KR101654776B1 - An apparatus and a method for automatic sample monitoring based on chromatography, and recording medium storing program for executing the same - Google Patents

An apparatus and a method for automatic sample monitoring based on chromatography, and recording medium storing program for executing the same Download PDF

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KR101654776B1
KR101654776B1 KR1020160033441A KR20160033441A KR101654776B1 KR 101654776 B1 KR101654776 B1 KR 101654776B1 KR 1020160033441 A KR1020160033441 A KR 1020160033441A KR 20160033441 A KR20160033441 A KR 20160033441A KR 101654776 B1 KR101654776 B1 KR 101654776B1
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sample
component
measuring
chromatography
error range
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KR1020160033441A
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Korean (ko)
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이응선
전광수
박무성
김대희
유승교
김동철
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주식회사 위드텍
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/24—Automatic injection systems
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/86—Signal analysis
    • G01N30/8675—Evaluation, i.e. decoding of the signal into analytical information
    • G01N30/8679—Target compound analysis, i.e. whereby a limited number of peaks is analysed
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8804—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 automated systems

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Abstract

The present invention relates to a chromatography-based automatic specimen measuring device and a measuring method thereof. More specifically, the present invention relates to a chromatography-based automatic specimen measuring device enabling a qualitative and quantitative analysis on a specimen automatically by setting a detection time and an error range therefor after measuring a standard substance of which components thereof is already known and then comparing the detection time by measuring the specimen to analyze. Particularly, by automatically updating the detection time which can be a comparative standard after re-measuring the standard substance depending on the predetermined condition or period, the accurate analysis is possible all the time. The present invention further relates to a measuring method thereof.

Description

[0001] The present invention relates to an automatic sample measurement apparatus and a measurement method based on chromatography, and a recording medium in which a program for implementing the same is stored.

More particularly, the present invention relates to a chromatographic-based automatic sample measurement apparatus and method, and more particularly, to a method and apparatus for measuring a sample The present invention relates to a chromatographic-based automatic sample measurement apparatus and a measurement method capable of automatically qualitatively and quantitatively analyzing the sample sample by measuring the sample and comparing the detection time.

In particular, the present invention relates to a chromatographic automatic sample measurement device and a measurement method for automatically correcting the reference time by automatically re-measuring the reference material in accordance with a predetermined condition or cycle and automatically updating the detection time as a comparison standard .

Chromatography refers to the fact that a sample injected into a measuring device is measured separately by the interaction of a mobile phase and a stationary phase and is measured with time. In the same measurement condition and the same measuring device, And the qualitative and quantitative analysis is carried out by using the characteristic that the included components exhibit different detection times (peak occurrence time).

More specifically, when a sample containing various components is mixed with a mobile phase and the sample is flowed in a fixed phase, the moving speed through the fixed phase varies depending on the characteristics of each component contained in the sample, and the detection time differs for each component. Therefore, by using a reference material that indicates a sample that already contains a certain component, the detection time for each component included in the reference material is set in advance, and the sample to be analyzed is measured to compare the detection time. The contained components are identified (qualitative analysis), and the sensitivity of the peaks is compared and quantitatively analyzed.

On the other hand, Korean Patent No. 10-1359941 ("Liquid Chromatography Apparatus for Rapid Measurement ", Registered Date: 2014.02.03) has been disclosed as a prior art related thereto.

Recently, on-line monitoring devices for automatic continuous measurement of samples based on chromatography are beginning to be used in the industrial field.

Such continuous use of the automatic sample measuring device causes a change in the performance of the mobile phase and the fixed phase due to the life of the components constituting the device and the external environment, even if the analysis conditions are the same.

Therefore, the detection time of the reference material that is initially set is changed, so that the component is not accurately recognized during the measurement of the sample, or the other peaks are misinterpreted, thereby causing problems in qualitative and quantitative analysis. Accordingly, conventionally, there has been a problem that the detection time has to be reset by measuring the standard material by periodically inputting the attraction force.

Also, in the industrial field, the sample to be measured is frequently changed, and the amount of the sample is very small, so that it is often necessary to measure only once. For example, if you want to analyze the FOUP internal contaminants and ionic contaminants on the wafer, you will extract the contaminants and analyze them with an ion chromatographic-based automated sample analyzer. At this time, although the amount of the sample is very small, only the sample has to be able to grasp the contamination state, so accurate measurement and analysis must always be performed.

As another example, when monitoring the emission gas of the stack, it is legally controlled for the emission concentration, and it is judged whether or not the emission allowance standard is used, and it is used as the administrative disposition data. If an error occurs in the measurement result, Accurate measurement and analysis must be made.

Accordingly, there is a growing need for an apparatus and a method for continuously and precisely analyzing the qualities and quantities of a sample by compensating for changes in the mobile phase and the stationary phase as time elapses during the online automatic sample measurement.

Korean Patent No. 10-1359941

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems described above, and it is an object of the present invention to provide a method and apparatus for detecting and changing a reference detection time caused by changes in measurement conditions and environment, And to provide a chromatographic-based automatic sample measurement apparatus and a measurement method which enable the measurement of the measurement results.

The present invention relates to a sample measuring apparatus for continuously and automatically measuring components of a sample on the basis of a chromatographic method, which comprises a reference material for setting a detection time (hereinafter referred to as 'RT' A channel integrating module (100) for selectively transporting any one of the sample samples; A sample injection unit 200 including a sample loop 210 into which the sample and the mobile phase material are injected; A column 300 into which a sample is injected and separated from the sample injection unit 200; A measurement unit 400 for measuring a signal of components contained in the sample separated in the column 300; If RT is detected from the signal measured by the measuring unit 400, the reference RT is stored as a reference RT according to a reference material. If the sample is a sample, A data processing unit 500 for analyzing the data; And a control unit (600) for controlling the reference material to be moved to the sample injection unit (200) according to a predetermined condition or cycle to update the reference RT for each component.

If the detected RT of the sample is within the tolerance range of the reference RT with respect to the previously stored specific component, the data processor 500 can determine the component as the corresponding component.

If the detected RT of at least one of the sample samples is out of the tolerance range of RT with respect to the previously stored specific component and is within an approximate range set by the controller 600, After the reference material is re-measured, the reference RT for each component may be corrected and then reapplied to the RT of the previously-measured sample or may be applied from the subsequently injected sample.

In addition, when a matrix peak occurs in the detection result of the measurement unit 400, the data processing unit 500 can determine whether the standard material is re-measured or the abnormality of the apparatus using the matrix peak have.

In addition, when the reference material is not included in all of the items previously stored in the reference material, the data processor 500 reflects the RT change rate of the redundant component, The reference RT can also be corrected.

In addition, in the present invention, the chromatography may be performed by a gas chromatograph (GC), a gas chromatography-mass spectrometry (GC-MS), a liquid chromatography (LC) (Ion Chromatography-Mass Spectrometry), IC-MS (Ion Chromatography-Mass Spectrometry), and the like. Lt; / RTI >

The present invention relates to a method of measuring a sample continuously and automatically measuring components of a sample on a chromatographic basis, comprising the steps of measuring a reference material and detecting and storing a detection time (hereinafter, referred to as 'RT' a) step SlOO; B) measuring (S200) a sample sample to detect RT for a component contained in the sample sample; And c) analyzing a component of the sample sample by comparing the RT detected in step b) with the reference RT stored in step a) (step S300).

If the sample is injected after the step c), the procedure goes back to the step b), and if the condition or the cycle becomes a predetermined period, .

In the step d), when the reference material does not contain all the components previously stored in the reference material, it is preferable to reflect the change rate of the RT with respect to the redundant component, The reference RT can also be updated.

In addition, the step a) may include a-1) S110 injecting a reference material; A-2) a step (S120) of measuring the reference material to detect and store a reference RT for each component; And a-3) setting (S 130) an error range of the reference RT for each component; And the step c) may be determined as a corresponding component when the RT detected in step b) is within the error range of the reference RT of the specific component set in step a-3).

In addition, the step a) includes: a-4) a step (S140) of setting an approximate range wider than the error range set in the step a-3); (C-1) step (S310) of determining that the at least one RT detected in step (b) is a corresponding component when the RT is within the error range of the reference RT with respect to the previously stored specific component, ; C-2) (S320) of re-measuring the standard material and updating the reference RT according to the composition when the RT is out of the error range but within the approximate range; And c-3) analyzing components of the sample sample by re-applying the updated reference RT to the RT of the sample sample detected in the step b) or from the sample sample injected thereafter; . ≪ / RTI >

If the reference material and the sample sample include a matrix component, the step c) may include determining whether the RT of the matrix component detected in step b) is within an error range of the reference RT with respect to the predetermined matrix component (C-1 ') step (S310') for discriminating whether or not it is possible to discriminate between the two groups; And c-2 for analyzing the components of the sample sample by comparing the RT for the remaining components with the reference RT when the RT for the matrix component is out of the error range, ') Step S320'.

In addition, the present invention can provide a computer-readable recording medium on which a program for implementing the chromatography-based automatic sample measurement method is stored.

Finally, the present invention can be provided by a program stored in a computer-readable recording medium in order to implement the chromatography-based automatic sample measurement method.

The chromatographic-based automatic sample measurement apparatus and method of the present invention are advantageous in that accurate reference qualitative and quantitative analysis can always be performed by automatically re-measuring a reference material and correcting a reference RT according to a predetermined condition or cycle.

Further, according to the present invention, by setting the approximate range that is wider than the error range with respect to the reference RT of each component, the sample is measured, and if the detected RT deviates from the error range and exists in the approximate range, By reanalyzing the measured data, it is possible to analyze the sample more accurately.

In addition, when the matrix material is included in the reference material and the sample sample, there is an advantage that the mattress peak and the RT of the remaining components can be simultaneously managed to determine whether the measurement apparatus is abnormal or whether the reference material is re-measured.

Lastly, the present invention can also correct the reference RT of a component that is not included in the reference material by reflecting the rate of change of the RT with respect to the redundant component when all the items stored in the reference material are not included in the reference material re-measurement Thereby making it possible to efficiently update the reference RT.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing an automatic sample measurement apparatus according to an embodiment of the present invention; FIG.
2 is a flowchart showing Embodiment 1 of the automatic sample measurement method of the present invention.
FIG. 3 is a graph showing a process of analyzing components of a sample using a reference RT.
4 is a flowchart showing a second embodiment of the automatic sample measurement method of the present invention.
5 is a flowchart showing a third embodiment of the automatic sample measurement method of the present invention
Figure 6 is an example of a graph in which RT for a matrix component is detected.
7 is an example of a graph showing a reference RT setting process according to the fourth embodiment of the present invention.

Hereinafter, the technical idea of the present invention will be described more specifically with reference to the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which are included to provide a further understanding of the technical concept of the present invention, are incorporated in and constitute a part of the specification, and are not intended to limit the scope of the present invention.

FIG. 1 is a schematic block diagram showing an automatic sample measurement apparatus according to an embodiment of the present invention.

The present invention relates to a sample measuring apparatus for automatically measuring a component of a sample on the basis of a chromatograph. The sample measuring apparatus includes a channel integrating module 100, a sample injecting unit 200, a column 300, a measuring unit 400, a data processing unit 500, and a control unit 600.

The chromatographic analytical method used in the present invention may be a gas chromatographic method, a gas-chromatography-mass spectrometry (GC-MS) method, a liquid chromatography (LC) (Ion Chromatography-Mass Spectrometry), IC (Ion Chromatography-Mass Spectrometry), IC (Chromatography-Mass Spectrometry) Lt; / RTI >

GC and GC-MS are cases where the mobile phase is gas, and LC, LC-MS, IC, IC-MS are cases where the mobile phase is liquid. At this time, IC and IC-MS belong to the category of LC, but they are distinguished in that they are intended to separate ions. Also, MS means mass spectrometry, in which mass spectrometry as well as chromatographic analysis is performed.

As shown in FIG. 1, the channel integration module 100 is a module for channel integration. The channel integration module 100 selectively connects a sample stored in the reference material storage 10 or a sample to be measured, 200). Here, the reference material is used to set the detection time (referred to as "RT" hereinafter) as a reference for each component, which is a sample that already knows what component is contained. In the case of GC and GC-MS, the reference material is gas, and in the case of LC, LC-MS, IC, IC-MS, solution is used.

Also, at least one of the sample and reference materials is used, and flows into the channel integration module 100 so that the sample is periodically supplied to the sample loop 210 by a pump or pressure.

The sample injection unit 200 includes a sample loop 210 in which a sample of a reference material or a sample transferred from the channel integration module 100 and a mobile phase material transferred from the mobile phase storage unit 20 are respectively injected . The sample injection unit 200 injects a predetermined amount of sample and mobile phase material into the column 300, and the sample injected from the column 300 is separated.

The column 300 is used as a fixed phase in chromatography. When the mobile phase injects a sample filled in the sample loop 210 in a fixed phase, separation occurs depending on the characteristics of the components contained in the sample.

Then, the measuring unit 400 measures a signal of components contained in the sample separated from the column 300, and the data processing unit 500 detects RT from the signal measured by the measuring unit 400. At this time, when the sample is a standard material, it is possible to know which RT of the detected RT is with respect to which component. Therefore, the RT is set as a reference RT for each component and stored in a database (DB). Alternatively, if the sample is a sample, the detected RT is compared with the RT of the stored component to analyze the components of the sample.

The control unit 600 includes a channel integration module 100, a sample injection unit 200, a column 300, a measurement unit 400, and a data processing unit 500, which constitute a sample measurement apparatus according to an embodiment of the present invention. ).

The control unit 600 controls the flow integrating module 100 such that the sample sample to be analyzed is supplied automatically or manually to the sample injecting unit 200 so that the sample can be continuously subjected to qualitative and quantitative analysis .

In addition, the control unit 600 controls the flow path integration module 100 to move the reference material to the sample injection unit 200 according to preset conditions or cycles. The injected reference material is measured while passing through the measuring unit 400, receives the measurement signal from the data processing unit 500, calculates the component RT, and updates the reference RT.

That is, the control unit 600 may periodically transmit the reference material stored in the reference material storage unit 10 to the sample injection unit 200 at predetermined time intervals to periodically update the reference RT, Temperature, humidity, etc.) are changed more than the set value, it is possible to automatically control the reference material to be re-measured.

Although the data processor 500, the database DB, and the controller 600 are separately configured according to their respective roles, it is needless to say that the data processor 500, the database DB, and the controller 600 may be one processing device such as a computer device.

An automatic sample measurement method according to an embodiment of the present invention will be described step by step by using the automatic sample measurement apparatus having the above-described configuration.

FIG. 2 is a flow chart showing the first embodiment of the automatic sample measurement method of the present invention, and FIG. 3 is an example of a process of analyzing a sample sample using the reference RT.

As shown in FIG. 2, a) step S100 is performed in which the reference material is first measured and the reference RT for each component is detected and stored. That is, under the control of the control unit 600, the reference material is transferred from the channel integration module 100 to the sample injection unit 200, and the standard material and the mobile phase material are injected into the column 300 by the sample injection unit 200 do. Thereafter, the measuring unit 400 measures the signals of the components contained in the reference material separated from the column 300, and the data processing unit 500 detects the RTs of the components from the measurement signals. At this time, since the data processing unit 500 already knows the components included in the reference material, the detected data of each component is stored in the database as the reference RT.

In step b), the RT of the sample contained in the sample is measured in step S200. In step c), the data processor 500 detects the RT detected in step b) Is compared with the reference RT stored in step a) to analyze the components of the sample sample (S300). In addition, the data processing unit 500 performs quantitative analysis by comparing the sensitivity of the peak with the peak sensitivity of each stored reference material.

In addition, according to an embodiment of the present invention, if another sample sample for analysis is injected after step c), it returns to step b) and continuously qualitatively and quantitatively analyzes the samples. D) step (S400) of updating the reference RT for each component so that the material is re-measured.

In the case of analyzing sample samples continuously using the initial reference RT, the stationary phase changes its characteristics over time, and the mobile phase is exposed to the outside, so that contaminants may be included. In addition, RT is changed.

Therefore, in the case of the conventional automatic sample measuring apparatus, there is a disadvantage that it is difficult to accurately analyze the time after the setting of the reference RT since the apparatus for automatically resetting the reference RT is not provided. In particular, if the sample is very small, re-measurement is not possible, so even if the analysis is wrong, it can not be reanalyzed.

As described above, according to the present invention, the reference material is automatically re-measured when the preset condition is reached, and the reference RT according to each component is corrected, so that accurate qualitative and quantitative analysis is always possible.

On the other hand, as shown, step a) can be divided into the following detailed steps. 2) a step (S120) of detecting and storing a reference RT for each component by measuring a reference material, and a (2) a step (S120) of setting an error range of the reference RT -3) step S130.

That is, when the reference material is injected and measured, the data processing unit 500 detects the RT of each component of the reference material and sets the error range of the detected RT of each component. At this time, the error range may be set within the range of ± x% collectively by the center value of the reference RT, or separately for each component.

When the sample is injected in step b), the data processing unit 500 checks whether the RT detected by the measuring unit 400 is within an error range of the reference RT of the specific component set in step a-3) If it is within the error range, it is determined to be the component (S200). If it is not within the error range, qualitative, quantitative analysis can be performed, or data error or inaccuracy can be indicated in the result value after analysis.

The graph shown in FIG. 3 (a) is a graph in which the abscissa is the time and the ordinate is the intensity, and is an example of the result detected by the measuring unit 400 in the standard material measurement. As shown, component A generates a peak after a lapse of time, so the data processing unit sets the reference RT of the component A to r1 and the reference RT of the component B to r2.

3 (b) is an example of the result detected by the measuring unit 400 when the sample is measured. When the time at which the peak occurs is within a + a1, it is confirmed that the sample A contains the component A, The sensitivity is compared and quantified.

4 is a flowchart showing a second embodiment of the automatic sample measurement method of the present invention. In the case of Embodiment 2, since all the steps of Embodiment 1 described above are included, only the added portions will be described in detail.

As shown in FIG. 4, the reference material is measured through the steps a-1) to a-3) to set the reference RT for each component and sets the error range thereof. Additionally, in the step a-4) A wider approximation range is set (S140).

The next step b) is the same as that of the first embodiment, and the subsequent step c) consists of the following three steps.

That is, step c-1) is a step S310 in which the data processing unit 500 determines that the at least one RT detected in step b) is a corresponding component when it is within the error range of the reference RT with respect to the previously stored specific component If the RT is out of the error range and is within the set approximate range, the controller 600 controls the device so that the reference material RT is updated in step c-2) . Finally, in step c-3), the data processing unit 500 applies the updated reference component RT to the RT of the sample sample detected in step b) (S330). ≪ / RTI >

In this case, although the process of reapplying the sample to the RT of the sample sample detected in the step b) is shown in the drawing, instead of reapplication, the step b) is performed after the step c-2) can do.

That is, the fact that the RT of the sample is present in the approximate range in the second embodiment of the present invention means that the RT of the sample is not within the error range when compared with the reference RT, Is changed, it is necessary to correct the reference RT and to reanalyze the previously measured data.

Fig. 3 (c) is a graph when the RT for a specific component is within the approximate range of the reference RT with respect to the component A, when the sample is measured after a certain period of time. Here, the approximate range is a-a2 to a-a1 and a + a1 to a + a2. If the RT for the component A 'after the reference RT correction is still not within the error range of the reference RT, then the component A' is not qualified and quantified as the component A.

Therefore, according to the second embodiment of the present invention, there is an advantage that the sample RT can be more accurately analyzed through the approximate range setting while periodically re-measuring the reference material to correct the reference RT.

FIG. 5 is a flowchart showing a third embodiment of the automatic sample measurement method of the present invention, and FIG. 6 is an example of a graph in which RT for a matrix component is detected. Embodiment 3 is a case where a matrix component is included in a standard material and a sample sample, and a description overlapping with Embodiment 1 will be omitted, and only different portions will be described.

The measurement method according to the third embodiment of the present invention is a method in which when the matrix peak is generated in the detection result of the measurement unit 400, the data processing unit 500 performs a remeasurement of the reference material using the matrix peak M Or whether the device is abnormal.

When using ion chromatograph-based sample measurement equipment, DI water becomes a matrix component when a solution in which various components are dissolved in ionic state in DI (Deionized) water is used as a standard material (sample sample is also the same). Since DI water is a solution from which ions are removed, the conductivity is low, and as a result, a negative peak is generated as shown in FIG. 6, and this is called a matrix peak (M). For reference, the matrix peak may be a positive peak or a negative peak depending on the property.

For example, when analyzing Cl - ions present in DI water in ion chromatography, the matrix component is DI water and the target component is Cl - . At this time, the matrix component has no influence on the correlation between the fixed phase and the moving phase, and is determined by hardware factors such as the flow rate of the mobile phase (the supply flow rate of the pump), the volume of the flow path and the distance to the measurement unit 400, A matrix peak is generated at the same time using the device. On the other hand, in the case of Cl - ions, the RT varies depending on the performance factors of the stationary phase and the mobile phase in addition to the above-mentioned hardware factors.

In the case of an automated measuring device, the performance of the stationary phase is gradually deteriorated when CO2 is continuously used, and CO2, moisture and the like are absorbed by the mobile phase, resulting in a change of the moving phase naturally resulting in a change of RT.

Therefore, when a matrix component is included, RT (rm) of the detected matrix peak can be utilized as a reference value. That is, as shown in FIG. 5, step c) comprises steps c-1 ') and c-2').

Step c-1 ') is a step S310' of determining whether or not the RT of the detected matrix component is within the error range of the reference RT for the predetermined matrix component. When setting the reference RT using the reference material in the step a-3), the reference RT for the matrix component is also set so that the RT for the matrix component is first compared.

If the RT of the matrix component deviates from the error range in step c-2 ', it is judged that there is an abnormality in the measuring apparatus. Since the matrix peaks must always be detected at the same time when the hardware conditions are the same, it is determined that there is an abnormality in the apparatus when the matrix peak is not within the error range, and the apparatus check is performed. Or, if it is within the error range, the RT of the remaining components is compared with the reference RT to analyze the components of the sample (S320 ').

Specifically, if at least one of the RTs for the remaining components except for the matrix peak deviates from the error range of the reference RT, the standard RT is re-measured to update the reference RT for each component, Lt; RTI ID = 0.0 > RT < / RTI >

Thus, according to the third embodiment of the present invention, the RT of the remaining components is simultaneously managed in conjunction with the matrix peak, thereby enabling to check whether the apparatus is being inspected or qualitative and quantitative analysis of the sample sample through re- .

Also, in the case of a device in which a system peak is generated that is not related to the action of the mobile phase and the stationary phase, the change of the peak can be used for the same purpose as the matrix peak.

Finally, a fourth embodiment of the automatic sample measurement method of the present invention will be described with reference to FIG. In the fourth embodiment, when the standard material is not included in all of the items previously stored in the reference material, the data processor 500 may include the standard deviation of the RT change rate for the redundant component in step d) And the reference RT of the component that does not exist is also corrected and updated.

Figure 7 (a) is a graphical representation of the reference RT for each component stored in the database through standard material measurements. As shown, it is assumed that the reference RT for components A and B is stored.

FIG. 7 (b) is a graph that is detected by the measuring unit 400 when the standard material (reference material 2) changed after a predetermined time has been re-measured. At this time, component B can not be corrected if only component A is included in reference material 2. In Example 4 of the present invention, the rate of change of RT of the previously measured reference material and the overlapped content of the reference material 2 measured later is calculated. That is, if the degree of change in the case of the component A is a ', it is also applied to the component B to correct the reference RT for the component B as indicated by the dotted line.

As described above, in the case where the components of all the items previously stored in the reference material are not included in the reference material, the reference RT of the components not included in the reference material is also reflected Thereby making it possible to efficiently update the reference RT.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Although the automatic sample measurement method based on the chromatography according to various embodiments of the present invention has been described above, it is possible to provide a computer-readable recording medium on which a program for implementing the automatic sample measurement method is stored and a computer Of course, a program stored in a readable recording medium can also be implemented.

That is, those skilled in the art will readily understand that the above-described automatic sample measurement method can be provided in a recording medium that can be read by a computer by tangibly embodying a program of instructions for implementing the same.

In other words, it can be implemented in the form of a program command that can be executed through various computer means, and can be recorded on a computer-readable recording medium.

The computer-readable recording medium may include program commands, data files, data structures, and the like, alone or in combination.

The program instructions recorded on the computer-readable recording medium may be those specially designed and configured for the present invention or may be those known and available to those skilled in the computer software. Examples of the computer-readable medium include magnetic media such as hard disks, floppy disks and magnetic tape, optical media such as CD-ROMs and DVDs, and optical disks such as floppy disks. Magneto-optical media and hardware devices specifically configured to store and execute program instructions such as ROM, RAM, flash memory, USB memory, and the like.

The computer-readable recording medium may be a transmission medium such as a light or metal line, a wave guide, or the like, including a carrier wave for transmitting a signal designating a program command, a data structure, and the like.

Examples of program instructions include machine language code such as those produced by a compiler, as well as high-level language code that can be executed by a computer using an interpreter or the like.

The hardware device may be configured to operate as one or more software modules to perform the operations of the present invention, and vice versa.

10: standard material storage unit 20: mobile phase storage unit
100: Euro integration module
200: sample injection unit 210: sample loop
300: column
400:
500:
600:

Claims (14)

A sample measuring apparatus for automatically measuring a component of a sample based on chromatography,
A channel integration module (100) for selectively transporting a sample of a standard material or a sample for measurement to set a detection time (Retention Time, hereinafter referred to as 'RT') as a reference for each component;
A sample injection unit 200 including a sample loop 210 into which the sample and the mobile phase material are injected;
A column 300 into which a sample is injected and separated from the sample injection unit 200;
A measurement unit 400 for measuring a signal of components contained in the sample separated in the column 300;
The RT is detected from the signal measured by the measuring unit 400. If the sample is a reference material, the detected RT is stored as a reference RT for each component. If the sample is a sample, A data processing unit 500 for analyzing the components of the sample sample in comparison with the reference RT; And
A control unit 600 for controlling the reference material to be moved to the sample injection unit 200 according to preset conditions or cycles to update the reference RT for each component;
/ RTI >
The data processing unit 500
Sets an error range of the reference RT for each component,
And determining, when the detected RT of the sample sample is within the error range of the reference RT of the specific component set, the component.
delete The method according to claim 1,
The data processing unit (500)
If at least one RT of the detected sample sample is within an approximate range that is out of the error range of RT with respect to the specific component set,
And the reference material is re-measured by the controller 600 so as to correct the reference RT for each component, and then reapplied to the RT of the sample sample measured before or applied from the sample sample to be injected thereafter. Automatic sample measuring device.
The method according to claim 1,
The data processing unit (500)
Wherein a matrix peak is used to determine whether the reference material is re-measured or whether the apparatus is abnormal, when a matrix peak occurs in the measurement result of the measurement unit (400) Measuring device.
The method according to claim 1,
The data processing unit (500)
Wherein the reference RT of the component not included in the reference material is also reflected by reflecting the rate of change of RT with respect to the redundant component when the reference material does not contain any of the components previously stored in the reference material. Chromatography - based automated sample measurement device.
The method according to claim 1,
The chromatography can be carried out using,
Gas chromatography, mass spectrometry (GC-MS), liquid chromatography (LC), liquid chromatography-mass spectrometry (LC-MS) Chromatography-based mass spectrometry (IC-MS), which is characterized in that it is one of the analytical methods selected from chromatography (Ion Chromatography), ion chromatography (IC), and ion chromatography (mass spectrometry) Automatic sample measuring device.
A sample measuring method for automatically measuring a component of a sample based on chromatography,
a) detecting and storing a reference time (Retention Time, hereinafter referred to as 'RT') (S100) by measuring a reference material;
b) measuring the sample sample to detect the RT of the components contained in the sample sample (S200); And
c) comparing the RT detected in step b) with the reference RT stored in step a) (S300), analyzing the components of the sample sample;
And,
The step a)
a-1) injecting a reference material (S110);
a-2) measuring the reference material to detect and store a reference RT for each component (S120); And
a-3) setting each error range of the reference RT for each component (S130);
And,
The step c)
And determining that the RT detected in the step b) is a corresponding component when the RT is within the error range of the reference RT of the specific component set in the step a-3).
8. The method of claim 7,
After step c)
d) if the sample is injected, returning to step b), and if the condition or cycle has been set in advance, re-measuring the reference material to update the reference RT for each component (S400);
The method comprising the steps of:
9. The method of claim 8,
The step d)
When the reference material is not included in all of the items previously stored in the reference material, the reference RT for components not included in the reference material is also updated by reflecting the rate of change in RT with respect to the redundant component Based on an automatic sample measurement method.
delete 8. The method of claim 7,
The step a)
a-4) setting an approximate range wider than the error range set in the step a-3); Further comprising:
The step c)
c-1) determining (S310) that at least one RT detected in step b) is a corresponding component when the RT is within an error range of the reference RT with respect to the previously stored specific component;
c-2) when the RT is out of the error range but within the approximate range, re-measuring the reference material and updating the reference RT according to the component (S320); And
c-3) analyzing the component of the sample sample by re-applying the updated reference RT to the RT of the sample sample detected in the step b) or applying the reference RT from the sample sample injected thereafter (S330);
Wherein the first and second chromatograms are generated in a time domain.
8. The method of claim 7,
When the standard material and the sample sample include a matrix component,
The step c)
c-1 ') determining whether the RT of the matrix component detected in the step b) is within an error range of the reference RT with respect to the predetermined matrix component (S310'); And
If the RT of the matrix component is out of the error range, it is determined that there is an abnormality in the measuring device. If the RT is within the error range, the RT of the remaining components is compared with the reference RT to analyze the components of the sample. (S320 ');
Wherein the first and second chromatograms are generated in a time domain.
A computer-readable recording medium on which a program for implementing a chromatography-based automatic sample measurement method according to any one of claims 7 to 9, 11, and 12 is stored.
A program stored in a computer-readable recording medium for implementing a chromatographic automatic sample measurement method according to any one of claims 7 to 9, 11 and 12.
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