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Related Concept Videos

¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

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The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
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Relative Stabilities of Alkenes01:59

Relative Stabilities of Alkenes

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The relative stability of alkenes can be determined by comparing their heats of hydrogenation. The lower heat of hydrogenation indicates the more stable alkene.  The three main factors determining the relative stability of alkenes are i) the number of substituents attached to the double-bond carbon atoms, ii) hyperconjugation, and iii) the stereochemistry of the double bond.
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Constitutional Isomers of Alkanes02:18

Constitutional Isomers of Alkanes

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Organic compounds of the same molecular formula can have different structural formulas called constitutional isomers, and the phenomenon is known as constitutional isomerism. Alkanes with four or more carbons showing multiple structures with the same molecular formula thereby exhibit constitutional isomerism.
The linear isomer of an alkane is prefixed by the term “n”; hence a linear isomer of pentane is known as n-pentane. Based on the type of branching, some of the...
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Structure of Alkanes02:23

Structure of Alkanes

27.6K
The formation of carbon-carbon bonds leading to the creation of the carbon chain is the basis of organic chemistry. August Kekulé and Archibald Scott Couper independently developed this idea of carbon chain formation.
Hydrocarbons are the simplest organic compounds composed of carbons and hydrogens. Based on the bond order between carbons, the hydrocarbons are further classified into alkanes, alkenes, and alkynes. 
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27.6K
¹³C NMR: ¹H–¹³C Decoupling01:04

¹³C NMR: ¹H–¹³C Decoupling

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The probability of having two carbon-13 atoms next to each other is negligible because of the low natural abundance of carbon-13. Consequently, peak splitting due to carbon-carbon spin-spin coupling is not observed in spectra. However, protons up to three sigma bonds away split the carbon signal according to the n+1 rule, resulting in complicated spectra.
A broadband decoupling technique is used to simplify these complex, sometimes overlapping, signals. Broadband decoupling relies on a...
1.1K
¹H NMR of Conformationally Flexible Molecules: Temporal Resolution00:52

¹H NMR of Conformationally Flexible Molecules: Temporal Resolution

834
At room temperature, the chair conformer of cyclohexane undergoes rapid ring flipping between two equivalent chair conformers at a rate of approximately 105 times per second. These two chair conformers are in equilibrium. The rapid ring flipping results in the interconversion of the axial proton to an equatorial proton and an equatorial to the axial proton. Such interconversions are too rapid and cannot be detected on the NMR timescale. Hence, the NMR spectrometer cannot distinguish between the...
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Collective long-lived zero-quantum coherences in aliphatic chains.

Kirill F Sheberstov1, Anna Sonnefeld1, Geoffrey Bodenhausen1

  • 1Laboratoire des Biomolécules, LBM, Département de Chimie, École Normale Supérieure, PSL University, Sorbonne Université, CNRS, 75005 Paris, France.

The Journal of Chemical Physics
|April 11, 2024
PubMed
Summary
This summary is machine-generated.

Researchers demonstrate exciting collective long-lived coherences in nuclear magnetic resonance (NMR) using polychromatic spin-lock induced crossing (poly-SLIC) pulses. This technique enables spin order propagation in methylene chains, offering enhanced sensitivity for applications like drug screening.

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Area of Science:

  • Nuclear Magnetic Resonance (NMR) Spectroscopy
  • Quantum Coherence Phenomena
  • Molecular Spectroscopy

Background:

  • Long-lived coherences (LLCs) are zero-quantum (ZQ) coherences with extended lifetimes beyond transverse relaxation (T2).
  • Previously observed in two-spin systems (I=1/2), LLCs involve singlet (S0) and triplet (T0) states.
  • Extending LLC observation to larger spin systems is crucial for advanced NMR applications.

Purpose of the Study:

  • To report the excitation and detection of collective LLCs in complex spin systems (AA'MM'XX') within molecules containing multiple methylene (-CH2-) groups.
  • To introduce and validate novel polychromatic spin-lock induced crossing (poly-SLIC) pulse sequences for manipulating these coherences.
  • To explore the potential of these LLCs for high-resolution NMR measurements, particularly in contexts like drug screening.

Main Methods:

  • Development and application of several variants of polychromatic spin-lock induced crossing (poly-SLIC) pulse sequences.
  • Excitation of collective ZQ coherences (e.g., S0S0T0S0S0T0, S0T0S0S0T0S0) in molecules with at least three methylene groups.
  • Observation of ZQ precession as spin order propagation along the methylene chain, followed by reconversion to observable magnetization.

Main Results:

  • Successful excitation and detection of collective LLCs in AA'MM'XX' spin systems.
  • Demonstration of spin order propagation along methylene chains, leading to ZQ precession.
  • Achieved narrow ZQ signal linewidths (~0.1 Hz) in 2D spectra, insensitive to magnetic field inhomogeneity but sensitive to chemical exchange.

Conclusions:

  • Collective LLCs can be effectively generated and manipulated in multi-methylene spin systems using poly-SLIC.
  • The observed spin order propagation mechanism provides a new route for enhancing NMR sensitivity and resolution.
  • The technique shows promise for applications requiring high spectral resolution, such as chemical exchange studies and drug screening.