Fourier transform ion cyclotron resonance mass spectrometry for the analysis of molecular composition and batch‐to‐batch consistency of plant‐derived polyphenolic ligands developed for biomedical application

Abstract

RationaleComplex plant‐derived polyphenols are promising for biomedical application. Their high complexity prevents the use of conventional pharmacopoeia techniques to perform quality control. The goal of this study was to apply ultra‐high‐resolution mass spectrometry to evaluate the batch‐to‐batch consistency of the molecular composition of a polyphenolic ligand using appropriate statistical metrics.MethodsPolyphenols were obtained by hydrolyzed‐lignin oxidation. Manufacturing was performed under a range of reaction conditions: heating cycles, oxygen flows, purification. Direct‐injection Fourier transform ion cyclotron resonance mass spectrometry (DI FTICR‐MS) was applied to analyze reaction products. For pairwise comparison Jaccard and Tanimoto similarities calculations were proposed. In addition, principal component analysis (PCA) was applied for sample grouping based on the molecular class contributions.ResultsFTICR‐MS analysis revealed moderate Jaccard similarity of products synthesized under the same conditions, which shared about 50% of the formulae calculated in each sample. The intensity‐based Tanimoto index indicated high similarity of major components distribution of samples synthesized under standard conditions, while products obtained with variations in synthetic conditions were significantly different. PCA of molecular class contributions showed similar grouping with a high cumulative score.ConclusionsFTICR‐MS provides robust metrics for the examination of batch‐to‐batch consistency of synthetic polyphenol materials. This approach can be proposed for the analysis of reference samples and for development of complementary methods for quality control of medicinal agents based on various biologically active matrices.

Vacuum Pyrolysis of Hybrid Poplar Milled Wood Lignin with Fourier Transform-Ion Cyclotron Resonance Mass Spectrometry Analysis of Feedstock and Products for the Elucidation of Reaction Mechanisms

“…Among the most significant of these analytical techniques is advanced mass spectrometry (MS) analysis. Some recently published work on lignin MS analysis can be found from Bowman et al (synthesized model oligomers), Qi et al, Kubatova et al, Mikhael et al, and Prothmann et al ,− A particularly robust MS technique for the characterization of complex matrices is Fourier transform-ion cyclotron resonance (FT-ICR) MS, which is capable of assigning molecular formulas (i.e., C x H y O z ) to detected MS peaks from the m/z value alone. − FT-ICR MS has been successfully applied for the characterization and/or description of lignin directly as well as for similar/relevant reactive processes and systems. ,− …”

Humic Acid Extracted from Danty via Catalytic Oxidation Using H2O2/Birnessite: Characteristics and Agricultural Beneficial Effects

“…The Van Krevelen diagrams illustrate the molecular compositions of HA b (Figure A) and the danty (Figure B). According to the H/C and O/C ratios, the HA b and danty were composed of the following seven groups of components: lipid-like (H/C: 1.5–2.0; O/C: 0–0.3), protein-like (H/C: 1.5–2.2; O/C: 0.3–0.67), carbohydrate-like (H/C: 1.5–2.2; O/C: 0.67–1.2), unsaturated hydrocarbon-like (H/C: 0.7–1.5; O/C: 0–0.1), lignin-like (H/C: 0.7–1.5; O/C: 0.1–0.67), tannin-like (H/C: 0–1.5; O/C: 0.67–1.2), and condensed aromatic component (H/C: 0.2–0.7; O/C: 0–0.67) (Figure C). ,, Compared with the danty, HA b extracted via catalytic oxidation showed significantly lower relative abundances of lipid, protein, unsaturated hydrocarbon, and lignin (Figure A,B). For instance, lipid and protein relative abundances in the danty were 4.2 and 0.15%, compared to 0.5 and 0.03% in the HA b .…”

“…Before ESI-FT-ICR-MS analysis, the purified danty and HA b were purified according to the procedure described by Melendez-Perez et al, dissolved in NH 3 solution (10%, analytical grade), and passed through a column packed with protonated cation exchange resin (Agilent, USA, Bond Elut-PPL, 1 g 6 mL, 30/PK) . Then, ultrahigh-resolution mass spectra were obtained using a SolariX XR mass spectrometer (Bruker Daltonics, USA) equipped with a 9.4 T superconducting magnet and a dual-mode ESI/MALDI ion source. − …”

“…5C). 26,27,37 Compared with the danty, HA b extracted via catalytic oxidation showed significantly lower relative abundances of lipid, protein, unsaturated hydrocarbon, and lignin (Figure 5A,B). For instance, lipid and protein relative abundances in the danty were 4.2 and 0.15%, compared to 0.5 and 0.03% in the HA b .…”

Hepatoprotective Activity of Lignin-Derived Polyphenols Dereplicated Using High-Resolution Mass Spectrometry, In Vivo Experiments, and Deep Learning

“…In the particular case of BP-Cx-1, the results are promising from a practical point of view. In fact, synthetic lignin derivatives have batch-tobatch reproducibility [40]. With the proven mechanism, it may be introduced as a bivalent drug: As a dietary fiber, which helps in the elimination of residues in the intestinal tract and improves the intestinal environment [41,42], and as a hepatoprotective agent, which prevents or reduces liver damage.…”