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Related Concept Videos

Protein Dynamics in Living Cells01:19

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Different fluorescence-based techniques are used to study the protein dynamics in living cells. These techniques include FRAP, FRET, and PET.
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Polarimetry finds application in chemical kinetics to measure the concentration and reaction kinetics of optically active substances during a chemical reaction. Optically active substances have the capability of rotating the plane of polarization of linearly polarized light passing through them—a feature called optical rotation. Optical activity is attributed to the molecular structure of substances. Normal monochromatic light is unpolarized and possesses oscillations of the electrical...
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Updated: Mar 16, 2026

Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method
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Path Sampling Methods for Enzymatic Quantum Particle Transfer Reactions.

M W Dzierlenga1, M J Varga1, S D Schwartz1

  • 1University of Arizona, Tucson, AZ, United States.

Methods in Enzymology
|August 7, 2016
PubMed
Summary
This summary is machine-generated.

Computational methods now incorporate enzyme dynamics and quantum effects for studying particle transfer reactions. New techniques reveal tunneling

Keywords:
Centroid molecular dynamicsEnzymatic reactionsFree energyHydride transferKinetic isotope effectsMolecular dynamicsNuclear quantum effectsTransition path sampling

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Area of Science:

  • Biochemistry
  • Computational Chemistry
  • Enzyme Kinetics

Background:

  • Enzymatic reaction mechanisms are typically studied using computational techniques.
  • Existing methods often neglect enzyme dynamics, potentially leading to inaccurate results, especially for particle transfer reactions involving nuclear tunneling.

Purpose of the Study:

  • To outline previous computational methods for studying enzymatic reactions.
  • To discuss newly developed dynamical methods for investigating enzymatic particle transfer reactions.
  • To incorporate quantum effects and full enzyme dynamics into mechanism studies.

Main Methods:

  • Centroid Molecular Dynamics (CMD) for incorporating quantum effects.
  • Transition Path Sampling (TPS) for capturing enzyme dynamics.
  • Application of CMD and TPS to calculate free energy barriers and kinetic isotope effects (KIEs).

Main Results:

  • Tunneling was found to be insignificant in yeast alcohol dehydrogenase (YADH) but significant, though not dominant, in lactate dehydrogenase (LDH).
  • Calculated primary H/D KIE for YADH using TPS and CMD aligned with experimental values.
  • The developed methods accurately reflect particle transfer kinetics within enzymes.

Conclusions:

  • Newly developed dynamical methods, incorporating protein and quantum dynamics, offer advanced tools for studying enzyme mechanisms.
  • These methods provide accurate calculations of free energy barriers and KIEs, improving our understanding of enzymatic particle transfer.