Prediction of solubility parameters of lignin and ionic liquids using multi-resolution simulation approaches

Mohan, Mood; Huang, Kaixuan; Pidatala, Venkataramana R.; Simmons, Blake A.; Singh, Seema; Sale, Kenneth L.; Gladden, John M.

doi:10.1039/d1gc03798f

Cited by 39 publications

(38 citation statements)

References 73 publications

(123 reference statements)

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“…In addition, the results were further analyzed with Hansen solubility parameters (HSPs), and the performance of the HSP model has previously been demonstrated for lignin solubility using different solvent systems. 75 The HSP of a solvent or solute is broken down into three meaningful contributors, such as polar (δ p ), hydrogen-bonded (δ h ), and dispersion (δ d ) forces. It is a usual practice to depict a solvent as a point in Hansen's space, which is a three-dimensional space whose axis is comprised of the individual HSP contributors.…”

Section: Dissolution Of Lignin In Cyrene and Cyrene:watermentioning

confidence: 99%

“…For good solvents, the value of RED should be less than 1 (i.e., R a < R 0 ). 75 The solubility of lignin in Cyrene, water, and Cyrene:water mixtures is analyzed and shown in Figure S3 (Supporting Information). Lower RED values indicate greater lignin solubility, and a 4:1 molar ratio of Cyrene to water results in lower RED values and greater lignin solubility.…”

Section: Dissolution Of Lignin In Cyrene and Cyrene:watermentioning

confidence: 99%

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Multiscale Molecular Simulation Strategies for Understanding the Delignification Mechanism of Biomass in Cyrene

Mohan

Sale

Kalb

et al. 2022

ACS Sustainable Chem. Eng.

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In recent years, the cellulose-derived solvent Cyrene has piqued considerable interest in the green chemistry community despite only recently being available in the quantities required for solvent applications. Deconstruction of cellulose is an essential step in the production of fuel and value-added chemicals from lignocellulosic biomass. However, the high recalcitrance and heterogeneity of lignin hinder this process, necessitating the need to solubilize lignin. To understand the dissolution of lignin in Cyrene and Cyrene−cosolvent systems, multiscale molecular simulation approaches have been employed. Initially, the conductor-like screening model for real solvent (COSMO-RS) model was used to assess the thermodynamic properties of lignin in Cyrene and Cyrene−cosolvent systems. From the COSMO-RS calculations, the correlation between the predicted activity coefficient and the experimental lignin solubility was excellent. Further, classical molecular dynamics (MD) simulations were performed to evaluate the delignification of biomass by predicting structural and dynamic properties of lignin−solvent systems. The microscopic properties such as interaction energies, radius of gyration, solvent-accessible surface area, radial and spatial distribution functions (RDFs/ SDFs), and hydrogen bonds were assessed to characterize lignin dissolution in these solvent mixtures and were validated with experimental data. From the MD simulations, it was observed that lignin adopts a coil-like structure in Cyrene and Cyrene:water mixtures, thereby dissolving the lignin, while lignin adopts a collapsed-like structure in the presence of water. The occupancy density of Cyrene is highly surrounded by the aryl and hydroxyl groups of lignin polymer rather than by water. The interaction energies between lignin and Cyrene and Cyrene−cosolvent were much stronger than that between lignin and water, explaining the higher biomass delignification in Cyrene-based solvents.

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Section: Dissolution Of Lignin In Cyrene and Cyrene:watermentioning

confidence: 99%

Section: Dissolution Of Lignin In Cyrene and Cyrene:watermentioning

confidence: 99%

Multiscale Molecular Simulation Strategies for Understanding the Delignification Mechanism of Biomass in Cyrene

Mohan

Sale

Kalb

et al. 2022

ACS Sustainable Chem. Eng.

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“…Based on the solubility parameters of benzothiophene and DFT calculations, it was also confirmed that both van der Waals (vdW) and electrostatic interactions played a predominant role in the extraction of the sulfur compound, whereas in the case of n-decane, the weak noncovalent interactions govern the extraction process based on solubility in the DES. 41,42…”

Section: Lle Results and Cosmo-sac Predictionmentioning

confidence: 99%

Molecular Mechanism and Solubility Performance Evaluation for Separation of Benzothiophene and Model Diesel Compounds through Deep Eutectic Solvents as Extractants

Kumar

Banerjee

2022

Ind. Eng. Chem. Res.

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During combustion, sulfur compounds in fuels are oxidized to SO x , poisoning automatic catalytic converters and posing severe environmental risks (e.g., acid rain). As an outcome, effective liquid fuel desulphurization is a vital step in reducing SO x emissions and their inherent ecological impacts. The extraction of ultralow benzothiophene from n-decane as representative model diesel fuel was analyzed using phosphonium-based deep eutectic solvents (DESs) at 308.15 K and 1 bar pressure. Liquid−liquid equilibrium (LLE) studies were conducted on a ternary system of DES− benzothiophene−n-decane for all six feed point concentrations. 1 H NMR analysis was used to determine the molar composition of each raffinate and extract phase. The LLE experimental findings were examined using a conductor-like screening model for segment activity coefficient (COSMO-SAC) based on quantum calculations. The average root-mean-square deviation (RMSD) of the studied LLE ternary system was 1.07%, which was suitable considering the prior nature of the approach. The σ-profile calculations using the COSMO-SAC model and Hansen solubility parameters (HSPs) using different predicted models were used to provide insights into the molecular mechanism of benzothiophene extraction efficacy using DES. We observed higher extraction of benzothiophene due to the higher proportion of hydrogen-bonding and dispersion-type interactions. Charge transfer analysis using the density functional theory (DFT) calculation of the DES cluster suggested that bromide (Br − ) ions can act as a charge transfer bridge between the methyltriphenylphosphonium (MTP) cation and the hydrogen bond donor. The MTP cation and ethylene glycol also aided in the extraction of benzothiophene by dislocating charge from the aromatic sulfur compound. The bromide (Br − ) ion is essentially noninteractive with benzothiophene due to retention of the conventional hydrogen bond network existing within the initial components of DES, mainly hydrogen bond donors and hydrogen bond acceptors.

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“…Yao et al extended the application of COSMO-RS prediction to demonstrate the synergistic advantages of multiple ions in a cholinium-based ionic liquid system for the pretreatment of sorghum biomass (Yao et al, 2021). Mood et al showed that solubility parameters of ionic liquids and deep eutectic solvents calculated using COSMO-RS are predictive of lignin solubility under the likedissolves-like principal and developed a new method to calculate solubility parameters from MD simulation trajectories, allowing predictions to be made for much larger lignin polymers (Mohan et al, 2021;Mohan et al, 2022).…”

Section: Understanding the Interactions Of Biomass With Pretreatment ...mentioning

confidence: 99%

Revisiting Theoretical Tools and Approaches for the Valorization of Recalcitrant Lignocellulosic Biomass to Value-Added Chemicals

et al. 2022

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Biorefinery processes for converting lignocellulosic biomass to fuels and chemicals proceed via an integrated series of steps. Biomass is first pretreated and deconstructed using chemical catalysts and/or enzymes to liberate sugar monomers and lignin fragments. Deconstruction is followed by a conversion step in which engineered host organisms assimilate the released sugar monomers and lignin fragments, and produce value-added fuels and chemicals. Over the past couple of decades, a significant amount of work has been done to develop innovative biomass deconstruction and conversion processes that efficiently solubilize biomass, separate lignin from the biomass, maximize yields of bioavailable sugars and lignin fragments and convert the majority of these carbon sources into fuels, commodity chemicals, and materials. Herein, we advocate that advanced in silico approaches provide a theoretical framework for developing efficient processes for lignocellulosic biomass valorization and maximizing yields of sugars and lignin fragments during deconstruction and fuel and chemical titers during conversion. This manuscript surveys the latest developments in lignocellulosic biomass valorization with special attention given to highlighting computational approaches used in process optimization for lignocellulose pretreatment; enzyme engineering for enhanced saccharification and delignification; and prediction of the genome modification necessary for desired pathway fine-tuning to upgrade products from biomass deconstruction into value-added products. Physics-based modeling approaches such as density functional theory calculations and molecular dynamics simulations have been most impactful in studies aimed at exploring the molecular level details of solvent-biomass interactions, reaction mechanisms occurring in biomass-solvent systems, and the catalytic mechanisms and engineering of enzymes involved in biomass degradation. More recently, with ever increasing amounts of data from, for example, advanced mutli-omics experiments, machine learning approaches have begun to make important contributions in synthetic biology and optimization of metabolic pathways for production of biofuels and chemicals.

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Prediction of solubility parameters of lignin and ionic liquids using multi-resolution simulation approaches

Abstract: The solubility parameter (SP) of a molecular species is a vital feature that evaluates polarity and quantifies the ‘like-seeks-like' principle, which is used in chemistry to screen solvents for dissolution....

Cited by 39 publications

References 73 publications

Multiscale Molecular Simulation Strategies for Understanding the Delignification Mechanism of Biomass in Cyrene

Multiscale Molecular Simulation Strategies for Understanding the Delignification Mechanism of Biomass in Cyrene

Molecular Mechanism and Solubility Performance Evaluation for Separation of Benzothiophene and Model Diesel Compounds through Deep Eutectic Solvents as Extractants

Revisiting Theoretical Tools and Approaches for the Valorization of Recalcitrant Lignocellulosic Biomass to Value-Added Chemicals

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