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Catalysis02:50

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The theory of catalytically perfect enzymes was first proposed by W.J. Albery and J. R. Knowles in 1976. These enzymes catalyze biochemical reactions at high-speed. Their catalytic efficiency values range from 108-109 M-1s-1. These enzymes are also called 'diffusion-controlled' as the only rate-limiting step in the catalysis is that of the substrate diffusion into the active site. Examples include triose phosphate isomerase, fumarase, and superoxide dismutase.
 
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Chemical Fuel-Driven Networked Catalytic Machinery.

Amit Ghosh1, Sohom Kundu1, Michael Schmittel1

  • 1Center of Micro- and Nanochemistry and Engineering, Organische Chemie I, Adolf-Reichwein-Str. 2, Siegen, D-57068, Germany.

Chemistry (Weinheim an Der Bergstrasse, Germany)
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Summary
This summary is machine-generated.

This study introduces networked molecular machinery that combines chemical fuel-driven communication and catalysis. It demonstrates pulsed, time-programmed catalysis mimicking biological complexity.

Keywords:
chemical fuelmolecular machinerotaxanesupramolecular chemistryswitchable catalysis

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Area of Science:

  • Supramolecular Chemistry
  • Chemical Engineering
  • Catalysis

Background:

  • Networked molecular machinery represents a frontier in creating complex systems with programmable functions.
  • Integrating communication and catalysis within these machines is crucial for advanced applications.
  • Previous systems lacked the dynamic, fuel-driven control demonstrated here.

Purpose of the Study:

  • To develop a novel networked molecular machine integrating chemical-fuel-driven communication and catalysis.
  • To demonstrate pulsed operation and time-programmed catalytic activity.
  • To mimic the complexity and responsiveness of biological systems.

Main Methods:

  • Utilized a self-sorted system comprising zinc hexacyclen, a silver(I)-loaded receptor, and a [2]rotaxane (NetState-I).
  • Employed 2-cyano-2-phenylpropanoic acid as a chemical fuel to trigger molecular translocation events.
  • Quantified catalytic activity of the transiently generated silver(I) [2]rotaxane using kinetic measurements (k298 = 176 kHz).

Main Results:

  • Demonstrated a cascade process involving the translocation of Zn2+ and Ag(I) ions upon addition of chemical fuel.
  • Showcased that catalytic activity of silver(I) is masked in the initial networked state and activated upon translocation.
  • Successfully catalyzed the 6-endo cyclization of 2-alkynylbenzaldoxime using the fuel-driven system.

Conclusions:

  • Presents a pivotal advancement in networked molecular machinery through integrated chemical communication and catalysis.
  • Establishes a novel paradigm for cascaded signaling and time-programmed catalysis via pulsed operation.
  • Highlights the potential for mimicking biological system complexity with synthetic molecular machines.