Quantitative MALDI-TOF mass spectrometric analysis of biocidal polyhexamethylene guanidine (PHMG) oligomers in consumer products

Jung eun Bae, Myungjun Park, Jung min Lee, Insu Song, Yunha Ju, Choong Sik Lee, Jung-Hwan Kwon, Bongjin Moon, Han Bin Oh

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

In Korea, biocides, which were used for sterilizing household humidifiers, caused a large number of casualties. The biocides used were either guanidine-containing oligomers, such as polyhexamethylene guanidine (PHMG), or thiazolinone-based small molecules such as methylisothiazolinone/methylchloroisothiazolinone (MIT/CMIT). For the guanidine-containing oligomers, a quantitative analysis method has not yet been developed, as the quantification of the oligomers is very challenging due to their polydispersed molecular weight distribution. In this paper, we describe a new MALDI-TOF mass spectrometry (MS)-based quantitative analysis method for the PHMG oligomers contained in wet wipe products. Quantification was made using internal standard 13C labeled PHMG oligomers that were custom synthesized. To get rid of matrix molecules, for example, polyethylene glycols (PEGs), included in the wet wipes, solid phase extraction (SPE) with an MCX SPE cartridge was carried out. In addition, an ionic liquid matrix (ILM) of 1-methylimadazolium α-cyano-4-hydroxycinnamate (1-MeIm-CHCA) was used to improve the reproducibility of the MALDI-TOF MS measurements. This new quantitative analysis method was validated, and good linearity was obtained in the calibration plot. This approach is expected to be equally applicable to other guanidine-containing oligomers, such as polyhexamethylene biguanide (PHMB) and oligo-(2-(2-ethoxy)-ethoxyethyl)-guanidinium-chloride (PGH) as well as to other consumer products.

Original languageEnglish
Pages (from-to)298-304
Number of pages7
JournalInternational Journal of Mass Spectrometry
Volume435
DOIs
Publication statusPublished - 2019 Jan 1

Fingerprint

guanidines
Consumer products
Guanidine
oligomers
Oligomers
products
quantitative analysis
Biocides
Disinfectants
Mass spectrometry
solid phases
mass spectroscopy
Chemical analysis
casualties
cartridges
Ionic Liquids
Molecules
Korea
Molecular weight distribution
matrices

Keywords

  • Internal standard
  • Ionic liquid matrix (ILM)
  • Isotope-Labeling
  • MALDI-TOF MS
  • Polyhexamethylene guanidine (PHMG)

ASJC Scopus subject areas

  • Instrumentation
  • Condensed Matter Physics
  • Spectroscopy
  • Physical and Theoretical Chemistry

Cite this

Quantitative MALDI-TOF mass spectrometric analysis of biocidal polyhexamethylene guanidine (PHMG) oligomers in consumer products. / Bae, Jung eun; Park, Myungjun; Lee, Jung min; Song, Insu; Ju, Yunha; Lee, Choong Sik; Kwon, Jung-Hwan; Moon, Bongjin; Oh, Han Bin.

In: International Journal of Mass Spectrometry, Vol. 435, 01.01.2019, p. 298-304.

Research output: Contribution to journalArticle

Bae, Jung eun ; Park, Myungjun ; Lee, Jung min ; Song, Insu ; Ju, Yunha ; Lee, Choong Sik ; Kwon, Jung-Hwan ; Moon, Bongjin ; Oh, Han Bin. / Quantitative MALDI-TOF mass spectrometric analysis of biocidal polyhexamethylene guanidine (PHMG) oligomers in consumer products. In: International Journal of Mass Spectrometry. 2019 ; Vol. 435. pp. 298-304.
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abstract = "In Korea, biocides, which were used for sterilizing household humidifiers, caused a large number of casualties. The biocides used were either guanidine-containing oligomers, such as polyhexamethylene guanidine (PHMG), or thiazolinone-based small molecules such as methylisothiazolinone/methylchloroisothiazolinone (MIT/CMIT). For the guanidine-containing oligomers, a quantitative analysis method has not yet been developed, as the quantification of the oligomers is very challenging due to their polydispersed molecular weight distribution. In this paper, we describe a new MALDI-TOF mass spectrometry (MS)-based quantitative analysis method for the PHMG oligomers contained in wet wipe products. Quantification was made using internal standard 13C labeled PHMG oligomers that were custom synthesized. To get rid of matrix molecules, for example, polyethylene glycols (PEGs), included in the wet wipes, solid phase extraction (SPE) with an MCX SPE cartridge was carried out. In addition, an ionic liquid matrix (ILM) of 1-methylimadazolium α-cyano-4-hydroxycinnamate (1-MeIm-CHCA) was used to improve the reproducibility of the MALDI-TOF MS measurements. This new quantitative analysis method was validated, and good linearity was obtained in the calibration plot. This approach is expected to be equally applicable to other guanidine-containing oligomers, such as polyhexamethylene biguanide (PHMB) and oligo-(2-(2-ethoxy)-ethoxyethyl)-guanidinium-chloride (PGH) as well as to other consumer products.",
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AU - Bae, Jung eun

AU - Park, Myungjun

AU - Lee, Jung min

AU - Song, Insu

AU - Ju, Yunha

AU - Lee, Choong Sik

AU - Kwon, Jung-Hwan

AU - Moon, Bongjin

AU - Oh, Han Bin

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N2 - In Korea, biocides, which were used for sterilizing household humidifiers, caused a large number of casualties. The biocides used were either guanidine-containing oligomers, such as polyhexamethylene guanidine (PHMG), or thiazolinone-based small molecules such as methylisothiazolinone/methylchloroisothiazolinone (MIT/CMIT). For the guanidine-containing oligomers, a quantitative analysis method has not yet been developed, as the quantification of the oligomers is very challenging due to their polydispersed molecular weight distribution. In this paper, we describe a new MALDI-TOF mass spectrometry (MS)-based quantitative analysis method for the PHMG oligomers contained in wet wipe products. Quantification was made using internal standard 13C labeled PHMG oligomers that were custom synthesized. To get rid of matrix molecules, for example, polyethylene glycols (PEGs), included in the wet wipes, solid phase extraction (SPE) with an MCX SPE cartridge was carried out. In addition, an ionic liquid matrix (ILM) of 1-methylimadazolium α-cyano-4-hydroxycinnamate (1-MeIm-CHCA) was used to improve the reproducibility of the MALDI-TOF MS measurements. This new quantitative analysis method was validated, and good linearity was obtained in the calibration plot. This approach is expected to be equally applicable to other guanidine-containing oligomers, such as polyhexamethylene biguanide (PHMB) and oligo-(2-(2-ethoxy)-ethoxyethyl)-guanidinium-chloride (PGH) as well as to other consumer products.

AB - In Korea, biocides, which were used for sterilizing household humidifiers, caused a large number of casualties. The biocides used were either guanidine-containing oligomers, such as polyhexamethylene guanidine (PHMG), or thiazolinone-based small molecules such as methylisothiazolinone/methylchloroisothiazolinone (MIT/CMIT). For the guanidine-containing oligomers, a quantitative analysis method has not yet been developed, as the quantification of the oligomers is very challenging due to their polydispersed molecular weight distribution. In this paper, we describe a new MALDI-TOF mass spectrometry (MS)-based quantitative analysis method for the PHMG oligomers contained in wet wipe products. Quantification was made using internal standard 13C labeled PHMG oligomers that were custom synthesized. To get rid of matrix molecules, for example, polyethylene glycols (PEGs), included in the wet wipes, solid phase extraction (SPE) with an MCX SPE cartridge was carried out. In addition, an ionic liquid matrix (ILM) of 1-methylimadazolium α-cyano-4-hydroxycinnamate (1-MeIm-CHCA) was used to improve the reproducibility of the MALDI-TOF MS measurements. This new quantitative analysis method was validated, and good linearity was obtained in the calibration plot. This approach is expected to be equally applicable to other guanidine-containing oligomers, such as polyhexamethylene biguanide (PHMB) and oligo-(2-(2-ethoxy)-ethoxyethyl)-guanidinium-chloride (PGH) as well as to other consumer products.

KW - Internal standard

KW - Ionic liquid matrix (ILM)

KW - Isotope-Labeling

KW - MALDI-TOF MS

KW - Polyhexamethylene guanidine (PHMG)

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