid-TMS and the signal intensity of one indicator substance selected from a second group consisting of glutamine-3TMS, glutamic acid-3TMS, phenylalanine-2TMS, histidine-3TMS, asparagine-3TMS, threitol-4TMS, 3-aminogutaric acid-2TMS, N-Acetyl-Ornithine-4TMS, cysteine-3TMS, alanine-2TMS, 4-Hydroxyproline-3TMS, and methyonine-2TMS.

5. The aforementioned consumable is a column, In the signal intensity acquisition step, the signal intensity of one indicator substance selected from the third group consisting of 2-Hydroxyisobutyric acid-2TMS, Malic acid-3TMS, 3-Aminopropanoic acid-3TMS, Gluconic acid-methyloxime-5TMS, Uric acid-4TMS, Glucosamine-5TMS, Hippuric acid-TMS, Fructose-meto-5TMS, Sorbose-meto-5TMS, and 2-Aminoadipic acid-3TMS is obtained, along with the signal intensity of one indicator substance selected from the third group consisting of 2-Hydroxyisobutyric acid-2TMS, Malic acid-3TMS, 3-Aminopropanoic acid-3TMS, Gluconic acid-methyloxime-5TMS, Uric acid-4TMS, Glucosamine-5TMS, Hippuric acid-TMS, Fructose-meto-5TMS, Sorbose-meto-5TMS, and 2-Aminoadipic acid-3TMS, and Citric A method for evaluating the wear and tear of a gas chromatograph consumable according to claim 3, comprising obtaining the signal intensity of one indicator substance selected from a fourth group consisting of acid-4TMS, glucose-meto-5TMS, kynurine-3TMS, rhhamnose-meto-4TMS, xylulose-meto-4TMS, valine-2TMS, cystine-4TMS, glutamic acid-3TMS, phenylalanine-2TMS, glutamine-3TMS, and alanine-2TMS.

6. The method for evaluating the wear and tear of consumables for a gas chromatograph according to claim 1, wherein the indicator substance is labeled with a stable isotope.

7. An evaluation sample used in the method for evaluating the degree of wear of consumables for a gas chromatograph according to claim 4, A sample for evaluating the wear and tear of gas chromatograph consumables, comprising at least one indicator substance selected from the first group and at least one indicator substance selected from the second group.

8. An evaluation sample used in the method for evaluating the degree of wear of consumables for a gas chromatograph according to claim 5, A sample for evaluating the wear and tear of gas chromatograph consumables, comprising at least one indicator substance selected from the third group and at least one indicator substance selected from the fourth group.

9. An analytical step of mass spectrometry in which an evaluation sample containing an indicator substance is subjected to mass spectrometry using a mass spectrometer equipped with consumables that come into contact with the sample, A signal intensity acquisition step is performed to obtain the signal intensity of the indicator substance from the results of mass spectrometry in the analysis step, An evaluation step in which the degree of wear of the consumable is evaluated by comparing the signal strength obtained in the signal strength acquisition step with a preset reference signal strength, A method for evaluating the wear and tear of consumables for a mass spectrometer.

10. The method for evaluating the wear and tear of a consumable for a mass spectrometer according to claim 9, wherein the consumable is an ionization chamber or a filament.

11. The evaluation sample comprises at least two types of the indicator substances, In the signal intensity acquisition step, the signal intensity of two types of indicator substances is acquired. A method for evaluating the degree of wear of consumables for a mass spectrometer according to claim 9 or 10, wherein the degree of wear of the consumables is evaluated in the evaluation step by comparing the ratio of the signal intensities of two types of indicator substances obtained in the signal intensity acquisition step with a preset reference signal intensity ratio.

12. The aforementioned consumable is an ionization chamber. In the signal intensity acquisition step, the signal intensity of one indicator substance selected from the fifth group consisting of 2-Aminoethanol-3TMS, myo-Inositol-6TMS, 2-Aminopimelic acid-3TMS, Sorbose-meto-5TMS, 3-Aminopropanoic acid-3TMS, Isocitric acid-4TMS, Psicose-meto-5TMS, Glycerol-3TMS, 2-Isopropylmalic acid-3TMS, 3-Hydroxybutyric acid-2TMS, Inositol-6TMS, Citric acid-4TMS, Uric acid-4TMS, Fructose-meto-5TMS, Glucuronic acid-meto-5TMS, and Arabinose-meto-4TMS is acquired, and the signal intensity of 2-Aminobutyric acid-2TMS, Phenylalanine-2TMS, Glutamic A method for evaluating the wear and tear of a mass spectrometer consumable according to claim 11, comprising obtaining the signal intensity of one indicator substance selected from a sixth group consisting of acid-3TMS, alanine-2TMS, isoleucine-2TMS, leucine-2TMS, arginine-3TMS, threonine-3TMS, glucosamine-5TMS, serine-3TMS, 3-aminogutaric acid-2TMS, 4-Hydroxyproline-3TM, cysteine-3TMS, octanoic acid-TMS, and cystine-4TMS.

13. The method for evaluating the wear and tear of consumables for a mass spectrometer according to claim 9, wherein the indicator substance is labeled with a stable isotope.

14. An evaluation sample used in the method for evaluating the degree of wear of consumables for a mass spectrometer according to claim 12, A sample for evaluating the wear and tear of consumables for a mass spectrometer, comprising at least one indicator substance selected from the fifth group and at least one indicator substance selected from the sixth group.

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