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WO2016001979A1 - Appareil d'introduction automatique d'échantillons, procédé d'introduction d'échantillons et programme - Google Patents

Appareil d'introduction automatique d'échantillons, procédé d'introduction d'échantillons et programme Download PDF

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Publication number
WO2016001979A1
WO2016001979A1 PCT/JP2014/067409 JP2014067409W WO2016001979A1 WO 2016001979 A1 WO2016001979 A1 WO 2016001979A1 JP 2014067409 W JP2014067409 W JP 2014067409W WO 2016001979 A1 WO2016001979 A1 WO 2016001979A1
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WO
WIPO (PCT)
Prior art keywords
internal standard
sample
standard solution
tip
needle
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PCT/JP2014/067409
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English (en)
Japanese (ja)
Inventor
俊和 箕畑
Original Assignee
株式会社島津製作所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社島津製作所 filed Critical 株式会社島津製作所
Priority to PCT/JP2014/067409 priority Critical patent/WO2016001979A1/fr
Priority to JP2016530704A priority patent/JPWO2016001979A1/ja
Publication of WO2016001979A1 publication Critical patent/WO2016001979A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation

Definitions

  • the present invention relates to an automatic sample introduction device, a sample introduction method, and a program.
  • sample / internal standard mixed solution a solution containing an internal standard substance (internal standard solution) is added to each well in which the filter paper is accommodated, and blood components in the filter paper are extracted into the solution.
  • sample / internal standard mixed solution a solution containing an internal standard substance
  • autosampler an automatic sample introduction device
  • a sample introduction procedure using a conventional automatic sample introduction apparatus will be described with reference to FIGS.
  • the tip of the needle 316 provided in the automatic sample introduction device is inserted into the well 312 of the sample plate 311.
  • the ports a to l provided in the two flow path switching valves 322 and 323 are in communication with each other as shown in FIG. That is, the needle 316 and the sample loop 318 connected to the proximal end thereof are connected to the metering pump 319 via the flow path switching valve 322.
  • the sample / internal standard mixed solution in the well 312 is sucked from the tip of the needle 316 by the action of the metering pump 319.
  • the tip of the needle 316 is inserted into the injection port 320 and the flow path is switched by the flow path switching valve 322.
  • the ports a to f provided in the flow path switching valve 322 are in communication with each other as shown in FIG. That is, the needle 316 and the sample loop 318 are inserted into the flow of the carrier liquid channel from the carrier liquid reservoir 324 to the mass spectrometer (MS).
  • MS mass spectrometer
  • each component in the introduced sample / internal standard mixture is ionized and separated and detected for each mass.
  • a mass spectrum is generated with the mass-to-charge ratio (m / z) on the horizontal axis and the signal intensity on the vertical axis, and the ratio of the signal intensity of the disease indicator substance to the signal intensity of the internal standard substance on the mass spectrum Based on this, the disease indicator substance is quantified. And when this fixed value exceeds the predetermined threshold value, it determines with it being positive.
  • the internal standard substance it is necessary to use a substance having characteristics similar to the substance to be quantified and having a peak at a position that is close to the peak of the substance to be quantified on the mass spectrum and can be separated from the peak. is there. Therefore, as an internal standard substance in the above-mentioned neonatal mass screening, a substance obtained by substituting a part of a predetermined amino acid or a predetermined acylcarnitine as a disease indicator substance with a stable isotope is used. However, these are generally expensive to manufacture and expensive. In the newborn mass screening, a mixture of multiple types (for example, 20 types) of internal standard substances corresponding to multiple disease index substances is used as the above internal standard solution so that many diseases can be examined by one mass analysis. In addition, the cost of the internal standard solution is one factor that increases the inspection cost. Therefore, it is required to reduce the amount of the internal standard solution used in one inspection.
  • neonatal mass screening is used as an example.
  • the amount of internal standard used to reduce analysis costs in quantitative analysis for various purposes using mass spectrometers and other analyzers is not limited thereto. It is hoped that this will be suppressed.
  • the present invention has been made in view of the above points, and its object is to reduce the amount of internal standard substance used in quantitative analysis (internal standard method) using an internal standard substance. is there.
  • An automatic sample introduction device which has been made to solve the above problems, a) a tubular needle; b) an injection port communicating with the analysis flow path; c) moving means for changing a relative position between the needle, the sample solution container, the internal standard solution container, and the injection port; d) suction / discharge means for sucking and discharging liquid through the needle; e) control means for controlling the moving means and the suction / discharge means; With Further, the control means includes f) An internal standard solution in which the tip of the needle is inserted into the internal standard solution container, and an internal standard solution that is a liquid containing an internal standard substance contained in the internal standard solution container is sucked from the tip into a predetermined amount.
  • Suction control means g) a sample liquid suction control means for inserting the tip of the needle into the sample liquid container and sucking a predetermined amount of the sample liquid stored in the sample liquid container from the tip; h) a discharge control means for inserting the tip of the needle into the injection port, and discharging the internal standard solution and the sample solution from the tip;
  • the control unit may cause the needle to suck either the sample solution or the internal standard solution first.
  • the moving means may change the relative position by moving only the needle, and moves at least one of the sample liquid container, the internal standard liquid container, and the injection port in addition to or instead of the needle. Thus, the relative position may be changed.
  • a person in charge of inspection stores a sample and an internal standard in advance in a sample solution container (well), and the automatic sample introduction device uses the sample solution container.
  • a predetermined amount of the liquid inside was sucked and introduced into the analysis channel from the injection port.
  • the person in charge of the test extracts a dry filter paper blood sample with an internal standard solution of 100 ⁇ L, and then the obtained extract (mixture of blood component and internal standard substance) is used as the sample solution.
  • the sample was contained in a container, and an automatic sample introduction device collected 1 ⁇ L of the extract with a needle and introduced it into the analysis channel. Therefore, most of the internal standard solution contained in the sample solution container (99 ⁇ L in 100 ⁇ L in this example) was not used for analysis and was wasted.
  • the sample solution and the internal standard solution stored in separate containers are needled. Then, the needle is inserted into the injection port, and the sample solution and the internal standard solution are introduced into the analysis channel at once.
  • the dry filter paper blood sample is extracted with 100 ⁇ L of a predetermined solvent (for example, methanol) not containing an internal standard substance, and the obtained extract (sample solution) is stored in a sample solution container. Keep it.
  • the internal standard solution is stored in an internal standard solution container provided separately from the sample solution container.
  • the automatic sample introduction device collects 1 ⁇ L each of the internal standard solution in the internal standard solution container and the sample solution in the sample solution container, and injects them into the analysis channel at once.
  • the internal standard solution that is not sucked by the needle and remains in the internal standard solution container is used in the next analysis, that is, when the sample solution stored in another sample solution container is introduced. Therefore, most of the internal standard solution is not wasted as in the prior art.
  • the internal standard solution consumed in one analysis that is, the analysis of the sample solution contained in one sample solution container
  • the minimum amount (1 ⁇ L in this example) used for the analysis It becomes possible.
  • a sample introduction method according to the present invention made to solve the above problems is as follows. a) An internal standard solution in which the tip of a tubular needle is inserted into an internal standard solution container, and an internal standard solution that is a liquid containing an internal standard substance contained in the internal standard solution container is sucked from the tip into a predetermined amount.
  • a suction process b) a sample solution suction step of inserting the tip into a sample solution container and sucking a predetermined amount of the sample solution stored in the sample solution container from the tip; In this order or vice versa, c) a discharge step of inserting the tip into an injection port communicating with the analysis channel and discharging the sample liquid and the internal standard solution from the tip;
  • the sample is introduced into the analysis flow path by executing It is characterized in that the internal standard solution is sucked from the same internal standard solution container in each of the plurality of sample introductions.
  • the automatic sample introduction device and the sample introduction method of the present invention it is possible to suppress the consumption of the internal standard substance in the quantitative analysis by the internal standard method.
  • the schematic diagram which shows schematic structure of the automatic sample introduction apparatus by one Embodiment of this invention The block block diagram of the control part in the said automatic sample introduction apparatus.
  • sucked sample liquid in the said automatic sample introduction apparatus The schematic diagram which shows the state which has inject
  • FIG. 1 is a schematic configuration diagram of an automatic sample introduction apparatus according to an embodiment of the present invention.
  • the automatic sample introduction apparatus of the present embodiment introduces a sample into a mass spectrometer (MS), and includes an operation unit 110 that performs sample introduction operation and a control unit 130 that controls the operation unit 110. Is done.
  • MS mass spectrometer
  • the operation unit 110 includes a plate mounting unit 113 on which the sample plate 111 is set, an internal standard solution container mounting unit 115 on which the internal standard solution container 114 is set, and a cylindrical needle having a tapered tip.
  • a needle drive mechanism 117 including a motor and the like for moving the needle 116 in the horizontal and vertical directions, a sample loop 118 connected to the proximal end of the needle 116, a metering pump 119, an injection port 120, a needle 116, a cleaning port 121 for cleaning the sample loop 118, a first flow path switching valve 122, and a second flow path switching valve 123 are included.
  • Each of the first flow path switching valve 122 and the second flow path switching valve 123 is a 6-port 2-position valve.
  • the communication state between matching ports can be switched.
  • the port a of the first flow path switching valve 122 has a liquid feeding pump 125 connected to the carrier liquid reservoir 124, the port b has a sample loop 118, the port c has a metering pump 119, and the port d has a second flow.
  • a port g of the path switching valve 123 is connected to the port e, the injection port 120 is connected to the port e, and a flow path (hereinafter referred to as “analysis flow path 126”) to the mass spectrometer is connected to the port f.
  • the port g of the second flow path switching valve 123 is the port d of the first flow path switching valve 122, the port h is the drain, the port i is the metering pump 119, the port j is the cleaning port 121, A cleaning liquid reservoir 127 storing a cleaning liquid is connected to the port l, and the port k is closed.
  • the metering pump 119 and the liquid feed pump 125 correspond to the suction / discharge means in the present invention.
  • the control unit 130 is a computer such as a personal computer, and as shown in FIG. 2, a monitor (display unit) including a CPU (Central Processing Unit) 131 that is a central processing unit, a memory 132, an LCD (Liquid Crystal Display), and the like. ) 133, an input unit 134 made up of a keyboard, a mouse, and the like, and a storage unit 135 made up of a mass storage device such as an HDD (Hard Disk Drive) or an SSD (Solid State Drive) are connected to each other.
  • the storage unit 135 stores an OS (Operating System) 136 and an injection operation control program 137.
  • OS Operating System
  • the control unit 130 further has an interface (I / F) for direct connection with an external device (here, the operation unit 110) and connection with the external device via a network such as a LAN (Local Area Network). 138 and is connected to the operation unit 110 via the I / F 138 via a network cable or a wireless LAN.
  • I / F interface for direct connection with an external device (here, the operation unit 110) and connection with the external device via a network such as a LAN (Local Area Network).
  • a network such as a LAN (Local Area Network).
  • FIG. 2 shows an internal standard solution suction control unit 139, a sample solution suction control unit 140, and a discharge control unit 141 as related to the injection operation control program 137.
  • These are basically functional means realized by software by the CPU 131 reading the injection operation control program 137 into the memory 132 and executing it.
  • the injection operation control program 137 is not necessarily a single program, and may be a function incorporated in a part of a program for controlling the mass spectrometer, for example, and its form is not particularly limited.
  • sample pretreatment is performed in the following procedure. That is, the person in charge of the test cuts out a portion containing the blood of each subject from the dried filter paper blood sheet sent from a medical institution or the like, and accommodates each in a well on the sample plate. Then, a predetermined amount (for example, 100 ⁇ L) of blood component extraction liquid is added to each well in which the filter paper is accommodated.
  • a liquid for example, methanol
  • a liquid containing an internal standard substance is used instead of a liquid containing an internal standard substance as in the prior art.
  • sample liquid the liquid stored in each well 112 (corresponding to the sample liquid container in the present invention) of the sample plate 111 is referred to as “sample liquid”.
  • the person in charge of the inspection sets the internal standard solution container 114 containing the liquid containing the internal standard substance (internal standard solution) on the internal standard solution container mounting unit 115 of the automatic sample introduction device.
  • the sample solution and the internal standard solution are collected in the operation unit 110 under the control of the injection operation control program 137, and the mass spectrometer. To be introduced. A procedure for introducing the sample solution and the internal standard solution at this time will be described with reference to the flowchart of FIG. 3 and FIGS. 1, 4, and 5.
  • the injection operation control program 137 sets a variable n representing the number of the well 112 on the sample plate 111 to 1 (step S11).
  • the internal standard solution suction control unit 139 causes the needle 116 to suck the internal standard solution stored in the internal standard solution container 114 (step S12). Specifically, first, the first flow path switching valve 122 and the second flow path switching valve 123 are controlled to bring the ports a to f and g to l into the communication state shown in FIG. As a result, the sample loop 118 and the metering pump 119 are connected via the first flow path switching valve 122 and the second flow path switching valve 123, and further attached to the carrier liquid reservoir 124 via the first flow path switching valve 122. The liquid feed pump 125 and the analysis flow path 126 are connected.
  • the needle drive mechanism 117 is controlled to insert the tip of the needle 116 into the internal standard solution container 114 (FIG. 1), and a predetermined amount (for example, 1 ⁇ L) of the internal standard solution is sucked by the metering pump 119.
  • the sample liquid suction control unit 140 controls the needle driving mechanism 117 to insert the tip of the needle 116 into the nth (that is, first) well 112 on the sample plate 111 (FIG. 4), and further measures.
  • the pump 119 is controlled to cause the sample liquid in the well 112 to be sucked into the needle 116 by a predetermined amount (for example, 1 ⁇ L) (step S13). As described above, a predetermined amount of the sample solution and the internal standard solution are collected in the needle 116.
  • the discharge control unit 141 controls the needle drive mechanism 117 to insert the needle 116 into the injection port 120, and puts the first flow path switching valve 122 into the state shown in FIG. Thereby, a flow path is formed from the carrier liquid reservoir 124 to the analysis flow path 126 through the liquid feed pump 125, the port a, the port b, the needle 116, the injection port 120, the port e, and the port f.
  • the carrier liquid fed by the liquid feeding pump 125 passes through the sample loop 118 and the needle 116, the sample liquid and the internal standard liquid that existed in the sample loop 118 and / or the needle 116 are used. Is pushed away by the carrier liquid and introduced into the mass spectrometer through the injection port 120 and the analysis flow path 126 (step S14).
  • the injection operation control program 137 executes needle cleaning using the cleaning port 121 (step S15). Specifically, the second flow path switching valve 123 is switched as shown in FIG. 6 so that the cleaning liquid reservoir 127 and the metering pump 119 communicate with each other, and the cleaning liquid in the cleaning liquid reservoir 127 is transferred to the syringe of the metering pump 119 by the suction operation of the metering pump 119. Aspirate into. Subsequently, the needle 116 and the sample loop 118 are disconnected from the flow of the carrier liquid by switching the first flow path switching valve 122 as shown in FIG.
  • the needle driving mechanism 117 is controlled to insert the needle 116 into the cleaning port 121, and the cleaning liquid in the syringe is sent out by the discharge operation of the metering pump 119.
  • the cleaning liquid is fed into the sample loop 118, passes through the needle 116, and is discharged to the cleaning port 121.
  • the cleaning liquid is repeatedly sucked and discharged, and the cleaning operation is finished when a predetermined amount of liquid is delivered.
  • the injection operation control program 137 determines whether or not all the samples on the sample plate 111 have been introduced (step S16). The variable n is incremented (step S17). Then, it waits for a predetermined time until the next analysis can be performed in the mass spectrometer (step S18), and the process returns to step S12. Thereafter, steps S12 to S18 are repeatedly executed, and a series of sample injection operations are completed when introduction of all the samples is completed (when it becomes Yes in step S16).
  • the internal standard solution and the sample solution stored in separate containers are sequentially collected by the needles, and these are simultaneously introduced into the mass spectrometer. .
  • the sample solution is sucked from different wells 112 (sample solution containers) each time, whereas the internal standard solution is collected from the same internal standard solution container 114 each time. That is, the internal standard solution remaining in the internal standard solution container 114 when one sample introduction is completed is used when the sample is introduced next time. For this reason, the internal standard substance is not consumed more than the amount necessary for analysis as in the prior art.
  • Such a sample introduction method can be suitably used for analysis using a dry filter paper blood sample as a sample, such as the above-described neonatal mass screening, and can be similarly applied to analysis using a normal liquid as a sample.
  • the internal standard solution is accommodated in a container prepared separately from the sample plate 111 and set in the internal standard solution container mounting unit 115.
  • the present invention is not limited to this, and the internal standard solution is used as the sample plate.
  • the sample liquid on 111 may be stored in a well 112 that does not store the sample liquid.
  • the well 112 corresponds to the internal standard solution container in the present invention.
  • Two or more internal standard solution containers may be set in the sample introduction device according to the present invention. In this case, for example, the internal standard solution is sucked from one internal standard solution container until a predetermined number of sample introductions are completed, and thereafter, the internal standard solution is collected from another internal standard solution container.
  • the sample introduction device after inserting the front-end
  • the sample solution and the internal standard solution are discharged from the tip and introduced into the analysis channel
  • the sample introduction device according to the present invention is not limited to this.
  • the sample solution and the internal standard solution are discharged from the tip of the needle by the discharge operation of the metering pump, and the sample solution and the internal standard solution are introduced into the analysis channel. May be.
  • a liquid sample introducing device having such a configuration will be described with reference to FIGS.
  • subjected, and description is abbreviate
  • omitted suitably.
  • the flow path switching valve 222 is a 6-port 2-position valve.
  • the port a has a liquid feed pump 225 connected to the carrier liquid reservoir 224, the port b has an upstream side of the sample loop 218, the port c has a drain,
  • the injection port 220 is connected to the port d, the downstream side of the sample loop 218 is connected to the port e, and the analysis flow path 226 reaching the mass spectrometer is connected to the port f.
  • the metering pump 219 is provided independently of the flow path switching valve 222, and a pipe having a needle 216 is connected to the metering pump 219.
  • a needle cleaning flow path 228 including a cleaning liquid container, a liquid feeding pump, a needle cleaning port, and a pipe connecting them is provided. It has been.
  • the configuration of the control unit 230 is the same as that in FIG. In this embodiment, the metering pump 219 corresponds to the suction / discharge means in the present invention.
  • step S 12 the flow path switching valve 222 is brought into the communication state shown in FIG. 8, the needle 216 is inserted into the internal standard solution container 214, and a predetermined amount of the internal standard solution is supplied by the suction operation of the metering pump 219.
  • step S13 as shown in FIG. 9, the needle 216 is inserted into a predetermined well 212 (nth well) on the sample plate 211, and a predetermined amount of sample liquid is collected in the needle 216 by the suction operation of the metering pump 219. To do.
  • step S14 the needle 216 is inserted into the injection port 220 as shown in FIG. 10, and the internal standard solution and the sample solution collected in steps S12 and S13 are introduced into the sample loop 218 by the discharge operation of the metering pump 219. Thereafter, the flow path switching valve is switched to the communication state shown in FIG. As a result, the sample loop 218 is inserted in the flow of the carrier liquid, and the internal standard solution and the sample liquid held in the sample loop 218 are introduced into the mass spectrometer through the analysis flow path 226.
  • the sample was introduced into the mass spectrometer using the sample introduction method according to the present invention and the conventional sample introduction method, and the results of quantitative analysis using the mass spectrometer were compared.
  • the same dry filter paper blood sample as described above was accommodated in the well of the sample plate, 100 ⁇ L of methanol was added, and blood components were extracted by shaking at 45 ° C. for 45 minutes. And the obtained extract (sample liquid) was moved to the well of another sample plate, and was set to the automatic sample introduction apparatus. Further, an appropriate amount of the same internal standard solution as described above was accommodated in a vial and set in an automatic sample introduction apparatus. In the automatic sample introduction device, 1 ⁇ L each of the extract in the well and the internal standard solution in the vial was sampled and introduced into the mass spectrometer at the same time.
  • the mass spectrometer performs mass spectrometry based on the conditions defined in the kit, and based on the obtained mass spectrum, 20 kinds of indicator substances (amino acids Ala, Cit, Leu, Met, Phe , Tyr, Val, acylcarnitine C0, C2, C3, C4, C5, C5DC, C6, C8, C10, C12, C14, C16, C18) and their corresponding internal standard peak areas were derived. Then, using the ratio of the peak areas of each indicator substance and internal standard substance thus obtained, and a calibration curve prepared by measuring a plurality of types of samples having different concentration ratios of the indicator substance and internal standard substance in advance. The concentration of each indicator substance in the extract was calculated.
  • indicator substances amino acids Ala, Cit, Leu, Met, Phe , Tyr, Val

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Sampling And Sample Adjustment (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)

Abstract

La présente invention concerne l'exécution des étapes suivantes, lorsqu'un échantillon et une substance étalon interne sont introduits dans un dispositif d'analyse : une étape (S12) d'aspiration de solution étalon interne afin d'introduire la pointe d'une aiguille tubulaire dans un récipient de solution étalon interne et d'aspirer, à partir de la pointe, une quantité prescrite d'une solution étalon interne, qui est une solution comprenant la substance étalon interne, reçue dans le récipient de solution étalon interne ; une étape (S13) d'aspiration de solution d'échantillon afin d'introduire la pointe dans un récipient de solution d'échantillon et d'aspirer, à partir de la pointe, une quantité prescrite d'une solution d'échantillon qui est reçue dans un récipient de solution d'échantillon ; et une étape (S14) d'évacuation, afin d'insérer ensuite la pointe dans un orifice d'injection communiquant avec un trajet d'écoulement vers le dispositif d'analyse et d'évacuer la solution d'échantillon et la solution étalon interne depuis la pointe. Dans la description, l'aspiration de la solution étalon interne à partir du même récipient de solution étalon interne pour chaque introduction parmi une pluralité d'introductions d'échantillon permet de limiter à la quantité minimale qui doit être utilisée pour l'analyse la solution étalon interne consommée dans une seule introduction d'échantillon.
PCT/JP2014/067409 2014-06-30 2014-06-30 Appareil d'introduction automatique d'échantillons, procédé d'introduction d'échantillons et programme WO2016001979A1 (fr)

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PCT/JP2014/067409 WO2016001979A1 (fr) 2014-06-30 2014-06-30 Appareil d'introduction automatique d'échantillons, procédé d'introduction d'échantillons et programme
JP2016530704A JPWO2016001979A1 (ja) 2014-06-30 2014-06-30 自動試料導入装置、試料導入方法、及びプログラム

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
CN106841427A (zh) * 2016-12-30 2017-06-13 广州市达瑞生物技术股份有限公司 一种检测pku和cah的串联质谱试剂盒制备及其应用
JP2019124563A (ja) * 2018-01-16 2019-07-25 国立大学法人山梨大学 質量分析装置、質量分析方法、質量分析システム、及び質量分析解析プログラム

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JP2013170925A (ja) * 2012-02-21 2013-09-02 Isuzu Motors Ltd 注射器、マイクロシリンジ、及び分析装置への注入方法

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JPH087202B2 (ja) * 1990-01-08 1996-01-29 株式会社日立製作所 生体試料のクロマトグラフイー分析法および液体クロマトグラフ装置
EP0770212A1 (fr) * 1994-07-11 1997-05-02 Tekmar Company Auto-echantillonneur modulaire a flacons
US6998095B2 (en) * 2003-08-15 2006-02-14 Metara, Inc. Loop dilution system
JP2006242720A (ja) * 2005-03-02 2006-09-14 Shimadzu Corp 自動試料導入装置

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JP2013170925A (ja) * 2012-02-21 2013-09-02 Isuzu Motors Ltd 注射器、マイクロシリンジ、及び分析装置への注入方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106841427A (zh) * 2016-12-30 2017-06-13 广州市达瑞生物技术股份有限公司 一种检测pku和cah的串联质谱试剂盒制备及其应用
CN106841427B (zh) * 2016-12-30 2019-05-14 广州市达瑞生物技术股份有限公司 一种检测pku和cah的串联质谱试剂盒
JP2019124563A (ja) * 2018-01-16 2019-07-25 国立大学法人山梨大学 質量分析装置、質量分析方法、質量分析システム、及び質量分析解析プログラム
JP7158642B2 (ja) 2018-01-16 2022-10-24 国立大学法人山梨大学 質量分析装置及び質量分析システム

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