Advanced Molecular Dynamics Model for Investigating Biological-Origin Microfibril Structures.

Understanding the atomic-scale structure of wood microfibrils is essential for establishing fundamental properties in various wood-based research aspects, including moisture impact, wood modification, and pretreatment. In this study, we employed molecular dynamics simulations to investigate the arrangement of wood polymers, including cellulose, hemicellulose, and lignin, with a primary focus on the composition of softwood, specifically Norway Spruce wood. We assessed the accuracy of our molecular dynamics model by comparing it with available experimental data, such as density, Young's modulus, and glass transition temperature, which ensures the reliability of our approach. A key aspect of our study involved modeling the active sorption site for water interaction with wood polymers. Our findings revealed that the interaction between water and hemicellulose, particularly within the hemicellulose-cellulose interphase, was the most prominent binding site. This observation aligns with prior research in this field, further strengthening the validity of our results.

Elucidating intermolecular forces to improve compatibility of kraft lignin in poly(lactic acid).

Owing to its abundant supply from renewable resources, lignin has emerged as a promising functional filler for the development of sustainable composite materials. However, achieving good interfacial compatibility between lignin and synthetic polymers, particularly poly (lactic acid) (PLA), remains a fundamental challenge. To advance the development of high-performance bio-based composites incorporating lignin and PLA, our study has scrutinized to unravel the nuances of interfacial binding interactions with the lignin and PLA composite system. Molecular level and experimental examinations were employed to decipher fundamental mechanisms governing and demonstrating the interfacial adhesion. We synthesized casted films of lignin/PLA and acetylated lignin/PLA at varying weight percentages of lignin (5%, 10%, and 20%) and comprehensively investigated their physicochemical and mechanical properties. The inclusion of acetylated lignin in the composites resulted in improved mechanical strength and Young's modulus, while the glass transition temperature and melting point were reduced compared to neat PLA. Systematic variations in these properties revealed distinct compatibility behaviors between unmodified lignin and acetylated lignin when incorporated into PLA. Molecular dynamics (MD) simulation results elucidated that the observed changes in material properties were primarily attributed to the acetylation of lignin. Acetylated lignin exhibited lower Coulombic interaction energy and higher van der Waals forces, indicating a stronger affinity to PLA and a reduced propensity for intermolecular aggregation compared to unmodified lignin. Our findings highlight the critical role of controlling intermolecular interactions and lignin aggregation to develop PLA composites with predictable performance for new applications, such as functional packaging materials.

Fungal enzyme degradation of lignin-PLA composites: Insights from experiments and molecular docking simulations.

Fungal enzymes are effective in degrading various polymeric materials. In this study, we assessed the initial degradation of composites consisting of lignin-poly(lactic acid) (PLA) with both unmodified lignin (LIG) and oxypropylated lignin (oLIG) incorporated at 10 % and 40 % weight within the PLA matrix in a fungal environment. Trametes versicolor fungi were used, and the samples were treated only for eight weeks. Although there was no significant difference in weight loss, the degradation process impacted the chemical and thermal properties of the composites, as shown by Fourier transform infrared spectroscopy (FTIR) and Differential scanning calorimetry (DSC) analyses. After the degradation process, the carbonyl index values decreased for all composites and the hydroxyl index values increased for LIG/PLA and a reverse trend was observed for oLIG/PLA composites. The first heating scan from DSC results showed that the melting peak and the cold crystallization peak disappeared after the degradation process. Microscopic analysis revealed that LIG/PLA exhibited higher roughness than oLIG/PLA. Molecular docking simulations were carried out using guaiacylglycerol-ß-guaiacyl ether (GGE) and lactic acid (LA) as model compounds for lignin and PLA, respectively, with laccase (Lac) enzyme for Trametes versicolor. The docking results showed that GGE had the strongest binding interaction and affinity with Lac than lactic acid and oxypropylated GGE. The oxypropylated GGE formed a shorter hydrogen bonding with the Lac enzyme than GGE and LA. The trend associated with the degradation of composites from experimental and molecular docking findings was consistent. This combined approach provided insights into the degradation process using fungi and had the potential to be applied to different polymeric composites.

Fractionation of lignin using organic solvents: A combined experimental and theoretical study.

Refining of industrial lignin to produce homogeneous fractions is essential for high-value applications. However, the understanding of key interactions between a variety of solvents with lignin polymer is still uncertain. In this work, single-step fractionation of industrial hardwood kraft lignin (HKL) using organic solvents of different polarities - ethanol, acetone, diethyl ether and hexane - was investigated by combining an experimental and theoretical approach. Experimental results revealed that higher polarity solvents (ethanol and acetone) exhibited higher solubility yield compared to moderate and low polarity solvents. The chemical differences between lignin fractions were proven by pyrolysis gas chromatography mass spectrometry and near infrared spectroscopy. Density functional theory (DFT) results indicated that ethanol presented higher interaction energy followed by acetone, diethyl ether and hexane, which was consistent with experimental findings. Hydrogen bond and non-covalent interaction results from DFT demonstrated that the predominant interaction was found for high polarity of ethanol over other solvents and γ-OH in the lignin model is the key site.

Multiscale modelling investigation of wood modification with acetic anhydride.

Density functional theory (DFT) and molecular dynamics (MD) simulations were employed to investigate the interaction of cellulose and lignin with acetic anhydride for explaining the wood modification process. Cellulose was modelled with a cellobiose unit and dibenzodioxocin was used to represent the lignin model. Results obtained from both methods revealed that acetic anhydride interacted substantially more with the cellobiose model than the lignin model. The interaction energy of cellobiose-acetic anhydride was higher (about 20 kJ mol-1) than that of lignin-acetic anhydride. DFT results on hydrogen bonding indicated that the hydroxyl group from cellobiose and the aromatic hydroxyl group from lignin models have similar energy values, which explain the equal strength of hydrogen bond interaction. The same trend was also obtained for the substitution of acetyl group in the hydroxyl group. MD results have also predicted that acetic anhydride forms a stronger interaction with cellobiose than with the lignin model, and these findings were in agreement with the DFT results.

The Anion Effect on Li(+) Ion Coordination Structure in Ethylene Carbonate Solutions.

Rechargeable lithium ion batteries are an attractive alternative power source for a wide variety of applications. To optimize their performances, a complete description of the solvation properties of the ion in the electrolyte is crucial. A comprehensive understanding at the nanoscale of the solvation structure of lithium ions in nonaqueous carbonate electrolytes is, however, still unclear. We have measured by femtosecond vibrational spectroscopy the orientational correlation time of the CO stretching mode of Li(+)-bound and Li(+)-unbound ethylene carbonate molecules, in LiBF4, LiPF6, and LiClO4 ethylene carbonate solutions with different concentrations. Surprisingly, we have found that the coordination number of ethylene carbonate in the first solvation shell of Li(+) is only two, in all solutions with concentrations higher than 0.5 M. Density functional theory calculations indicate that the presence of anions in the first coordination shell modifies the generally accepted tetrahedral structure of the complex, allowing only two EC molecules to coordinate to Li(+) directly. Our results demonstrate for the first time, to the best of our knowledge, the anion influence on the overall structure of the first solvation shell of the Li(+) ion. The formation of such a cation/solvent/anion complex provides a rational explanation for the ionic conductivity drop of lithium/carbonate electrolyte solutions at high concentrations.