MALDI-TOF Analysis of Polyhexamethylene Guanidine (PHMG) Oligomers Used as a Commercial Antibacterial Humidifier Disinfectant

Abstract

Polyhexamethylene guanidine (PHMG) polymers used as an active ingredient in an antibacterial humidifier disinfectant were reported to cause harm to the human health when inhaled, although physical contact with this material was known to present low toxicity to humans. It is therefore necessary to develop an optimal analysis method which enables detection and analysis of PHMG polymers. MALDI-TOF investigations of PHMG are performed with a variety of matrices, and it is found that CHCA and 2,5-DHB are excellent matrices which well reflects the polymer population even at high mass. For the provided PHMG sample, the number-average (M n ) and weight-average (M w ) molecular masses were determined to be 744.8 and 810.7, respectively, when the CHCA was used as a matrix. The rank of the matrices in terms of averaged molecular weight was CHCÃ 2,5-DHB > 5-NSA > DHAP, THAP > ATT > IAA ~ super-DHB ~ HABA. In addition, PSD of the PHMG oligomer ions exhibited a few unique fragmenation characteristics. The formation of a-and c-type fragments was the major fragmentation pathway, and the 25-Da loss peaks generally accompanied a-and c-type fragments.

Quantitative analysis of polyhexamethylene guanidine (PHMG) oligomers via matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry with an ionic‐liquid matrix

“…In our previous study, a variety of MALDI matrices, including α‐cyanohydroxycinnamic acid (CHCA), 2,5‐dihydroxybenzoic acid (DHB), sinapinic acid (SA), and 1,8‐dihydroxyanthracen‐9(10 H )‐one (dithranol), were evaluated for the qualitative analysis of PHMG . CHCA was the most effective matrix for analyzing PHMG because it provided wide oligomer coverage and sensitivity.…”

“…In our previous study, a variety of MALDI matrices, including α-cyanohydroxycinnamic acid (CHCA), 2,5-dihydroxybenzoic acid (DHB), sinapinic acid (SA), and 1,8-dihydroxyanthracen-9(10H)-one (dithranol), were evaluated for the qualitative analysis of PHMG. [2] CHCA was the most effective matrix for analyzing PHMG because it provided wide oligomer coverage and sensitivity. Therefore, in the present study, we only used CHCA-derived ILMs, such as 1-methylimidazolium, diethyl ammonium, butylammonium, tributylammonium, pyridinium, and N,N-diisopropylethyl ammonium α-cyano-4hydroxycinnamates, to quantify PHMG.…”

“…In the MALDI‐TOFMS analysis of synthetic polymers, the sample preparation, solvent, cationization agent (salt), and matrix should be optimized for different polymers. It has recently been shown that MALDI‐TOFMS is an excellent tool for characterizing PHMG polymers, and when an appropriate MALDI matrix was used, it provided information about the number‐average molecular mass ( M n ), weight‐average molecular mass ( M w ), polydispersity ( M w / M n ), and branching structures of the PHMG polymers …”

“…It has recently been shown that MALDI-TOFMS is an excellent tool for characterizing PHMG polymers, and when an appropriate MALDI matrix was used, it provided information about the number-average molecular mass (M n ), weight-average molecular mass (M w ), polydispersity (M w /M n ), and branching structures of the PHMG polymers. [2,20] Despite the widespread use of MALDI-MS in the qualitative analysis of synthetic polymers, the technique has been viewed as unsuitable for quantifying analytes because of its poor sample-to-sample, spot-to-spot, and shot-to-shot reproducibility. [21] In recent years, a variety of experimental strategies have been implemented to quantify amino acids, lipids, drugs, small molecules, oligonucleotides, carbohydrates, peptides, proteins, and polymers.…”

Antimicrobial Activity of Polyhexamethylene Guanidine Derivatives Introduced into Polycaprolactone

“…PCL containing 1% of PHMG sulfanilate strongest inhibited hydrolases activity, whereas PCL modified with 1% of PHMG granular polyethylene wax cases creatingionic bindings with monophosphate groups present in the bacterial cell and in the nucleic acid. PHMG used as an active ingredient in an antibacterial humidifier disinfectant were reported to cause harm to human health when inhaled, although physical contact with this material was known to present low toxicity to humans [5].…”