Atomistic molecular dynamics simulation and COSMO-SAC approach for enhanced 1,3-propanediol extraction with imidazolium-based ionic liquids

Raj Akshat; Anand Bharti; Padmini Padmanabhan

doi:10.1007/s00894-024-05964-7

Atomistic molecular dynamics simulation and COSMO-SAC approach for enhanced 1,3-propanediol extraction with imidazolium-based ionic liquids

J Mol Model. 2024 May 11;30(6):164. doi: 10.1007/s00894-024-05964-7.

Authors

Raj Akshat¹, Anand Bharti², Padmini Padmanabhan³

Affiliations

¹ Department of Bioengineering and Biotechnology, Birla Institute of Technology Mesra, Ranchi, Jharkhand, 835215, India.
² Department of Chemical Engineering, Birla Institute of Technology, Ranchi, Jharkhand, 835215, India. abharti@bitmesra.ac.in.
³ Department of Bioengineering and Biotechnology, Birla Institute of Technology Mesra, Ranchi, Jharkhand, 835215, India. padmini@bitmesra.ac.in.

PMID: 38733431
DOI: 10.1007/s00894-024-05964-7

Abstract

Context: 1,3-Propanediol (1,3-PDO) is a key chemical in various industries, including pharmaceuticals and material sciences, and is projected to see significant market growth. However, the current challenges in its downstream processing, particularly in terms of cost and efficiency, highlight the need for innovative solutions. Our study delves into using ionic liquids (ILs) as a potential alternative, aiming to address these critical separation challenges more sustainably and efficiently. In this study, we utilized molecular dynamics (MD) simulations and the COSMO-SAC to examine 1,3-propanediol (1,3-PDO) extraction using four imidazolium-based ionic liquids with 1-butyl-3-methylimidazolium [Bmim] cation and with different anions bis(pentafluoroethanesulfonyl)imide [NPF2]^-, bis(trifluoromethylsulfonyl)imide [NTF2]^-, thiocyanate [SCN]^-, and trifluoromethanesulfonate [TFO]^-. Molecular dynamics simulations, incorporating analysis of radial distribution functions (RDF) and spatial distribution functions (SDF), revealed that [Bmim][SCN] and [Bmim][TFO] exhibit enhanced interactions with 1,3-PDO. Notably, [Bmim][SCN] formed the most hydrogen bonds, averaging 1.639 per molecule, due to its coordinating [SCN]^- anion. This was in contrast to the fewer hydrogen bonds formed by non-coordinating anions in [Bmim][NPF2] and [Bmim][NTF2]. In ternary systems, [Bmim][SCN] and [Bmim][TFO] demonstrated superior selectivity for 1,3-PDO extraction compared to the other ionic liquids, with selectivity values around 29. These findings, supported by COSMO-SAC predictive modeling, highlight the potential of [Bmim][SCN] as a promising candidate for 1,3-PDO extraction, emphasizing the importance of anion selection in optimizing ionic liquid properties for this application.

Methods: In our study, we employed MD simulations, incorporating the OPLS-AA force field, and COSMO-SAC to investigate the extraction of 1,3-PDO using imidazolium-based ionic liquids: [Bmim][NTF2], [Bmim][NPF2], [Bmim][SCN], and [Bmim][TFO]. The MD simulations were conducted using LAMMPS software, focusing on elucidating the RDF, SDF, and hydrogen bonding. Analysis of the distribution coefficient (β) and selectivity (S) for the ternary mixture was also conducted. These aspects of the simulation were analyzed using TRAVIS and VMD software. Additionally, the COSMO-SAC model was employed to determine the activity coefficients of 1,3-PDO in the ionic liquids, with molecular optimization conducted using Gaussian16 and sigma profile calculations performed using COSMO-SAC.

Keywords: 1,3-Propanediol; COSMO-SAC; Ionic liquids; Molecular dynamics.