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

Kariyawasam, Lasith S.; Kron, Julie C.; Jiang, Run; Sommer, André J.; Hartley, C. Scott

doi:10.1021/acs.joc.9b02746

Cited by 30 publications

(43 citation statements)

References 63 publications

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“…Their use in similar systems is discussed further in our previous work. 3 These plots, plus the bootstrapping analysis discussed above, ensure that the parameters are well-constrained by the data. download file view on ChemRxiv SI.pdf (1.94 MiB)…”

Section: Fit Parametersmentioning

confidence: 99%

“…The "yield" in the main text refers to the total quantity of anhydride produced [An] net relative to the amount of EDC added [EDC] 0 . 3 The [An] net cannot be observed directly, but it can be calculated for a particular set of starting concentrations using the kinetic parameters from a mechanistic simulation. For the above-described mechanism [An] net , is given by either:…”

Section: Data Fittingmentioning

confidence: 99%

“…The features of this program and the resulting data simulations are discussed in our previous work. 3 A copy of the version used for the current work is included separately.…”

Section: Data Fittingmentioning

confidence: 99%

“…The 95% confidence intervals were determined using a nonparametric bootstrapping method with 10,000 iterations, which has been discussed previously. 3 Briefly, new datasets are randomly generated from the experimental data (i.e., by choosing from the experimental datapoints) and the fitting is rerun. 4 The confidence intervals represent the variation in the resulting fits.…”

Section: Fit Parametersmentioning

confidence: 99%

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Chemically Fueled Transient Geometry Changes in Diphenic Acids

et al. 2020

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Transient changes in molecular geometry are key to the function of many important biochemical systems. Here, we show that diphenic acids undergo out-of-equilibrium changes in dihedral angle when reacted with a carbodiimide chemical fuel. Treatment of appropriately functionalized diphenic acids with EDC (N-(3-(dimethylamino)propyl)-N′-ethylcarbodiimide hydrochloride) yields the corresponding diphenic anhydrides, reducing the torsional angle about the biaryl bond by ∼45°, regardless of substitution. In the absence of steric resistance, the reaction is well-described by a simple mechanism; the resulting kinetic parameters can be used to derive important properties of the system, such as yields and lifetimes. The reaction tolerates steric hindrance ortho to the biaryl bond, although the competing formation of (transient) byproducts complicates quantitative analysis.

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Section: Fit Parametersmentioning

confidence: 99%

Section: Data Fittingmentioning

confidence: 99%

“…The features of this program and the resulting data simulations are discussed in our previous work. 3 A copy of the version used for the current work is included separately.…”

Section: Data Fittingmentioning

confidence: 99%

Section: Fit Parametersmentioning

confidence: 99%

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Chemically Fueled Transient Geometry Changes in Diphenic Acids

et al. 2020

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“…To test whether this is occurring here, we examined the behavior of monoacid Ac1 , as shown in Scheme , which mimics the structure of the anhydrides within acyclic O1 n . We have previously used Ac1 to study the kinetics of EDC‐fueled anhydride formation . While the missing alkynyl group would certainly exert a substituent effect, it would be expected to accelerate anhydride hydrolysis, and thus the measurements on Ac1 provide a lower limit for the rate.…”

Section: Resultsmentioning

confidence: 99%

Dissipative Assembly of Macrocycles Comprising Multiple Transient Bonds

2020

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Dissipative assembly has great potential for the creation of new adaptive chemical systems.H owever,w hile molecular assembly at equilibrium is routinely used to prepare complex architectures from polyfunctional monomers,species formed out of equilibrium have,tothis point, been structurally very simple.I nm ost examples the fuel simply effects the formation of as ingle short-lived covalent bond. Herein, we show that chemical fuels can assemble bifunctional components into macrocycles containing multiple transient bonds. Specifically,d icarboxylic acids give aqueous dianhydride macrocycles on treatment with ac arbodiimide.T he macrocycles are assembled efficiently as aconsequence of both fueldependent and fuel-independent mechanisms;t hey undergo slower decomposition, building up as the fuel recycles the components,a nd are af avored product of the dynamic exchange of the anhydride bonds.T hese results create new possibilities for generating structurally sophisticated out-ofequilibrium species.

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Out‐of‐equilibrium supramolecular self‐assembling systems driven by chemical fuel

Wang

Chen

et al. 2021

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A rich variety of smart materials developed via supramolecular assembly strategies have been introduced in the past decades. However, most materials reside in the thermodynamic equilibrium state, opposed to those nonequilibrium structures with sophisticated functions that are observed in living systems. To develop advanced synthetic systems, chemists have begun to focus on how to use strategies similar to those used in biological systems for fabricating artificial out-of-equilibrium systems. Heretofore, a rich variety of artificial out-of-equilibrium systems have been developed. In this review, we have summarized the recent progress of artificial out-of-equilibrium systems and categorized them in terms of the chemical fuel used, including adenosine triphosphate (ATP), acid/base, carbodiimide reagents, and many others. For these self-assembling systems, their design strategies, potential applications, as well as advantageous features have been discussed. At the end of this review, the remaining challenges and an outlook of the chemical-fuel-driven out-of-equilibrium systems were also discussed. It is believed that this review has provided some insights and could be useful for those who are interested in the out-of-equilibrium supramolecular assembling systems and their subsequent constructing strategies for various transient materials.

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

Abstract: Structure-property Effects in the Generation of Transient Aqueous Benzoic Acid Anhydrides by Carbodiimide Fuels. ChemRxiv. Preprint.

Cited by 30 publications

References 63 publications

Chemically Fueled Transient Geometry Changes in Diphenic Acids

Chemically Fueled Transient Geometry Changes in Diphenic Acids

Dissipative Assembly of Macrocycles Comprising Multiple Transient Bonds

Out‐of‐equilibrium supramolecular self‐assembling systems driven by chemical fuel

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