<i>In silico</i> COSMO-RS predictive screening of ionic liquids for the dissolution of plastic

Mohan, Mood; Keasling, Jay D.; Simmons, Blake A.; Singh, Seema

doi:10.1039/d1gc03464b

Cited by 47 publications

(47 citation statements)

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“…The COSMO-RS model is a powerful computational approach for calculating equilibrium thermodynamic properties and screening solvents for polymer dissolution. , It requires structural data as the only input information to predict the solubility and other thermodynamic properties of a solute in any solvent environment. The chemical structures of all the studied molecules such as lignin, Cyrene, dimethyl isosorbide (DMI), and water were created and drawn using Avogadro .…”

Section: Computational Detailsmentioning

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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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: Computational Detailsmentioning

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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“…The ILs with lower excess enthalpy, H E , and lower activity coefficient, ln ( γ ), values of lignin should also be cross-checked for viscosity of a solvent. In our previous publication on plastic dissolution in ILs, we predicted the viscosity of ILs using the COSMO-RS model and showed that the predicted values were highly correlated with the experimental viscosities 59 . Therefore, the viscosity of tetrabutylammonium, tetrabutylphosphonium, cholinium, 1-ethyl-3-methylimidazolium, and 1,1-dipropylpyrrolidinium-based cations in combination with amino acid and carboxylate-based anions were predicted using the COSMO-RS model.…”

Section: Parameters That Influence Lignin Dissolutionmentioning

confidence: 77%

“…We then computationally screened thousands of ILs for cellulose and hemicellulose dissolution 27 , 32 , 58 . In addition, we have validated the COSMO-RS model against experimental data for plastic dissolution in ILs and successfully screened 9405 ILs for plastic dissolution 59 .…”

Section: Resultsmentioning

confidence: 99%

“…The COSMO files for all cations and anions were generated based on the procedure outlined in the COSMO-RS calculations section. According to our previous study on plastic-IL screening, the anions and cations were selected with different functional groups 59 . The anions such as amino acid-based anions are considered for the screening study based on the Ohno and Fukumoto 65 study.…”

Section: Resultsmentioning

confidence: 99%

“…In general, ILs might either be modelled by different ‘conformers’ with respect to the relative arrangement of their ions in the COSMO calculation, or simply as two independent, equimolar, ionic species, whose sigma profiles can be combined freely. The second approach is much efficient and was successfully implemented in earlier works 27 , 54 , 59 , 66 . Similar to that, it is carried out in this study.…”

Section: Computational Detailsmentioning

confidence: 99%

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Multiscale molecular simulations for the solvation of lignin in ionic liquids

Mohan

Simmons

Sale

et al. 2023

Sci Rep

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Lignin, the second most abundant biopolymer found in nature, has emerged as a potential source of sustainable fuels, chemicals, and materials. Finding suitable solvents, as well as technologies for efficient and affordable lignin dissolution and depolymerization, are major obstacles in the conversion of lignin to value-added products. Certain ionic liquids (ILs) are capable of dissolving and depolymerizing lignin but designing and developing an effective IL for lignin dissolution remains quite challenging. To address this issue, the COnductor-like Screening MOdel for Real Solvents (COSMO-RS) model was used to screen 5670 ILs by computing logarithmic activity coefficients (ln(γ)) and excess enthalpies (HE) of lignin, respectively. Based on the COSMO-RS computed thermodynamic properties (ln(γ) and HE) of lignin, anions such as acetate, methyl carbonate, octanoate, glycinate, alaninate, and lysinate in combination with cations like tetraalkylammonium, tetraalkylphosphonium, and pyridinium are predicted to be suitable solvents for lignin dissolution. The dissolution properties such as interaction energy between anion and cation, viscosity, Hansen solubility parameters, dissociation constants, and Kamlet–Taft parameters of selected ILs were evaluated to assess their propensity for lignin dissolution. Furthermore, molecular dynamics (MD) simulations were performed to understand the structural and dynamic properties of tetrabutylammonium [TBA]+-based ILs and lignin mixtures and to shed light on the mechanisms involved in lignin dissolution. MD simulation results suggested [TBA]+-based ILs have the potential to dissolve lignin because of their higher contact probability and interaction energies with lignin when compared to cholinium lysinate.

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First principles prediction of NRTL binary interaction parameters for furfural derivatives

Joos,

Lugo,

Sabbe

et al. 2023

AIChE Journal

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Biobased molecules constitute sustainable alternatives for fossil‐based chemicals. However, to allow further valorization, the complex product mixtures resulting from biomass processing typically require downstream separation. Although many (semi)empirical thermodynamic models, like NRTL, are available for separation process design, their application for biobased molecules is hampered due to the lack of the necessary data to determine the binary interaction parameters used in these models. Therefore, in this work a case study comprising a set of furfural derivates has been used to showcase a methodology to efficiently determine these parameters. Based on first principles, COSMO‐RS is used to generate a dataset of thermodynamic activities, which is subsequently used to regress the NRTL model against. Comparison of NRTL‐HOC simulated vapor–liquid equilibria (VLE's) with experimental VLE's showed excellent agreement, confirming that COSMO‐RS can be used to extend the use of (semi)‐empirical models toward applications involving biobased molecules of which limited experimental data is available.

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In silico COSMO-RS predictive screening of ionic liquids for the dissolution of plastic

Abstract: Herein we report the screening of 9405 ionic liquids for plastic dissolution using the continuum solvation model (COMSO-RS) and the results are validated with experiments.

Cited by 47 publications

References 74 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

Multiscale molecular simulations for the solvation of lignin in ionic liquids

First principles prediction of NRTL binary interaction parameters for furfural derivatives

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