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Related Concept Videos

¹H NMR: Complex Splitting01:13

¹H NMR: Complex Splitting

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A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied...
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2D NMR: Overview of Homonuclear Correlation Techniques01:16

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Homonuclear correlation spectroscopy (COSY) is a powerful technique used in Nuclear Magnetic Resonance (NMR) spectroscopy to study the correlations between nuclei of the same type within a molecule. It provides information about scalar couplings between adjacent nuclei, which helps determine connectivity and structural information. There are several COSY variants, each with its unique strengths and experimental parameters.
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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

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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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2D NMR: Overview of Heteronuclear Correlation Techniques01:18

2D NMR: Overview of Heteronuclear Correlation Techniques

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Heteronuclear correlation spectroscopy is an analytical technique that investigates the coupling between different types of nuclei, often a proton and an X-nucleus, such as carbon-13 or nitrogen-15. This method is commonly used in nuclear magnetic resonance (NMR) spectroscopy to gain insights into complex chemical compounds' structural and compositional aspects. A typical heteronuclear correlation spectrum displays X-nucleus chemical shifts on one axis and a proton spectrum on the other...
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Double Resonance Techniques: Overview01:12

Double Resonance Techniques: Overview

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Double resonance techniques in Nuclear Magnetic Resonance (NMR) spectroscopy involve the simultaneous application of two different frequencies or radiofrequency pulses to manipulate and observe two distinct nuclear spins. One important application of double resonance is spin decoupling, which selectively suppresses coupling with one type of nucleus while observing the NMR signal from another nucleus, simplifying the spectrum and enhancing resolution.
Spin decoupling is usually achieved by...
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Investigating Cu(II) Complexes for MRI: A Comprehensive Approach Using EPR, Relaxometry, and Computational Modeling.

Maria Chiara Pagliero1, Marco Ricci2, Raúl Alvarado3

  • 1Department of Chemistry, University of Turin, Via Giuria 9, 10125 Torino, Italy.

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Summary
This summary is machine-generated.

Developing new MRI contrast agents requires understanding copper(II) complexes. This study reveals how structural changes in copper complexes significantly impact their relaxivity, guiding the design of safer, effective Gd-free MRI agents.

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Area of Science:

  • Inorganic Chemistry
  • Materials Science
  • Biomedical Imaging

Background:

  • Gadolinium-based contrast agents (GBCAs) are standard for MRI but carry risks.
  • Developing safer, Gadolinium-free (Gd-free) contrast agents is a critical research area.
  • Understanding paramagnetic relaxation in transition-metal complexes is key to designing novel agents.

Purpose of the Study:

  • To investigate the structure-relaxivity relationships in two copper(II) complexes, [Cu(TACN)]2+ and [Cu(TREN)]2+.
  • To determine how coordination environment, geometry, and hydration affect paramagnetic relaxation pathways.
  • To establish a framework for designing Cu(II)-based MRI contrast agents.

Main Methods:

  • Electron Paramagnetic Resonance (EPR) spectroscopy
  • Q-band Electron Nuclear Double Resonance (ENDOR)
  • Variable-temperature 17O Nuclear Magnetic Resonance (NMR)
  • Field-dependent 1H relaxometry
  • Density Functional Theory (DFT) calculations

Main Results:

  • EPR and ENDOR provided accurate rotational correlation times and metal-proton hyperfine couplings.
  • 1H relaxometry showed distinct water exchange dynamics for [Cu(TACN)]2+ (fast) and [Cu(TREN)]2+ (slow).
  • [Cu(TREN)]2+ exhibited significant scalar relaxation under basic conditions due to hydroxide (OH-) substitution.

Conclusions:

  • Cu(II) relaxivity is highly sensitive to subtle structural variations.
  • Geometric and hydration control can effectively modulate inner-sphere and prototropic exchange pathways.
  • The integrated experimental-computational approach enables rational design of Cu(II)-based MRI contrast agents.