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Chemical Shift: Internal References and Solvent Effects01:17

Chemical Shift: Internal References and Solvent Effects

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In an NMR sample, precise measurement of the absolute absorption frequencies of nuclei is difficult. A standard internal reference compound is added, and the frequency difference between the reference signal and sample signals is measured.
The internal reference compound generally used in NMR spectroscopy is tetramethylsilane (TMS). TMS is preferred because it is chemically inert, soluble in NMR solvents, and easily removable. Also, the highly shielded methyl protons in TMS yield an intense...
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π Electron Effects on Chemical Shift: Overview01:27

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An applied magnetic field causes loosely bound π-electrons in organic molecules to circulate, producing a local or induced diamagnetic field over a large spatial volume. As the molecules tumble in solution, the field generated by π-electrons in spherical substituents results in a zero net field. However, the net field generated by π-electrons in non-spherical substituents is not zero. The effect of this induced field depends on the orientation of the molecule with respect to B0,...
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Chemiosmosis and ATP Synthesis01:22

Chemiosmosis and ATP Synthesis

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The electron transport chain is a critical component of cellular respiration, occurring in the inner mitochondrial membrane. It facilitates the transfer of high-energy electrons from reduced cofactors NADH and FADH₂ to molecular oxygen, the final electron acceptor. This transfer of electrons through a series of protein complexes is tightly coupled to the translocation of protons across the membrane, generating a proton gradient essential for ATP synthesis.Electron Flow and Proton...
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Intermolecular Forces03:13

Intermolecular Forces

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Atoms and molecules interact through bonds (or forces): intramolecular and intermolecular. The forces are electrostatic as they arise from interactions (attractive or repulsive) between charged species (permanent, partial, or temporary charges) and exist with varying strengths between ions, polar, nonpolar, and neutral molecules. The different types of intermolecular forces are ion–dipole, dipole–dipole, hydrogen bonds, and dispersion; among these, dipole–dipole, hydrogen...
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ATP Driven Pumps I: An Overview01:27

ATP Driven Pumps I: An Overview

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ATP-driven pumps, also known as transport ATPases, are integral membrane proteins. They have binding sites for ATP located on the membrane's cytosolic side and the ion-conducting domain in the transmembrane region. These pumps use the free energy released from ATP hydrolysis to move the solutes across cell membranes against an electrochemical gradient.
There are four main types of ATP-driven pumps - P-type, V-type, F-type, and ABC transporter. All these pumps are of varying complexities and...
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Spin–Spin Coupling Constant: Overview01:08

Spin–Spin Coupling Constant: Overview

1.4K
In bromoethane, the three methyl protons are coupled to the two methylene protons that are three bonds away. In accordance with the n+1 rule, the signal from the methyl protons is split into three peaks with 1:2:1 relative intensities. The methylene protons appear as a quartet, with the relative intensities of 1:3:3:1.
Qualitatively, any spin plus-half nucleus polarizes the spins of its electrons to the minus-half state. Consequently, the paired electron in the hydrogen–carbon bond must...
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Related Experiment Video

Updated: Jan 9, 2026

Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method
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Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method

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Correlated solvent coordinates accelerate multi-donor proton-coupled electron transfer.

Gerald F Manbeck1, Brian N DiMarco1, Laura Rotundo1

  • 1Chemistry Division, Brookhaven National Laboratory Upton New York 11973-5000 USA gmanbeck@bnl.gov.

Chemical Science
|December 4, 2025
PubMed
Summary
This summary is machine-generated.

Investigating proton-coupled electron transfer (PCET) in ruthenium complexes with multiple donors reveals accelerated rates due to solvent reorganization. This work offers insights into designing efficient synthetic charge transfer systems.

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Area of Science:

  • Inorganic Chemistry
  • Photochemistry
  • Electron Transfer Theory

Background:

  • Semi-classical electron transfer theory accurately describes discrete donor-acceptor (D/A) pairs.
  • The influence of multiple equivalent redox sites on charge transfer rates is less understood.
  • Proton-coupled electron transfer (PCET) is crucial in various chemical and biological processes.

Purpose of the Study:

  • To investigate the effect of increasing the number of identical electron donors (N) on intramolecular PCET rates.
  • To isolate the impact of donor number while maintaining constant geometry, coupling, and driving forces.
  • To elucidate the role of solvent dynamics in supra-statistical acceleration of PCET.

Main Methods:

  • Synthesis of [Ru(L)3-N(OH)N]2+ complexes with N=1, 2, or 3 phenolic donors.
  • Flash photolysis and oxidative quenching with methyl viologen (MV2+).
  • Kinetic analysis of transient Ru(iii) oxidation via PCET.

Main Results:

  • PCET rates increased significantly with increasing donor number (3.4-fold for N=2, 5.7-fold for N=3).
  • Statistically corrected rates showed supra-statistical acceleration (1.7-fold for N=2, 1.9-fold for N=3).
  • Acceleration attributed to reduced outer sphere reorganization energy (λm) from partially shared solvent coordinate.

Conclusions:

  • Multiple equivalent redox sites can accelerate intramolecular PCET rates beyond statistical expectations.
  • Solvent reorganization energy plays a critical role in modulating PCET rates.
  • Provides a strategy for designing synthetic charge transfer systems with enhanced efficiency.