A Combined Experimental and Computational Study of Polyaromatic Hydrocarbon Aggregation – Isolating the Effect of Attached Functional Groups

Dorin Simionesie, Gregory O’callaghan, Raphael Laurent, Jon A. Preece, Robert Evans, Zhenyu J. Zhang

Research output: Contribution to journalArticle

Abstract

To establish, and isolate, the influence of different chemical functional groups on the aggregation of polyaromatic hydrocarbons, a series of triphenylene-based compounds were investigated using experimental and computational approaches together. Containing alkoxy- side chains of varying length and amide appendages, both with and without a terminating carboxylic acid, their aggregation structures, sizes, and kinetics in toluene were studied over several length scales, using a combination of Dynamic Light Scattering (DLS) and Diffusion-Ordered NMR spectroscopy (DOSY), complemented with Molecular Dynamics (MD) simulations. There is a strong correlation between molecular architecture and aggregation mechanisms across different length scales: addition of polar functional groups and heteroatoms resulted in compounds that are more prone to aggregation and form large, micrometer-sized clusters, while the increased steric hindrance imposed by alkoxy- side chains led to stable nanometer-sized aggregates. These conclusions underline the strong structure-function relationship of polyaromatic hydrocarbons, such as asphaltenes, examined here over multiple size-scales in a single solvent. We also demonstrated the importance of using complementary techniques to study the aggregation process of polyaromatic hydrocarbons that could form aggregates of various sizes over different timescales.
Original languageEnglish
JournalIndustrial and Engineering Chemistry Research
DOIs
Publication statusPublished - 22 Oct 2019

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Hydrocarbons
Functional groups
Agglomeration
Asphaltenes
Toluene
Dynamic light scattering
Carboxylic Acids
Carboxylic acids
Amides
Nuclear magnetic resonance spectroscopy
Molecular dynamics
Kinetics
Computer simulation
alkoxyl radical

Bibliographical note

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Ind. Eng. Chem. Res., copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.iecr.9b04105

Cite this

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abstract = "To establish, and isolate, the influence of different chemical functional groups on the aggregation of polyaromatic hydrocarbons, a series of triphenylene-based compounds were investigated using experimental and computational approaches together. Containing alkoxy- side chains of varying length and amide appendages, both with and without a terminating carboxylic acid, their aggregation structures, sizes, and kinetics in toluene were studied over several length scales, using a combination of Dynamic Light Scattering (DLS) and Diffusion-Ordered NMR spectroscopy (DOSY), complemented with Molecular Dynamics (MD) simulations. There is a strong correlation between molecular architecture and aggregation mechanisms across different length scales: addition of polar functional groups and heteroatoms resulted in compounds that are more prone to aggregation and form large, micrometer-sized clusters, while the increased steric hindrance imposed by alkoxy- side chains led to stable nanometer-sized aggregates. These conclusions underline the strong structure-function relationship of polyaromatic hydrocarbons, such as asphaltenes, examined here over multiple size-scales in a single solvent. We also demonstrated the importance of using complementary techniques to study the aggregation process of polyaromatic hydrocarbons that could form aggregates of various sizes over different timescales.",
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A Combined Experimental and Computational Study of Polyaromatic Hydrocarbon Aggregation – Isolating the Effect of Attached Functional Groups. / Simionesie, Dorin; O’callaghan, Gregory; Laurent, Raphael; Preece, Jon A.; Evans, Robert; Zhang, Zhenyu J.

In: Industrial and Engineering Chemistry Research, 22.10.2019.

Research output: Contribution to journalArticle

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AU - Evans, Robert

AU - Zhang, Zhenyu J.

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