WO2020055131A1 - Procédé de production de pièces d'essai de matériau insoluble dans l'eau destiné à une spectrométrie de masse maldi et procédé d'analyse quantitative de matériau insoluble dans l'eau à l'aide d'une spectrométrie de masse maldi - Google Patents

Procédé de production de pièces d'essai de matériau insoluble dans l'eau destiné à une spectrométrie de masse maldi et procédé d'analyse quantitative de matériau insoluble dans l'eau à l'aide d'une spectrométrie de masse maldi Download PDF

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WO2020055131A1
WO2020055131A1 PCT/KR2019/011775 KR2019011775W WO2020055131A1 WO 2020055131 A1 WO2020055131 A1 WO 2020055131A1 KR 2019011775 W KR2019011775 W KR 2019011775W WO 2020055131 A1 WO2020055131 A1 WO 2020055131A1
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WIPO (PCT)
Prior art keywords
water
specimen
insoluble substance
insoluble
matrix
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Application number
PCT/KR2019/011775
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English (en)
Korean (ko)
Inventor
배용진
임영희
윤여영
정주은
박병현
유현식
Original Assignee
주식회사 엘지화학
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.)
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Publication date
Priority claimed from KR1020190112140A external-priority patent/KR102385738B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2020532888A priority Critical patent/JP7031956B2/ja
Priority to EP19859265.1A priority patent/EP3708996B1/fr
Priority to US16/954,773 priority patent/US11282684B2/en
Priority to CN201980006839.7A priority patent/CN111527391B/zh
Publication of WO2020055131A1 publication Critical patent/WO2020055131A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/16—Amino-anthraquinones
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q

Definitions

  • the present invention relates to a method for manufacturing a water-insoluble material specimen for MALDI mass spectrometry and a quantitative analysis method using the same specimen, and more specifically, a method for manufacturing a water-insoluble material specimen for homogeneous and small thickness variation for MALDI mass spectrometry and This method relates to a method for obtaining a reproducible MALDI spectrum using a commercial MALDI-TOF MS instrument.
  • MALDI-TOF mass spectrometry (Matrix-Assisted Laser Desorption Ionization-Time of Flight Mass Spectrometry, hereinafter simply referred to as “MALDI”) is a mass spectrometry capable of analyzing insoluble materials.
  • MALDI is used for accurate quantitative analysis because the crystal made by mixing the sample and matrix is heterogeneous and the ion signal is not stable due to the laser shot-to-shot variability and the spectrum reproducibility is poor. It is known as a difficult technique.
  • the present inventors have prepared polymer specimens of uniform thickness by electrospray through a mask with holes for soluble polymer samples in order to increase the reproducibility of the MALDI spectrum. 10-2017-0130010, Application date: 2017.10.11, Applicant: LG Chemical Co., Ltd.). In addition, the present inventors discovered that the thickness of the specimen affects the reproducibility of the spectrum and obtained a reproducible MALDI spectrum using polymer specimens by concentrations with a small thickness variation, and then used a linear calibration curve using an internal standard. Has developed a technology to write (Korea Application No. 10-2017-0157161, filing date: 2017.11.23, Applicant: LG Chem). All contents disclosed in the above patent documents are incorporated herein by reference. However, these methods could not be applied to insoluble (or poorly soluble) substances.
  • CS technique compressed-sample technique
  • CS technology is a method of manufacturing a specimen by drilling a hole in a plate on which a specimen is placed, inserting a sample in a state where one side of the hole is blocked, and pressing.
  • the electric field is not uniformly formed in the specimen due to the hole in the plate, so the m / z of the peak appears differently in the spectrum obtained at the center and edge of the hole.
  • the problem to be solved by the present invention is to provide a method for preparing a specimen of uniform thickness in which a sample of a water-insoluble substance is homogeneously distributed in order to obtain a reproducible MALDI spectrum of a water-insoluble substance.
  • Another problem to be solved by the present invention is to obtain a reproducible MALDI spectrum for a specimen of a water-insoluble material having a uniform thickness and to quantitatively analyze the water-insoluble material therefrom.
  • the present invention is a method for preparing a specimen of water-insoluble material for MALDI mass spectrometry
  • the present invention is a method for quantitative analysis of a water-insoluble substance using a water-insoluble substance specimen prepared by the above method,
  • It provides a quantitative analysis method of a water-insoluble substance comprising the steps of calculating a signal intensity ratio of the water-insoluble substance and the matrix from the peak results of the spectrum and plotting it as a weight ratio of the water-insoluble substance and the matrix.
  • the present invention by producing a water-insoluble material specimen having a homogeneous and small thickness deviation.
  • the reproducible MALDI spectrum can be acquired, enabling quantitative analysis of water-insoluble materials using commercial MALDI-TOF MS equipment.
  • FIG. 1 illustrates a process for obtaining a homogeneous water-insoluble material sample in a method for preparing a MALDI mass spectrometer according to an embodiment of the present invention.
  • Figure 2 illustrates the process of obtaining a specimen from a water-insoluble material sample in the method of manufacturing a specimen for MALDI mass spectrometry according to an embodiment of the present invention.
  • Figure 3 illustrates the manufacturing process of the KBr pellet cup used in the manufacturing method of the specimen for MALDI mass spectrometry according to an embodiment of the present invention.
  • Figure 4 shows the manufacturing process of the specimen, including the production of pellet cups.
  • FIG. 5 is a photomicrograph of a water-insoluble material specimen obtained by a method of manufacturing a MALDI mass spectrometer according to an embodiment of the present invention.
  • Figure 8 shows the signal strength ratio of the analyte (water-insoluble substance) and the matrix from the results of the MALDI mass spectrum obtained for the water-insoluble substance specimen prepared according to the embodiment of the present invention as a weight ratio of the analyte and the matrix It shows the linear quantitative test line created by.
  • water insoluble is meant to include anything that is not soluble or difficult to dissolve in water.
  • homogeneity refers to a state in which components contained in a sample or a specimen are uniformly distributed to each other.
  • One embodiment of the present invention relates to a method for preparing a specimen of uniform thickness in which a sample of a water-insoluble substance is homogeneously distributed in order to obtain a MALDI spectrum of a reproducible water-insoluble substance, wherein the method is (S1) water-insoluble Obtaining a material sample; And (S2) obtaining a specimen from the sample using a pellet cup.
  • step (S1) after mixing the water-insoluble substance and the matrix, a volatile solvent is added to disperse the water-insoluble substance and the matrix until the volatile solvent evaporates, thereby obtaining a water-insoluble substance sample.
  • Figure 1 specifically illustrates the process of obtaining a homogeneous water-insoluble material sample in the method of manufacturing a specimen for MALDI mass spectrometry according to an embodiment of the present invention.
  • a water-insoluble substance and a matrix to be analyzed are mixed using a pestle and a mortar (a), and a volatile solvent is added to the mixture to dissolve the matrix, thereby generating it.
  • a water-insoluble substance can be obtained by dispersing the water-insoluble substance in the solution (b), and then stirring the dispersion with a spatula (c and c ') until all the volatile solvent used is evaporated.
  • the present invention is added to the step (a) of mixing the analyte (a water-insoluble substance) and the matrix using a pestle and a pestle to increase the homogeneity of the sample in the prior art, and the solution is dissolved using a volatile solvent Dispersing the water-insoluble substance in step (b) and while maintaining the dispersion state is characterized by performing the step (c and c ') of homogeneously mixing the matrix and the water-insoluble substance through solvent evaporation.
  • the homogeneity of the sample is improved and static electricity is not generated in the sample, thereby improving the handling property of the sample.
  • the degree to which each component is uniformly distributed in the sample obtained according to the present invention can be evaluated from the error range of the MALDI spectrum result of the specimen prepared therefrom, and the smaller the error range, the more uniform the distribution of the sample, i.e. homogeneity. It can be evaluated as excellent.
  • the water-insoluble substance is an anthraquinone pigment, such as Pigment Red 177 (PR177, 4,4'-diamino [1,1'-bianthracen] -9,9 ', 10,10'-tetraone), Copper phthalocyanic pigments, perylene pigments, diketopyrrolopyrrole pigments, benzimidazole pigments, isoindoline pigments, dioxazine pigments, and the like, but are not limited thereto.
  • Pigment Red 177 PR177, 4,4'-diamino [1,1'-bianthracen] -9,9 ', 10,10'-tetraone
  • Copper phthalocyanic pigments such as Pigment Red 177 (PR177, 4,4'-diamino [1,1'-bianthracen] -9,9 ', 10,10'-tetraone
  • Copper phthalocyanic pigments such as Pigment Red 177 (PR177, 4,4'-d
  • the matrix mixed with the water-insoluble substance is DCTB (trans-2- [3- (4-tert-butylphenyl) -2-methyl-2-propenylidene] malononitrile) as a substance having low solubility in water.
  • DCTB trans-2- [3- (4-tert-butylphenyl) -2-methyl-2-propenylidene] malononitrile
  • DPF ⁇ , ⁇ -diphenylfumaronitrile
  • ⁇ -cyano-4-hydroxycinnamic acid dithranol (1,8,9-trihydroxyanthracene
  • DPF ⁇ , ⁇ -diphenylfumaronitrile
  • ⁇ -cyano-4-hydroxycinnamic acid dithranol (1,8,9-trihydroxyanthracene
  • the content of the water-insoluble substance and the matrix is not particularly limited, but may be mixed in a weight ratio of 1:20 to 1: 100, such as 1:20.
  • the water-insoluble substance and the volatile solvent added to the matrix may be one or more selected from tetrahydrofuran (THF), chloroform, and the like, but is not limited thereto.
  • a ball mill in addition to the pestle and pestle when mixing the water-insoluble material and the matrix, a ball mill may be used.
  • the previously obtained sample is filled into a groove of a pellet cup made of a water-soluble material, and then inverted and pressed, the pellet cup is dissolved with water to obtain a water-insoluble material specimen.
  • Figure 2 specifically illustrates the process of obtaining a specimen from a water-insoluble material sample in a method for preparing a specimen for MALDI mass spectrometry according to an embodiment of the present invention.
  • a water-soluble material pellet cup is prepared to fill a sample of the water-insoluble material obtained before the groove thereof (d), the pellet cup filled with the sample is turned over (e), and the press is pressed in that state. After performing (f), the used pellet cup was dissolved with water (g) and further dried (h) to obtain a water-insoluble specimen. At this time, the press may be performed for 10 to 20 seconds at a pressure of 1 to 5 bar using a hot press.
  • a pellet cup is used.
  • the pellet cup may be used without limitation as long as it is a water-soluble material soluble in water.
  • a pellet cup made of KBr, NaBr, MgBr 2 , NaCl or a mixture thereof may be used.
  • Figure 3 illustrates the manufacturing process of the KBr pellet cup used in the manufacturing method of the specimen for MALDI mass spectrometry according to an embodiment of the present invention.
  • the KBr pellet cup manufacturing apparatus is placed on a flat square plate 6, a square frame 1 with a circular hole in the middle placed on the plate 6, and a circular hole of the square frame 1
  • the paper can use circular members (2), (3) and (4) and a circular member (5) which is placed on the circular member (4) and then pressed.
  • the manufacturing process of a specific KBr pellet cup is as follows.
  • the frame 1 with a circular hole in the center is placed on the plate 6, and the circular member 2 is inserted into the circular hole of the frame 1 (step i).
  • the plate 6 is a plate in which the entire process is performed from KBr pellet cup production to production of the specimen, and the shape, dimension, and material are not particularly limited, and the entire specimen production process can be easily performed.
  • the circular member 3 is put on the circular member 2 (step ii). At this time, the circular member 2 has a convex portion in the center, and the circular member 3 has a small circular hole in the center. Then, KBr is filled in the center hole of the circular member 3 (step iii).
  • the convex portion of the circular member 2 and its size and the hole in the center of the circular member 3 and its size correspond to the shape and dimensions of the KBr pellet cup later.
  • the circular member 4 is placed on it (step iv).
  • the circular member 4 has a convex portion at the center.
  • a press is performed (step vi). At this time, the same pressure is applied over the entire area of the circular member 5.
  • the circular members (2), (3) and (4) are placed in order in the circular holes of the frame (1), so they must be exactly the size of the circular holes of the frame (1).
  • the circular members 5 and 4 are removed, and the circular member 2 and the frame 1 are removed, leaving only the circular member 3 on the plate 6.
  • KBr is tightly filled in the center hole of the circular member 3 by a press.
  • the circular member 3 is removed to complete the KBr pellet cup (step vii).
  • the finished pellet cup has a grooved shape in the center by the convex portion of the circular member 2.
  • the shape and dimensions of the frame 1 are not particularly limited, but it is preferable that all the circular members 2, 3, and 4 enter the circular hole of the frame 1, so that the frame 1
  • the thickness of can be equal to or greater than the combined thickness of the circular members 2, 3 and 4, respectively.
  • the circular member 5 should be smaller than the size of the circular member 4 to be easy to press.
  • the material of the circular members (1) to (5) is not particularly limited, for example, stainless steel (stainless steel), aluminum (aluminium) or the like can be used.
  • the press can be performed using a hot press.
  • the press may be performed for 10 to 20 seconds at a pressure of 1 to 5 bar.
  • the size of the circular hole in the frame 1 and the hole in the center of the circular member 3 is not particularly limited.
  • the pellet cup may have a circular or polygonal shape.
  • FIG. 4 schematically shows the manufacturing process of the specimen including the production of the pellet cup, the pellet cup manufacturing apparatus 10 is filled with a pellet cup material such as KBr and then pressed to produce a pellet cup (the specific method is FIG. 3), filling the pellet cup with a sample of a water-insoluble substance, turning it over, mounting it on a MALDI sample plate, and pressing, and dissolving the pellet cup.
  • a pellet cup material such as KBr
  • FIG. 3 the specific method is FIG. 3
  • the pellet cup When the pellet cup is used in this way, it is not necessary to drill a hole in the plate on which the specimen is placed, as in the case of specimen preparation by a conventional CS technique (compressed sample technique).
  • CS technique compressed sample technique
  • the disadvantages can be overcome. That is, since the pellet cup applied in the present invention can press the same pressure per unit volume in a state in which a sample is limited therein, it is possible to manufacture a specimen having a uniform thickness. Also, by dissolving only the pellet cup with water for the sample pressed together with the pellet cup, it is possible to prevent the specimen surface from being damaged by the press.
  • the water-insoluble material specimen of the present invention prepared in the above manner may have a thickness of 20 ⁇ m or less, for example 10 ⁇ m or less.
  • the thickness deviation may be 30% or less.
  • the present invention provides a method for quantitative analysis of a water-insoluble substance using MALDI mass spectrometry of a water-insoluble substance specimen prepared using a pellet cup.
  • the analysis method includes obtaining a MALDI mass spectrum for a water-insoluble material specimen prepared using a pellet cup; And calculating a signal intensity ratio of the water-insoluble substance and the matrix from the peak results of the spectrum, and plotting the ratio of the signal strength of the water-insoluble substance and the matrix to create a quantitative calibration curve.
  • the MALDI mass spectrum can be obtained using commercial MALDI-TOF MS equipment. At this time, in order to obtain a spectrum having a good S / N ratio (signal-to-noise ratio), multiple points, for example, 50 to 200 shots per point in the specimen, for example, 3 or more, Alternatively, an average value is obtained by obtaining one spectrum for each point from five or more spots.
  • S / N ratio signal-to-noise ratio
  • the MALDI mass spectrum of the water-insoluble material specimen has a relative standard deviation (RSD) indicating the error of the result when three or more points are measured (spot-to-spot) in the same specimen. 40% or less, specifically 35% or less, such as 25 to 35% or 25 to 30%.
  • RSD of sample-to-sample MALDI mass spectrum results measured on three or more specimens prepared under the same conditions is 40% or less, specifically 30% or less, such as 20 to 30% Or 25 to 30%. This RSD range is to demonstrate the reproducibility of the MALDI spectrum obtained from specimens manufactured according to the present invention to ensure thickness uniformity.
  • the quantitative calibration curve created using the results of the reproducible MALDI spectrum that is, the quantitative calibration curve depicting the signal intensity ratio of the water-insoluble substance and the matrix as the weight ratio of the water-insoluble substance and the matrix are all linear (see FIG. 8). ), From which it is possible to quantitatively analyze water-insoluble substances.
  • Pigment Red 177 (PR177, C 28 H 16 N 2 O 4 , Exact Mass 444.11) represented by the following formula as a water-insoluble substance to be analyzed and DCTB (trans-2- [3- (4-tert-butylphenyl)) as a matrix -2-methyl-2-propenylidene] malononitrile) was used.
  • DCTB trans-2- [3- (4-tert-butylphenyl)
  • a matrix -2-methyl-2-propenylidene] malononitrile was used.
  • THF (2 mL) was added as a volatile solvent for dispersing the mixture, and mixing was continued.
  • stirring was continued while stirring with a spatula until the THF evaporated to obtain a sample in which the water-insoluble substance and the matrix were uniformly distributed.
  • the sample prepared in the above step was filled into the groove of the KBr pellet cup prepared as shown in FIG. 4.
  • the KBr pellet cup filled with the sample was turned over and mounted on the MALDI sample plate, and then 5 bar of pressure was applied to the KBr pellet cup for 20 seconds. Subsequently, KBr was dissolved in water to prepare a PR177 specimen having a thickness of about 10 ⁇ m.
  • 5 shows a micrograph of the prepared specimen, from which it can be confirmed that there is no surface damage of the sample.
  • a sample was prepared by adding PR 177 as a water-insoluble substance and DCTB as a matrix in a weight ratio of 1:20 in a mortar and grinding while changing to a pestle.
  • Specimens were prepared by placing the sample obtained in step 1 on a MALDI sample plate without using a KBr pellet cup and then simply pressing it.
  • the intensity pattern of the peaks in the three specimens and the reproducibility of the peak position can be confirmed.
  • the RSD between the base peak of the PR177 ion (A + ⁇ ) and the base peak of the ion (M + ) having the greatest intensity among DCTB-derived ions (A + ⁇ / M + intensity ratio) is 25 %. Therefore, the MALDI mass spectrum of the specimen prepared according to the present invention also has high sample-to-sample reproducibility.
  • the signal intensity ratio of the analyte (water-insoluble substance) and the matrix was calculated using the mass spectrum peak of FIG. 7, and a quantitative calibration curve was prepared by plotting this as the weight ratio of the analyte and the matrix, and the results are shown in FIG. 8. Shown.

Abstract

La présente invention concerne un procédé de production de pièces d'essai dans lesquelles l'épaisseur des échantillons de matériau homogène insoluble dans l'eau est uniforme, et un procédé d'analyse quantitative de matériau insoluble dans l'eau par l'analyse desdites pièces d'essai à l'aide d'une spectrométrie de masse MALDI. Plus particulièrement, les pièces d'essai peuvent être produites par : l'ajout d'un solvant volatil à un mélange matériau insoluble dans l'eau et matrice ; la mise en place, dans une coupelle pastillée en matériau soluble dans l'eau, et la pression, avec une pression régulière, de l'échantillon obtenu en mélangeant le mélange matériau insoluble dans l'eau et la matrice jusqu'à l'évaporation du solvant ; et la fusion de la coupelle pastillée avec de l'eau.
PCT/KR2019/011775 2018-09-11 2019-09-11 Procédé de production de pièces d'essai de matériau insoluble dans l'eau destiné à une spectrométrie de masse maldi et procédé d'analyse quantitative de matériau insoluble dans l'eau à l'aide d'une spectrométrie de masse maldi WO2020055131A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2020532888A JP7031956B2 (ja) 2018-09-11 2019-09-11 Ｍａｌｄｉ質量分析用の水不溶性物質試料の製造方法及びｍａｌｄｉ質量分析を利用した水不溶性物質の定量分析方法
EP19859265.1A EP3708996B1 (fr) 2018-09-11 2019-09-11 Procédé de production de pièces d'essai de matériau insoluble dans l'eau destiné à une spectrométrie de masse maldi et procédé d'analyse quantitative de matériau insoluble dans l'eau à l'aide d'une spectrométrie de masse maldi
US16/954,773 US11282684B2 (en) 2018-09-11 2019-09-11 Method for producing test pieces of water-insoluble material for MALDI mass spectrometry and method for quantitative analysis of water-insoluble material using MALDI mass spectrometry
CN201980006839.7A CN111527391B (zh) 2018-09-11 2019-09-11 Maldi质谱法用水不溶性物质的试验片的制备方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2018-0108097 2018-09-11
KR20180108097 2018-09-11
KR1020190112140A KR102385738B1 (ko) 2018-09-11 2019-09-10 Maldi 질량분석용 수불용성 물질 시편의 제조방법 및 maldi 질량분석법을 이용한 수불용성 물질의 정량분석방법
KR10-2019-0112140 2019-09-10

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012177689A (ja) * 2011-01-31 2012-09-13 Noguchi Institute Ｍａｌｄｉ質量分析法用測定試料調製方法
JP5422089B2 (ja) * 2007-09-25 2014-02-19 アークレイ株式会社 分光測定用ペレット、その製造方法および分光測定方法
US20150162176A1 (en) * 2011-07-26 2015-06-11 Kratos Analytical Limited Maldi sample preparation methods and targets
KR20170021398A (ko) * 2015-08-17 2017-02-28 연세대학교 산학협력단 말디톱 질량분석기에 이용가능한 시료 플레이트 및 상기 시료 플레이트의 제조방법
KR20170102685A (ko) * 2016-03-02 2017-09-12 (주)에나인더스트리 고분자 복합수지 시편 제작용 금형
KR20170130010A (ko) 2016-05-17 2017-11-28 삼성전자주식회사 반도체 소자 및 그 제조 방법
KR20180108097A (ko) 2017-03-24 2018-10-04 현대자동차주식회사 전기 자동차 및 전기 자동차의 배터리 충전 방법
KR20190112140A (ko) 2017-03-23 2019-10-02 미쓰비시덴키 가부시키가이샤 막 분리 장치 및 막 분리 방법

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5422089B2 (ja) * 2007-09-25 2014-02-19 アークレイ株式会社 分光測定用ペレット、その製造方法および分光測定方法
JP2012177689A (ja) * 2011-01-31 2012-09-13 Noguchi Institute Ｍａｌｄｉ質量分析法用測定試料調製方法
US20150162176A1 (en) * 2011-07-26 2015-06-11 Kratos Analytical Limited Maldi sample preparation methods and targets
KR20170021398A (ko) * 2015-08-17 2017-02-28 연세대학교 산학협력단 말디톱 질량분석기에 이용가능한 시료 플레이트 및 상기 시료 플레이트의 제조방법
KR20170102685A (ko) * 2016-03-02 2017-09-12 (주)에나인더스트리 고분자 복합수지 시편 제작용 금형
KR20170130010A (ko) 2016-05-17 2017-11-28 삼성전자주식회사 반도체 소자 및 그 제조 방법
KR20190112140A (ko) 2017-03-23 2019-10-02 미쓰비시덴키 가부시키가이샤 막 분리 장치 및 막 분리 방법
KR20180108097A (ko) 2017-03-24 2018-10-04 현대자동차주식회사 전기 자동차 및 전기 자동차의 배터리 충전 방법

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