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NMR Spectroscopy: Spin–Spin Coupling01:08

NMR Spectroscopy: Spin–Spin Coupling

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The spin state of an NMR-active nucleus can have a slight effect on its immediate electronic environment. This effect propagates through the intervening bonds and affects the electronic environments of NMR-active nuclei up to three bonds away; occasionally, even farther. This phenomenon is called spin–spin coupling or J-coupling. Coupling interactions are mutual and result in small changes in the absorption frequencies of both nuclei involved. While nuclei of the same element are involved...
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¹H NMR: Interpreting Distorted and Overlapping Signals01:02

¹H NMR: Interpreting Distorted and Overlapping Signals

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Spin systems where the difference in chemical shifts of the coupled nuclei is greater than ten times J are called first-order spin systems. These nuclei are weakly coupled, and their chemical shifts and coupling constant can generally be estimated from the well-separated signals in the spectrum.
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are...
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Colors and Magnetism03:02

Colors and Magnetism

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Color in Coordination Complexes
When atoms or molecules absorb light at the proper frequency, their electrons are excited to higher-energy orbitals. For many main group atoms and molecules, the absorbed photons are in the ultraviolet range of the electromagnetic spectrum, which cannot be detected by the human eye. For coordination compounds, the energy difference between the d orbitals often allows photons in the visible range to be absorbed and emitted, which is seen as colors by the human...
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Atomic Nuclei: Nuclear Spin State Overview01:03

Atomic Nuclei: Nuclear Spin State Overview

2.1K
NMR-active nuclei have energy levels called 'spin states' that are associated with the orientations of their nuclear magnetic moments. In the absence of a magnetic field, the nuclear magnetic moments are randomly oriented, and the spin states are degenerate. When an external magnetic field is applied, the spin states have only 2 + 1 orientations available to them. A proton with = ½ has two available orientations. Similarly, for a quadrupolar nucleus with a nuclear spin value of one, the...
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UV–Vis Spectroscopy: Molecular Electronic Transitions01:16

UV–Vis Spectroscopy: Molecular Electronic Transitions

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In Ultraviolet–Visible (UV–Vis) spectroscopy, the absorption of electromagnetic radiation is used to probe the electronic structure of molecules. This technique provides insights into molecular electronic transitions, particularly the movement of electrons between different molecular orbitals. Radiation is absorbed if the energy of the electromagnetic radiation passing through the molecule is precisely equal to the energy difference between the excited and ground states. During this...
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Valence Bond Theory02:42

Valence Bond Theory

11.5K
Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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Related Experiment Video

Updated: Mar 12, 2026

Measurement of Coherence Decay in GaMnAs Using Femtosecond Four-wave Mixing
15:58

Measurement of Coherence Decay in GaMnAs Using Femtosecond Four-wave Mixing

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RIDME spectroscopy on high-spin Mn2+ centers.

D Akhmetzyanov1, H Y V Ching2, V Denysenkov1

  • 1Goethe-University Frankfurt am Main, Institute of Physical and Theoretical Chemistry and Center for Biomolecular Magnetic Resonance, Max von Laue Str. 7, 60438 Frankfurt am Main, Germany. prisner@chemie.uni-frankfurt.de.

Physical Chemistry Chemical Physics : PCCP
|November 5, 2016
PubMed
Summary

High-spin manganese (Mn2+) probes enable precise distance measurements in biological macromolecules using pulsed electron paramagnetic resonance (EPR) dipolar spectroscopy. New experiments show relaxation-induced dipolar modulation enhancement (RIDME) offers superior results over PELDOR/DEER for these systems.

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Area of Science:

  • Biophysics
  • Structural Biology
  • Biomolecular NMR Spectroscopy

Background:

  • Pulsed electron paramagnetic resonance (EPR) dipolar spectroscopy is vital for measuring distances (1.5-10 nm) in biological macromolecules.
  • High-spin Mn2+ ions are biologically compatible spin probes for EPR distance measurements, but their use in dipolar spectroscopy is underexplored.

Purpose of the Study:

  • To explore the utility of high-spin Mn2+ as spin probes in pulsed EPR dipolar spectroscopy.
  • To compare the performance of PELDOR (DEER) and RIDME experiments using Mn2+ probes at high frequencies (W- and J-band).

Main Methods:

  • Performed W-band (94 GHz) and J-band (263 GHz) pulsed electron electron double resonance (PELDOR/DEER) and relaxation-induced dipolar modulation enhancement (RIDME) experiments.
  • Utilized a bis-MnDOTA model system with Mn2+ spin probes.
  • Applied Tikhonov regularization analysis, incorporating higher harmonics of the dipolar coupling frequency.

Main Results:

  • Obtained distance measurements consistent with predictions for the bis-MnDOTA model system.
  • RIDME experiments demonstrated significantly higher modulation depth compared to PELDOR/DEER.
  • Observed and accounted for higher harmonics of the dipolar coupling frequency due to Mn2+ relaxation and multi-component background functions.

Conclusions:

  • Pulsed EPR dipolar spectroscopy with Mn2+ probes is effective for structural and dynamic studies of biomacromolecules.
  • RIDME is a promising technique for distance measurements in biological samples using Mn2+ probes due to its higher sensitivity.
  • Advanced analysis methods are necessary to accurately interpret data involving high-spin probes and complex relaxation effects.