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Oxidation of Phenols to Quinones01:17

Oxidation of Phenols to Quinones

5.0K
In the presence of oxidizing agents, phenols are oxidized to quinones. Quinones can be easily reduced back to phenols using mild reducing agents. The electron-donating hydroxyl group enhances the reactivity of the aromatic ring, enabling oxidation of the ring even in the absence of an α hydrogen.
o-hydroxy phenols are oxidized to o-quinones and p-hydroxy phenols to p-quinones. Such redox reactions involve the transfer of two electrons and two protons. The reversible redox...
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Nuclear Overhauser Enhancement (NOE)01:06

Nuclear Overhauser Enhancement (NOE)

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Irradiation of a spin-active nucleus causes an increase or decrease in the signal intensity of neighboring nuclei that are not necessarily chemically bonded or involved in J-coupling. This phenomenon, called the nuclear Overhauser enhancement (NOE), results from through-space interactions between the nuclear spins. The NOE effect decreases with increasing internuclear distance and is generally not observed beyond 4 angstroms. In NOE, dipole-dipole interactions between neighboring spin-active...
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Redox Reactions01:24

Redox Reactions

59.2K
Oxidation-reduction or redox reactions involve the transfer of electrons from one molecule or atom to another. When an atom gains an electron, another atom must lose an electron, meaning oxidation and reduction must occur together. Since the redox occurs in pairs, the atom that gets oxidized is also called the reducing agent or reductant, and the atom that is reduced is also called the oxidizing agent or oxidant. A straightforward way to remember the definitions of oxidation and reduction is...
59.2K
Redox Reactions01:27

Redox Reactions

1.3K
Redox reactions are vital biochemical processes that underpin energy metabolism in cells. These reactions involve the transfer of electrons between molecules, occurring in tandem as oxidation and reduction. Oxidation refers to the loss of electrons, while reduction denotes their gain. This coupling ensures the seamless flow of electrons through metabolic pathways. For example, in bacterial metabolism, glucose undergoes oxidation to carbon dioxide, while oxygen is simultaneously reduced to...
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Redox Equilibria: Overview01:23

Redox Equilibria: Overview

1.7K
A reduction-oxidation reaction is commonly called a redox reaction. In a redox reaction, electrons are transferred from one species to another rather than being shared between or among atoms. The reducing agent or reductant is the species that loses electrons and gets oxidized in the process. The species that gains electrons and gets reduced in the process is the oxidizing agent or oxidant. Redox reactions are represented as two separate equations called half-reactions, where one equation...
1.7K
The Energies of Atomic Orbitals03:21

The Energies of Atomic Orbitals

30.6K
In an atom, the negatively charged electrons are attracted to the positively charged nucleus. In a multielectron atom, electron-electron repulsions are also observed. The attractive and repulsive forces are dependent on the distance between the particles, as well as the sign and magnitude of the charges on the individual particles. When the charges on the particles are opposite, they attract each other. If both particles have the same charge, they repel each other.
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Related Experiment Video

Updated: Mar 6, 2026

Electrochemical Detection of Deuterium Kinetic Isotope Effect on Extracellular Electron Transport in Shewanella oneidensis MR-1
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Electrochemical Detection of Deuterium Kinetic Isotope Effect on Extracellular Electron Transport in Shewanella oneidensis MR-1

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Nuclear Quantum Effects on Aqueous Electron Attachment and Redox Properties.

Vladimir V Rybkin1, Joost VandeVondele1

  • 1Nanoscale Simulations, Department of Materials, ETH Zürich , Wolfgang-Pauli-Str. 27, CH-8093 Zürich, Switzerland.

The Journal of Physical Chemistry Letters
|March 16, 2017
PubMed
Summary

Nuclear quantum effects (NQEs) significantly alter electron affinity and detachment energies for aqueous species. While NQEs impact solvent response, their net effect on redox potentials is small, suggesting they aren't always crucial for calculations.

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Area of Science:

  • Physical chemistry
  • Computational chemistry
  • Quantum mechanics

Background:

  • Nuclear quantum effects (NQEs) influence molecular properties in condensed phases.
  • Understanding NQEs is crucial for accurate modeling of chemical reactions in solution.

Purpose of the Study:

  • To quantify and rationalize the impact of NQEs on the reduction and oxidation properties of small aqueous species.
  • To investigate the influence of NQEs on vertical electron attachment/detachment energies and redox free energies.

Main Methods:

  • First-principles molecular dynamics simulations.
  • Thermodynamic integration calculations.
  • Quantum mechanical treatment of nuclear motion.

Main Results:

  • NQEs decrease vertical electron attachment/detachment energies by approximately 0.3 eV.
  • NQEs reduce solvent reorganization energy, affecting oxidation/reduction processes.
  • The net effect of NQEs on redox free energies is small (around 0.1 eV) due to opposing contributions.

Conclusions:

  • NQEs are important for accurate calculation of vertical electron energies but may not be essential for redox potentials unless high accuracy is required.
  • The findings on solvent reorganization energy are likely general for small solutes in water.