Catalysis: energy is the measure of all things

Solel, Ephrath; Tarannam, Naziha; Kozuch, Sebastian

doi:10.1039/c9cc00754g

Cited by 50 publications

(54 citation statements)

References 44 publications

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“…To provide an unambiguous description of catalytic activity within the molecular volcano plot framework, we [40] and others, [45] have previously illustrated the benefits of using Kozuch and Shaik ’s energy span model (ESM) [46–49] . The ESM defines catalytic activity in terms of an energy span, δ E , which essentially represents the highest free energy encountered by a catalyst while traversing the catalytic cycle.…”

Section: Resultsmentioning

confidence: 99%

Methoxycyclization of 1,5‐Enynes by Coinage Metal Catalysts: Is Gold Always Superior?

Wodrich

Corminbœuf

2021

Helvetica Chimica Acta

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Au(I) catalysts promote the intramolecular cycloisomerization of 1,n‐enynes, as well as facilitate reactions with alcohols, characteristics that have led to their wide‐spread in the synthesis of complex natural products. Literature reports of Cu and Ag species catalyzing the same or similar reactions are much less common. Here, we utilize molecular volcano plots to assess the activity of 45 coinage metal phosphine/phosphite catalysts possessing a variety of stereoelectronic properties for the methoxycyclization reaction of a prototypical 1,5‐enyne. Our analysis reveals that the intrinsic properties of gold allow it to be coupled with a wide range of ligands, all of which exhibit high catalytic activity. On the other hand, the coupling of silver and copper with more traditional phosphines, such as triphenylphosphine, leads to catalysts with diminished catalytic ability. The activity of Ag and Cu species, however, can be enhanced by appending ligands with strong π‐accepting character, which shifts these species closer to the volcano peak.

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Section: Resultsmentioning

confidence: 99%

Methoxycyclization of 1,5‐Enynes by Coinage Metal Catalysts: Is Gold Always Superior?

Wodrich

Corminbœuf

2021

Helvetica Chimica Acta

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“…Later development of the theory for the optimum catalyst was associated with an assessment of the optimal adsorption energies through the use of chemical potential [13][14][15], showing for example that the chemical potential of the adsorbed species on an optimal catalyst is approximately a half sum of the chemical potential of the reactants and products in the gas phase, which is analogous to the conclusion following from [7]. The energy span model [16][17][18] was applied [16] to elucidate the adsorption energy for the optimal catalyst using a generic two-step sequence and considering that either the first or the second steps are determining the rate.…”

Section: +1mentioning

confidence: 99%

On the optimum catalyst for structure sensitive heterogeneous catalytic reactions

Murzin

2020

Reac Kinet Mech Cat

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Reaction rates in a two-step catalytic sequence, when plotted vs adsorption energy of the key or the most abundant surface intermediate, result in volcano shaped curves. In the current work, the optimal catalyst is discussed for structure sensitive reactions, which display dependence of activity on the cluster size of the active catalytic phase. An expression is derived relating the Gibbs energy for formation of the intermediate with the Gibbs energy changes in the overall reaction, difference in adsorption thermodynamics on edges and terraces and the cluster size. The kinetic expressions display dependence of activity vs the Gibbs energy of the adsorbed intermediate formation. Numerical analysis demonstrates that when the overall equilibrium constant K is high and the reaction is thermodynamically very favorable, the maxima in the rates vs the adsorption constant for the optimal catalyst are much broader being less dependent on the cluster size. When structure sensitivity is pronounced, there are smaller differences in the rates for the optimum and less optimal catalysts in comparison with reactions showing weak structure sensitivity.

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“…To perform this calculation, I used the chemical affinity (A), which is the opposite of the non-standard Gibbs energy change of the reaction [46, p. 143] and can be computed from (e.g. [47])…”

Section: Theoretical Prediction Of Relative Stabilities Of Proteinsmentioning

confidence: 99%

A thermodynamic model for water activity and redox potential in evolution and development

Dick

2021

Preprint

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As gene sequences change through evolution, and as the abundances of different proteins change through development, the distinct elemental composition of the proteins at different times can be represented as an overall chemical reaction. Compositional and thermodynamic analysis of these reactions leads to novel insight on biochemical changes and enables predictions of intensive variables including redox potential. The stoichiometric hydration state refers to the number of H2O in theoretical reactions to form the proteins from a set of thermodynamic components. By analyzing published phylostratigraphy and transcriptomic and proteomic datasets, I found that of proteins decreases on evolutionary timescales (from single-celled organisms to metazoans) and on developmental timescales in Bacillus subtilis biofilms. Moreover, values of computed for a developmental proteome of fruit flies are aligned with organismal water content from larva to adult stages. I present a thermodyamic model for the equilibrium chemical activity of target proteins in a genomic background. Conditions that maximize the activity of the target proteins are found by optimizing the values of water activity and oxygen fugacity, which are then combined to calculate effective values of redox potential (Eh). The effective Eh values during evolution range between values reported for mitochondria, the cytosol, and extracellular compartments. These results suggest a central role for water, and water activity, in the biochemistry of evolution and development.

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Catalysis: energy is the measure of all things

Abstract: Is there any place in the extremely well-established field of catalytic kinetics for new interpretations or novel models that can change the basic doctrines and viewpoints of catalytic cycles?

Cited by 50 publications

References 44 publications

Methoxycyclization of 1,5‐Enynes by Coinage Metal Catalysts: Is Gold Always Superior?

Methoxycyclization of 1,5‐Enynes by Coinage Metal Catalysts: Is Gold Always Superior?

On the optimum catalyst for structure sensitive heterogeneous catalytic reactions

A thermodynamic model for water activity and redox potential in evolution and development

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