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Title: Structure–Property Effects in the Generation of Transient Aqueous Benzoic Acid Anhydrides by Carbodiimide Fuels

Abstract

The design of dissipative systems, which operate out-of-equilibrium by consuming chemical fuels, is difficult. As yet, there are a few examples of privileged fuel chemistries that can be broadly applied in abiotic systems in the same way that ATP hydrolysis is exploited throughout biochemistry. The key issue is that designing nonequilibrium systems is inherently about balancing the relative rates of coupled reactions. The use of carbodiimides as fuels to generate transient aqueous carboxylic anhydrides has recently been used in examples of new nonequilibrium materials and supramolecular assemblies. Here, we explore the kinetics of formation and decomposition of a series of benzoic anhydrides generated from the corresponding acids and EDC under typical conditions (EDC = N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride). The reactions can be described by a simple mechanism that merges known behavior for the two processes independently. Structure–property effects in these systems are dominated by differences in the anhydride decomposition rate. The kinetic parameters allow trends in concentration-dependent properties to be simulated, such as reaction lifetimes, peak anhydride concentrations, and yields. For key properties, there are diminishing returns with the addition of increasing amounts of fuel. These results should provide useful guidelines for the design of functional systems making use of this chemistry.

Authors:
ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Miami Univ., Oxford, OH (United States)
Publication Date:
Research Org.:
Miami Univ., Oxford, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1596013
Grant/Contract Number:  
SC0018645
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Organic Chemistry
Additional Journal Information:
Journal Volume: 85; Journal Issue: 2; Related Information: Raw experimental data: http://hdl.handle.net/2374.MIA/6572; Journal ID: ISSN 0022-3263
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; dissipative assembly; chemical kinetics

Citation Formats

Kariyawasam, Lasith S., Kron, Julie C., Jiang, Run, Sommer, André J., and Hartley, C. Scott. Structure–Property Effects in the Generation of Transient Aqueous Benzoic Acid Anhydrides by Carbodiimide Fuels. United States: N. p., 2019. Web. https://doi.org/10.1021/acs.joc.9b02746.
Kariyawasam, Lasith S., Kron, Julie C., Jiang, Run, Sommer, André J., & Hartley, C. Scott. Structure–Property Effects in the Generation of Transient Aqueous Benzoic Acid Anhydrides by Carbodiimide Fuels. United States. https://doi.org/10.1021/acs.joc.9b02746
Kariyawasam, Lasith S., Kron, Julie C., Jiang, Run, Sommer, André J., and Hartley, C. Scott. Fri . "Structure–Property Effects in the Generation of Transient Aqueous Benzoic Acid Anhydrides by Carbodiimide Fuels". United States. https://doi.org/10.1021/acs.joc.9b02746. https://www.osti.gov/servlets/purl/1596013.
@article{osti_1596013,
title = {Structure–Property Effects in the Generation of Transient Aqueous Benzoic Acid Anhydrides by Carbodiimide Fuels},
author = {Kariyawasam, Lasith S. and Kron, Julie C. and Jiang, Run and Sommer, André J. and Hartley, C. Scott},
abstractNote = {The design of dissipative systems, which operate out-of-equilibrium by consuming chemical fuels, is difficult. As yet, there are a few examples of privileged fuel chemistries that can be broadly applied in abiotic systems in the same way that ATP hydrolysis is exploited throughout biochemistry. The key issue is that designing nonequilibrium systems is inherently about balancing the relative rates of coupled reactions. The use of carbodiimides as fuels to generate transient aqueous carboxylic anhydrides has recently been used in examples of new nonequilibrium materials and supramolecular assemblies. Here, we explore the kinetics of formation and decomposition of a series of benzoic anhydrides generated from the corresponding acids and EDC under typical conditions (EDC = N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride). The reactions can be described by a simple mechanism that merges known behavior for the two processes independently. Structure–property effects in these systems are dominated by differences in the anhydride decomposition rate. The kinetic parameters allow trends in concentration-dependent properties to be simulated, such as reaction lifetimes, peak anhydride concentrations, and yields. For key properties, there are diminishing returns with the addition of increasing amounts of fuel. These results should provide useful guidelines for the design of functional systems making use of this chemistry.},
doi = {10.1021/acs.joc.9b02746},
journal = {Journal of Organic Chemistry},
number = 2,
volume = 85,
place = {United States},
year = {2019},
month = {12}
}

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