Application of ESI FT-ICR MS to Study Kraft Lignin Modification by the Exoenzymes of the White Rot Basidiomycete Fungus TrametesHirsutaLE-BIN 072

Trameteshirsuta is a wood rotting fungus that possesses a vast array of lignin degrading enzymes, including7 laccases, 7 ligninolyticmanganese peroxidases, 9 lignin peroxidases and 2 versatile peroxidases. In this study,electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI FT-ICR MS)was used to examine kraft lignin modification by the enzymatic system of this fungus.The observed pattern of lignin modification suggested that before the 6th day of cultivation,the fungal enzymatic system tended to degrade more oxidized moleculesand, hence, less recalcitrant molecules, with the production of hard-to-modify reduced molecular species. At some point after the 6th day of cultivation,the fungal enzymatic system tended to degrade more oxidized moleculesand, hence, less recalcitrant molecules, with the production of hard-to-modify reduced molecular species. At some point after the 6th day of cultivation,the fungus started to degrade less oxidized, more recalcitrant, compounds, converting them into the more oxidized forms. The altered pattern of lignin modification enabled changes in the fungal enzymatic system. These changes were further attributed to the appearance of the particular ligninolyticmanganese peroxides enzyme(MnP7), which was added by the fungus to the mixture of enzymes that had already been secreted (VP2 and MnP5). Keywords: wood rotting fungi, kraft lignin, mass spectrometry, peroxidases

Lignin Nanoparticles and Alginate Gel Beads: Preparation, Characterization and Removal of Methylene Blue

A novel and effective green system consisting of deep eutectic solvent (DES) was proposed to prepare lignin nanoparticles (LNPs) without any lignin modification. The LNPs are obtained through the dialysis of the kraft lignin-DES solution. The particle size distribution, Zeta potential and morphology of the LNPs are characterized by using dynamic light scattering (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The average diameter of LNPs is in the range 123.6 to 140.7 nm, and the LNPs show good stability and dispersibility in water. The composite beads composed of LNPs and sodium alginate (SA) are highly efficient (97.1%) at removing methylene blue (MB) from the aqueous solution compared to 82.9% and 77.4% by the SA/bulk kraft lignin composite and pure SA, respectively. Overall, the LNPs-SA bio-nanocomposite with high adsorption capacity (258.5 mg/g) could be useful in improving water quality and other related applications.

Preparation of highly water-resistant wood adhesives using ECH as a crosslinking agent

In this study, kraft lignin and epichlorohydrin (ECH) were used to prepare no-formaldehyde wood adhesives. The lignin was first treated by ball milling, then reacted with glyoxal to produce glyoxalated lignin under alkaline conditions, and then blended with ECH to prepare lignin-based formaldehyde-free adhesive. The influence of the content of ECH on the physicochemical properties of the adhesives was explored, and the possible synthesis mechanism of the ECH-modified glyoxalated lignin adhesives (glyoxalated kraft lignin-epoxy [GKLE]) was investigated. The results show that ECH was beneficial to improving the plywood shear strength and water resistance; the plywood prepared with GKLE-50 adhesive displays comparable water resistance as phenol–formaldehyde resins and its wet shear strength (type I) was 1.05 MPa, exceeding the Chinese National Standards GB/T 9846-2015. Scanning electron microscopy analysis showed that the increase of ECH content promoted the adhesive to penetrate the wood to form glue nails, improving the wet shear strength of the plywood. Chemical analysis indicated that glyoxalation was used to introduce hydroxyethyl groups into the ortho positions of the aromatic rings of lignin, and then the ring-opening reaction between glyoxalated lignin and ECH occurred forming ether bonds. Overall, lignin has displayed great potential in replacing formaldehyde-based adhesives for industrial applications.