Wood dimensional stability enhancement by multivalent metal-cation-induced lignocellulosic microfibrils crosslinking.

Wood is a hygroscopic material that responds to the moisture changes of the surrounding environment through swelling and shrinkage, making it dimensionally unstable. Here, we introduce a facile metal-ion-modification (MIM) approach to enhance the dimensional stability of wood. The MIM process involved swelling the wood samples with aqueous metal ion solutions and drying. The high valent metal cations, such as Fe3+, Al3+, and Zr4+, interacted with the hydrophilic groups (e.g., OH, COOH) present in the wood fibers, limiting their access to water and moisture, thereby enhancing the wood's hydrophobicity and dimensional stability. Evaluation of three wood species, southern yellow pine, poplar, and red oak, revealed water contact angles of 120-130° after MIM, indicative of enhanced surface hydrophobicity. Fe3+ treatment decreased southern yellow pine's swelling ratio from 6 % to 4 %. Fe3+-treated wood exhibited tangential anti-swelling efficiencies ranging from 39.83 % to 57.14 % and radial anti-swelling efficiencies from 34.74 % to 48.33 %, varying across wood species. The enhancement of wood dimensional stability can be attributed to the formation of irreversible coordination bonds between metal cations and lignocellulosic microfibrils in the wood cell wall. These bonds prevent the microfibrils from slipping in response to moisture absorption and desorption.

Laccase multi-point covalent immobilization: characterization, kinetics, and its hydrophobicity applications.

Laccase from Myceliophthora thermophila was immobilized using one-point and multi-point covalent attachment on both a native and a modified new commercial epoxy carrier (Immobead 150P). After 10 cycles of operation at pH 3.0 and temperature 70 °C, the multi-point covalently immobilized laccase on the modified Immobead 150P performed best in terms of immobilization characteristics, retaining 95% of its initial activity. Thermodynamic parameters of thermal inactivation emphasized the positive impact of the immobilization procedure. At 50 °C, the immobilized and free enzyme activity levels dropped by 27 and 73%, respectively, after 48 h of incubation. The immobilized enzyme enhanced its stability in alkaline conditions, resuming 95% of its original activity after 3 h at pH 9.0. Immobilization reduced substrate affinity because the free laccase's Km value was lower than that of the immobilized laccase. Finally, the application of immobilized laccase in an innovative wood treatment process was tested by grafting lauryl gallate (LG) in order to provide hydrophobic properties to the wood. The results showed a relative water contact angle of 85.7% for treated wood, whereas the control showed only 26.6%, after 4 min of contact between water and beechwood surface. KEY POINTS: • Multi-point covalent immobilization of a commercial laccase on a commercial support. • Enzymatic parameters generally improved by immobilization process. • New application of immobilized laccase: enzymatic-assisted wood hydrophobization.

Kinetic and thermodynamic study of laccase cross-linked onto glyoxyl Immobead 150P carrier: Characterization and application for beechwood biografting.

In this study, we cross-linked aminated Thermothelomyces thermophilus laccase onto Immobead 150P epoxy carrier, and achieved an immobilization yield of 99.84 %. The optimum temperature and pH values for the oxidation of ABTS by laccase were determined to be 70 °C and pH 3.0. After 6 h at 50 °C, laccase activity was diminished by about 13 % in the free form and 28 %, in the immobilized form. Km values for both free and cross-linked laccase were 0.051 and 0.567 mM, whereas Vmax values were 2.027 and 0.854 µmol. min-1, respectively. The immobilized laccase was able to preserve its full activity for 6 weeks, retaining approximately 95 % and 78 % of its initial activity after 8 and 20 weeks, respectively. The contact angles were two-fold higher when the laccase enzyme was occupied in the biografting reaction, revealing that the hydrophobic compound bonded stably onto beechwood samples.