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WO2004097395A1 - Matrice pour l'analyse de masse par ionisation par desorption laser assistee par matrice (maldi) - Google Patents

Matrice pour l'analyse de masse par ionisation par desorption laser assistee par matrice (maldi) Download PDF

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Publication number
WO2004097395A1
WO2004097395A1 PCT/JP2004/005363 JP2004005363W WO2004097395A1 WO 2004097395 A1 WO2004097395 A1 WO 2004097395A1 JP 2004005363 W JP2004005363 W JP 2004005363W WO 2004097395 A1 WO2004097395 A1 WO 2004097395A1
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Prior art keywords
group
matrix
hydrogen atom
formula
mass spectrometry
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PCT/JP2004/005363
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English (en)
Japanese (ja)
Inventor
Hideaki Nakajima
Hiroshi Takigawa
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Publication of WO2004097395A1 publication Critical patent/WO2004097395A1/fr
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0409—Sample holders or containers
    • H01J49/0418—Sample holders or containers for laser desorption, e.g. matrix-assisted laser desorption/ionisation [MALDI] plates or surface enhanced laser desorption/ionisation [SELDI] plates
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/68—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving proteins, peptides or amino acids
    • G01N33/6803—General methods of protein analysis not limited to specific proteins or families of proteins
    • G01N33/6848—Methods of protein analysis involving mass spectrometry
    • G01N33/6851—Methods of protein analysis involving laser desorption ionisation mass spectrometry

Definitions

  • the present invention relates to a matrix in a matrix-assisted laser desorption (hereinafter, referred to as MALDI) mass spectrometry.
  • MALDI matrix-assisted laser desorption
  • Mass spectrometry is used to determine the molecular weight and structure of organic compounds.
  • a solution of the substance to be measured is mixed with a matrix solution and, if necessary, an ionization aid, applied on a sample table called a target, and the solvent is removed.
  • the sample is removed, and the target with the sample attached is placed in a vacuum device.
  • the matrix changes the energy of the laser beam into heat energy and transmits it to the target substance, thereby ionizing the target substance.
  • a matrix is used to ionize the substance to be measured.
  • compounds that can be used as a matrix include 2,5-dihydroxybenzoic acid, disulanol, 2- (4-hydroxyphenylazo) benzoic acid (HAB A) (for example, “Bunseki”, In April 1996, see The Japan Society for Analytical Chemistry, p. 253-262, and 1,4-diphenylbutadiene have been proposed (see, for example, — See 1 5 3 8 4 2 gazette.
  • HAB A 2- (4-hydroxyphenylazo) benzoic acid
  • the intensity of the signal obtained decreases with the lapse of time since the target was placed in the device, and it can be obtained when the elapsed time is longer than 30 minutes.
  • the signal intensity is not sufficient, and there has been a demand for a matrix that can maintain a strong signal intensity even after being subjected to a vacuum for a long period of time ⁇ I.
  • An object of the present invention is to provide a matrix capable of maintaining a strong signal intensity even after being placed under vacuum for a long time in MALDI mass spectrometry.
  • the present inventor has continued intensive studies on the matrix used for MA LDI mass spectrometry, and has found that at least three substituents are present at the end of a hydrocarbon chain having two or more double bonds.
  • the present inventors have found that a compound represented by a specific formula to which is bonded becomes a matrix capable of maintaining a strong signal intensity even after being placed in a vacuum for a long time, and completed the present invention.
  • R 1, R 2, R 3, and R 4 may be the same or different, and at least two of them each have a total carbon number of 6 to 18 and are a halogen atom, a hydroxyl group, a sulfo An aryl group which may be substituted with an acid group, a carboxyl group, an alkyl group, or an alkoxy group;
  • Rl, R2, R3, and R4 are the aryl groups
  • the remaining two independently have a total carbon number of 1 to 10 and include a halogen atom, a hydroxyl group, and a sulfone.
  • R 5, R 6, R a or R bi may be the same or different and are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and n is 0 Is an integer from 3 to 3, and i is an integer from 1 to n.
  • a matrix for matrix-assisted laser desorption mass spectrometry comprising a compound represented by the formula:
  • the present invention also provides a composition for matrix-assisted laser desorption mass spectrometry comprising the matrix described above.
  • the present invention also provides a matrix-assisted laser desorption mass spectrometry method using the matrix described above. Further, the present invention provides a method for quality control of a synthetic polymer, characterized by using the matrix-assisted laser desorption mass spectrometry method described above.
  • FIG. 1 is a chart showing the results of Example 1.
  • the signal of polystyrene 1 hour after the sample installation was used. The measurement results are shown.
  • the scale of the vertical axis is arbitrary.
  • Figure 2 is a chart showing the results of Comparative Example 1.
  • the signal of polystyrene 1 hour after the sample was set when trans.trans, 1,4-diphenyl-1,3-butadiene was used as the matrix. 2 shows the measurement results.
  • the scale of the vertical axis is an arbitrary unit, but the same scale as in Fig. 1.
  • Fig. 3 is a chart showing the results of Comparative Example 2. Measurement of polystyrene signals one hour after sample installation when dithranol was used as the matrix. The results are shown. The scale of the vertical axis is an arbitrary unit, but is the same scale as in Fig. 1. BEST MODE FOR CARRYING OUT THE INVENTION
  • the matrix of the present invention has the formula (1)
  • R1, R2, R3, and R4 may be the same or different from each other, and at least two of them have a total carbon number of 6 to 18 and are a halogen atom, a hydroxyl group, a sulfonic acid group, An aryl group which may be substituted with a carboxyl group, an alkyl group, or an alkoxy group;
  • Rl, R2, R3, and R4 are the above aryl groups, the remaining two are each independently substituted with a halogen atom, a hydroxyl group, and a sulfonate group having a total carbon number of 1 to 10. However, one of the remaining two is a hydrogen atom, and the other one is the alkyl group.
  • Rl, R2, R3, and R4 all represent the aryl group.
  • R1 and R2, and further R3 and R4, may be linked by a carbon chain.
  • Rl, R2, R3, and R4 may be the same or different from each other, and at least two of them have a total of 6 to 18 carbon atoms each and have a halogen atom, a hydroxyl group, a sulfonic acid group, A aryl group which may be substituted with a carboxyl group, an alkyl group, or an alkoxy group;
  • Rl, R2, R3, and R4 are the aryl groups
  • the remaining Two are each independently an alkyl group having a total carbon number of 1 to 10 and which may be substituted by a halogen atom, a hydroxyl group, or a sulfonate group; one of the remaining two is a hydrogen atom, The other one is the aforementioned alkyl group.
  • Rl, R2, R3, and R4 all represent the aryl group.
  • Rl, R2, R3, and R4 are the above aryl groups, the remaining one has 1 total carbon number and is 10 and is substituted with a halogen atom, a hydroxyl group, or a sulfonic acid group. Or an alkyl or hydrogen atom which may be substituted.
  • Examples of the aryl group which may be substituted with a halogen atom, a hydroxyl group, a sulfonic acid group, an alkyl group, or an alkoxy group include a phenyl group, a 1-chlorophenyl group, a 2-chlorophenyl group, and a 3-chlorophenyl group.
  • alkyl group which may be substituted with a halogen atom, a hydroxyl group or a sulfonic acid group
  • examples of the alkyl group which may be substituted with a halogen atom, a hydroxyl group or a sulfonic acid group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group and a t-butyl group Group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, chloromethyl group, bromomethyl group, fluoromethyl group, 1-chloroethynole group, 2-chloroethynole group, 1-bromoethynole group, 2-bromoethyl group, 1-fluoroethyl group, 2-fluoroethyl group
  • Each of R1, R2, R3, and R4 is preferably a phenyl group or an alkyl-substituted phenyl group, and more preferably a phenyl group.
  • R5, R6, Rai, and Rbi are each a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • n there is no repeating unit shown in parentheses in equation (1), so R & i and Rbi do not exist, and when n is an integer of 1 or more, (1)
  • the i-th substituent R a or Rbi in the unit shown in parentheses in the formula is independent of each other.
  • the compound represented by the formula (1) has two or more double bonds in the molecule except for a six-membered ring.
  • alkyl group having 1 carbon atom and 10 alkyl groups examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butylinole group, a sec-butyl group, a t-butyl group, an n-pentyl group, 2-pentyl group, 3-pentyl group, 2-methyl-1-butyl group, 3-methyl-1-butyl group, 2-methyl-1-butyl group, 3-methyl-2-butyl group 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl, n-decyl group and the like.
  • R5, R6, Ra is R bi good Mashiku those are all hydrogen atom or a methyl group, those more preferably all hydrogen atoms.
  • the compound represented by the formula (1) has a structural isomer due to a double bond site, the compound represented by the formula (1) is easily absorbed by laser energy. (A bond in which all bonds in the double bond except for the 6-membered ring are in trans form).
  • the compound represented by the formula (1) preferably has a size that does not hinder the detection of sample molecules, and preferably has a molecular weight of 100,000 or less.
  • Examples of the compound represented by the formula (1) include compounds represented by the following formulas (2).
  • the matrix is preferably uniformly mixed with the substance to be measured on a metal sample table called a target.
  • a metal sample table called a target.
  • 1 og P which is the water Z-octanol distribution ratio of the matrix of the present invention, is set to 1 og P of the substance to be measured. It is desirable that the difference is close to 1 og P of the monomer unit. Specifically, it is desirable that the difference between 1 og P of the matrix and 1 og P of the monomer unit is within 10 or less.
  • the compound of formula (1) for example, 1,1,4,4-tetrafluoro-1,3-butadiene having a log P of 7.9 (molecular weight: 358) is suitable.
  • 1 og P is the distribution ratio of water Z octanol, which is known in the art.For example, OECD G. UIDEL I NE FOR THE TEST I NG OF CHEMI CALS (Ad opted by the council on 27th July 1995) It is described, but is not limited to this, and is also required by computer software C 1 og P (trade name, manufactured by Bio Byte, USA). For example, logP of 1,1,4,1-triphenyl-1,3-butadiene Is 6.5.
  • the purity of the compound used as the matrix is preferably 90% or more.
  • the component having a molecular weight of 100 or more is 5% by weight or less so that the sample can be clearly distinguished from the sample.
  • the sample can contain a substance to be measured and a matrix, and a metal salt such as silver trifluoroacetate, copper nitrate, sodium chloride, and potassium chloride, an ammonium salt, and an organic salt as an ionization initiator.
  • a metal salt such as silver trifluoroacetate, copper nitrate, sodium chloride, and potassium chloride, an ammonium salt, and an organic salt as an ionization initiator.
  • the method for preparing a mixture of the substance to be measured and the matrix on the target is not particularly limited.
  • the substance to be measured, the matrix, and the ionization initiator are each prepared in advance as a solution.
  • the mixture can be attached to a target with a micropiter or a microsyringe, and then the solvent can be distilled off.
  • the surface of the sample formed on the target is preferably uniform.
  • the substance to be measured is not particularly limited, but considering that the ionization of the matrix itself does not disturb the spectrum, when the substance to be measured has a single molecular weight, The molecular weight is preferably at least 500, more preferably at least 100. When the substance to be measured has a molecular weight distribution, the weight average molecular weight is preferably 500 or more in terms of polystyrene measured by size exclusion chromatography (GPC), and the weight average molecular weight is 100 or more. More preferably, it is a compound.
  • GPC size exclusion chromatography
  • MALDI mass spectrometry using the matrix of the present invention can be suitably used for quality control of synthetic polymers.
  • a sample is randomly sampled from the produced synthetic polymer, a solution of the substance to be measured is mixed with a matrix solution and, if necessary, an ionization aid, and applied on a target to remove the solvent, thereby obtaining a sample.
  • Data is obtained by placing the target on the MA LDI mass spectrometer and performing mass spectrometry on each sample in turn. From the signal intensity data for each mZ z, we estimate the standard deviation of the population using statistical quality control methods, estimate the average value of the population, etc. A test can be performed. In addition, a control chart can be created to manage the process so that it is kept stable.
  • the signal intensity maintenance performance under vacuum can be evaluated by the following method. After the target with a fixed amount of sample mixed with a fixed amount of matrix is inserted into the MA LDI mass spectrometer, it is left under vacuum for a certain period of time, and then the laser irradiation energy and the number of laser irradiations on the target are measured. The signal intensity of the mass spectrum of the sample obtained when the measurement was performed at a constant level was high, but the signal intensity maintenance performance under vacuum was high. At this time, the signal maintenance performance is high, and for matrixes, the signal intensity of the mass spectrum obtained when the target is measured immediately after insertion into the MALDI mass spectrometer is high, improving the measurement sensitivity. You can also.
  • a time-of-flight mass spectrometer is a device that separates and detects these ions, and is a device suitable for using a polymer compound as a substance to be measured. By combining with a time-of-flight mass spectrometer, it is possible to measure a high molecular compound having an extremely large molecular weight, and it can be suitably used for measuring a molecular weight distribution of a biopolymer or a synthetic polymer.
  • the target was inserted into the mass spectrometer, it was left under vacuum for 60 minutes, and then the measurement was performed in the positive ionization mode with an acceleration voltage of 26.5 kV and an integrated laser shot of 200 times. .
  • a sign nanore strength of mZz 2561, which indicates a styrene monomer trimer in the obtained mass spectrum, was used.
  • the signal intensity indicating the performance of maintaining the signal intensity when the matrix of Example 1 was used was 193232 counts.
  • 1,1,4,4-tetraphenyl-1,3-butadiene is trans-, trans-1,4-diphenyl-1,3-butadiene (Reagent from Lancaster)
  • the measurement was performed under the same conditions as in Example 1 except that the measurement was changed to.
  • the signal intensity showing the performance of maintaining the signal intensity when the matrix of Comparative Example 1 was used was 248 counts.
  • Example 1 For the matrix used in Example 1, the measurement was carried out under the same conditions as in Example 1 except that 1,1,4,4-tetraphenyl_13-butadiene was changed to disulanol (a reagent manufactured by Aldrich).
  • the signal intensity showing the performance of maintaining the signal intensity when the matrix of Comparative Example 1 was used was 249 counts.
  • Table 1 summarizes the results of Example 1 and Comparative Examples 1 and 2. 1, 1, 4, 4- When tetraphenyl-1,3-butadiene is used for matrix, even if the sample and matrix mixture are left under vacuum for 60 minutes, a very strong signal is obtained as compared to the conventional matrix used in Comparative Examples 1 and 2. Since the strength was obtained, it was found that the matrix of Example 1 was excellent in maintaining the signal strength under vacuum. table 1 Industrial applicability
  • the matrix of the present invention is excellent in that it maintains a high signal intensity even under a high vacuum for a long time. Therefore, the MALDI mass spectrometry method using the matrix of the present invention can be used to measure many substances to be measured at once, and the efficiency of the measurement can be increased, which is extremely industrially important.

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Abstract

L'invention concerne une matrice pour l'analyse de masse MALDI, laquelle comprend un composé correspondant à la formule (1). Dans ladite formule : au moins deux des symboles R1, R2, R3 et R4 représentent un groupe aryle éventuellement substitué par un atome d'halogène, un groupe hydroxyle, un groupe acide sulfonique, un groupe carboxyle, un groupe alkyle ou un groupe alcoxy, et présentant 6 à 18 atomes de carbone au total, et au maximum un desdits symboles représentant un atome d'hydrogène, tandis que les autres symboles représentent un groupe alkyle éventuellement substitué par un atome d'halogène, un groupe hydroxyle ou un groupe acide sulfonique, et présentant 1 à 10 atomes de carbone au total ; chacun des symboles R5, R6, Rai et Rbi représente un atome d'hydrogène ou un groupe alkyle ; et n est un nombre entier de 0 à 3 et i est un nombre entier de 1 à n. Ladite matrice, lors de son utilisation pour l'analyse de masse MALDI, peut conserver une grande intensité de signal également après avoir été exposée sous vide pendant une longue durée.
PCT/JP2004/005363 2003-04-30 2004-04-15 Matrice pour l'analyse de masse par ionisation par desorption laser assistee par matrice (maldi) Ceased WO2004097395A1 (fr)

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JP2003-124810 2003-04-30

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001153842A (ja) * 1999-11-25 2001-06-08 Mitsubishi Chemicals Corp 表面分析方法
JP2002513917A (ja) * 1998-05-07 2002-05-14 シークエノム・インコーポレーテツド 高分子の赤外マトリックス補助レーザー脱着／イオン化質量分析

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002513917A (ja) * 1998-05-07 2002-05-14 シークエノム・インコーポレーテツド 高分子の赤外マトリックス補助レーザー脱着／イオン化質量分析
JP2001153842A (ja) * 1999-11-25 2001-06-08 Mitsubishi Chemicals Corp 表面分析方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
TAKIGAWA, H. ET AL.: "MALDI-TOFMS Yo Shinki Matrix to Gosei Kobunshi eno Oyo", DAI 51 KAI SHITSURYO BUNSEKI SOGO TORONKAI KOEN YOSHISHU, 14 May 2003 (2003-05-14), pages 128 - 129, XP002983534 *
TANAKA, K.: "Matrix Shien Laser Datsuri Ion-ka Shitsuryo Bunseki Ho", BUNSEKI, 1996 NEN, no. 4, 5 April 1996 (1996-04-05), pages 253 - 261, XP002983535 *

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