Antioxidant activity of the lignins derived from fluidized-bed fast pyrolysis

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Abstract

A challenge in recent years has been the rational use of forest and agriculture residues for the production of bio-fuel, biochemical, and other bioproducts. In this study, potentially useful compounds from pyrolytic lignins were identified by HPLC-MS/MS and untargeted metabolomics. The metabolites identified were 2-(4-allyl-2-methoxyphenoxy)-1-(4-hydroxy-3-methoxyphenyl)-1-propanol, benzyl benzoate, fisetinidol, phenyllactic acid, 2-phenylpropionic acid, 6,3′-dimethoxyflavone, and vanillin. The 2,2-diphenyl-1-picrylhydrazyl radical scavenging activity (DPPH), trolox equivalent antioxidant capacity (TEAC), and total phenolics content (TPC) per gram of pyrolytic lignin ranged from 14 to 503 mg ascorbic acid equivalents, 35 to 277 mg trolox equivalents, and 0.42 to 50 mg gallic acid equivalents, respectively. A very significant correlation was observed between the DPPH and TPC (r = 0.8663, p ≤ 0.0001), TEAC and TPC (r = 0.8044, p ≤ 0.0001), and DPPH and TEAC (r = 0.8851, p ≤ 0.0001). The polyphenolic compounds in the pyrolytic lignins which are responsible for radical scavenging activity and antioxidant properties can be readily profiled with HPLC-MS/MS combined with untargeted metabolomics. The results also suggest that DPPH, TEAC, and TPC assays are suitable methods for the measurement of antioxidant activity in a variety of pyrolytic lignins. These data show that the pyrolytic lignins can be considered as promising sources of natural antioxidants and value-added chemicals.

Figures

  • Figure 1. Selected HPLC-MS chromatograms (base peak) obtained using LTQ-ORBITRAP (Discovery) in the positive mode: (a) non-PyL; (b) PyL 1; (c) PyL 7; and (d) PyL 24, revealing the diversity of separated compounds from selected samples.
  • Figure 2. The heat map (dendrogram view) of the pyrolytic lignins, generated using the XCMS bioinformatics platform, showing the comparison of metabolite features between different samples. In dendrogram, each row represents a metabolite feature and each column represents samples. Metabolite features, the level of which varies significantly (p < 0.05) are projected on the heat map and were used for sample clustering. The row Z score (scaled expression) value of each feature is plotted in red (high abundance) to green colours (low abundance).
  • Table 1. HPLC-MS/MS and metabolomic analysis (XCMS Bioinformatics Platform) was used for the putative identification of compounds from pyrolytic lignins. Formula, actual mass, M + H, Ring and Double-Bond (RDB), Retention Time (RT), and peak area (%) among reported compounds.
  • Figure 3. Antioxidant activity of pyrolytic lignins, as determined by (a) DPPH assay; (b) TEAC assay; and (c) total phenolics assay. Results are expressed: (a) mg ascorbic acid equivalents/g of pyrolytic lignin (PyL); (b) mg trolox equivalents/g of pyrolytic lignin (PyL); and (c) mg gallic acid equivalents (GAE)/g of pyrolytic lignin (PyL). Each value is presented as a mean ± SD (n = 3). Analysis of variance was performed using one-way completely-randomized ANOVA (CoStat version 6.4) and means are separated using the Student-Newman-Keuls test (p < 0.05). The bars with same alphabet superscript are not significantly different.
  • Figure 4. Principal component analysis (PCA), revealing the correlations between a variety of pyrolytic lignins (derived from fast pyrolysis). PCA plot was generated using XCMS bioinformatics platform for metabolomics. Clusters: Group A phenolics content (1–5 mg gallic acid equivalents (GAE)/g of pyrolytic lignin (PyL), Group B phenolics content (5–15 mg GAE equivalents/g of PyL), Group C, D, and E phenolics content (≥15 mg GAE equivalents/g of PyL).
  • Figure 5. Correlation between antioxidant assays and total phenolics content of pyrolytic lignins (PyL), (a) DPPH versus TPC, (r = 0.8663, p < 0.0001); (b) TEAC versus TPC (r = 0.8044, p < 0.0001); and (c) DPPH versus TEAC (r = 0.8851, p < 0.0001). Product moment correlation was performed using CoStat (version 6.4).
  • Figure 5. orrelation between antioxidant assays and total phenolics content of pyrolytic lignins (PyL), (a) DPPH versus TPC, (r = 0.8663, p < 0.0001); (b) TEAC versus TPC (r = 0.8044, p < 0.0001); an (c) ers s (r 0.8851, p 0.0001). Product o ent c rrelation as erf r e si

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APA

Qazi, S. S., Li, D., Briens, C., Berruti, F., & Abou-Zaid, M. M. (2017). Antioxidant activity of the lignins derived from fluidized-bed fast pyrolysis. Molecules, 22(3). https://doi.org/10.3390/molecules22030372

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