Enhanced Mobility during Diels–Alder Reaction: Results of Molecular Simulations

Reid, Korey M.; Leitner, David M.

doi:10.1021/acs.jpclett.2c00886

Cited by 3 publications

(2 citation statements)

References 54 publications

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“…The reaction produces a six-membered ring with the formation of two new σ bonds. We analyzed the change in Δ E and r during the proposed DA reaction path (Figure e). , Figure f shows that Δ E remains constant during the DA reaction while a small change in r was observed from 5.16 to 4.82 Å.…”

Section: Resultsmentioning

confidence: 99%

Single-Molecule Tracking of Reagent Diffusion during Chemical Reactions

Zhang

Chen

et al. 2023

J. Am. Chem. Soc.

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Recent experiments have shown that the diffusion of reagent molecules is inconsistent with what the Stokes−Einstein equation predicts during a chemical reaction. Here, we used singlemolecule tracking to observe the diffusion of reactive reagent molecules during click and Diels−Alder (DA) reactions. We found that the diffusion coefficient of the reagents remained unchanged within the experimental uncertainty upon the DA reaction. Yet, diffusion of reagent molecules is faster than predicted during the click reaction when the reagent concentration and catalyst concentration exceed a threshold. A stepwise analysis suggested that the fast diffusion scenario is due to the reaction but not the involvement of the tracer with the reaction itself. The present results provide experimental evidence on the faster-than-expected reagent diffusion during a CuAAC reaction in specific conditions and propose new insights into understanding this unexpected behavior.

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Section: Resultsmentioning

confidence: 99%

Single-Molecule Tracking of Reagent Diffusion during Chemical Reactions

Zhang

Chen

et al. 2023

J. Am. Chem. Soc.

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“…The Leitner group performed longer‐lasting molecular dynamics (MD) to understand the reaction dynamics that cause the enhanced diffusion of reactants. [ 9 ] They specifically chose to study the DA reaction since it is the only noncatalyzed reaction that showed an enhanced diffusion effect. Catalyzed reactions, such as click reactions, require intensive computation costs.…”

Section: Small Molecule Reactions and Catalysismentioning

confidence: 99%

Comparison of Measurements for Enhanced Diffusion Problem in Chemical Reaction Systems

Jee,

Wen,

Wang

2024

Chin. J. Chem.

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Comprehensive SummaryThe problem of molecular diffusion in the soup of chemical reactions attracts mounting interest across fields ranging from chemistry to biophysics to material science. Chemical reactions involve bond breakup and formation, whose time scale is typically on the orders of fs to ps, while molecular diffusion occurs at time scales of μs to ms. The two processes are often considered orthogonal, given the vastly different scales. The serial results show that the enzyme's diffusion is enhanced in a substrate‐dependent manner, which was further extended to small molecule reaction systems, challenging this classical paradigm. However, the results from different groups using different techniques do not quantitatively agree, and a general mechanism is yet to be understood. We summarize experimental studies on diffusion problems and seek to reconcile the interpretation with understanding the limits of measurement tools and the chemical nature of reaction systems. Understanding molecular diffusion in chemical reactions will provide fresh thoughts in designing chemical systems such as molecular machines that harvest work at the nanoscale in a controllable manner.

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