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¹H NMR of Conformationally Flexible Molecules: Temporal Resolution00:52

¹H NMR of Conformationally Flexible Molecules: Temporal Resolution

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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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¹H NMR of Conformationally Flexible Molecules: Variable-Temperature NMR01:15

¹H NMR of Conformationally Flexible Molecules: Variable-Temperature NMR

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The axial and equatorial protons in cyclohexane can be distinguished by performing a variable-temperature NMR experiment. In this process, except for one proton, the remaining eleven protons are replaced by deuterium. The deuterium substitution avoids the possible peak splitting caused by the spin-spin coupling between the adjacent protons. The remaining proton flips between the axial and equatorial positions.
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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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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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Colloids03:22

Colloids

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Children at play often make suspensions such as mixtures of mud and water, flour and water, or a suspension of solid pigments in water known as tempera paint. These suspensions are heterogeneous mixtures composed of relatively large particles that are visible to the naked eye or can be seen with a magnifying glass. They are cloudy, and the suspended particles settle out after mixing. On the other hand, a solution is a homogeneous mixture in which no settling occurs and in which the dissolved...
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¹H NMR of Labile Protons: Deuterium (²H) Substitution00:48

¹H NMR of Labile Protons: Deuterium (²H) Substitution

1.2K
This lesson illustrates the role of deuterium substitution in simplifying the NMR spectrum of compounds comprising labile protons. One method employed is the use of deuterium. Amongst the three isotopes of hydrogen, deuterium (2H) has a nucleus composed of one proton and one neutron. When the D2O solvent is added to a pure dry ethanol solution, its labile proton is substituted with deuterium.
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Rheo-NMR phenomena of wormlike micelles.

M R López-González1, W M Holmes2, P T Callaghan1

  • 1MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Chemical and Physical Sciences, Victoria University of Wellington, P.O. Box 600, New Zealand.

Soft Matter
|July 19, 2020
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Summary
This summary is machine-generated.

This study reveals shear banding fluctuations in micellar solutions using rheology and NMR. These fluctuations correlate with stress changes and amphiphile behavior, offering new insights into complex fluid dynamics.

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Area of Science:

  • Soft Matter Physics
  • Materials Science
  • Physical Chemistry

Background:

  • Wormlike micellar solutions exhibit complex flow behaviors.
  • Shear banding is a phenomenon where fluids form distinct bands under shear.
  • Understanding micellar dynamics is crucial for material design and processing.

Purpose of the Study:

  • To investigate shear banding fluctuations in cetylpyridinium chloride and sodium salicylate (CPyCl-NaSal) micellar systems.
  • To correlate these fluctuations with rheological and nuclear magnetic resonance (NMR) measurements.
  • To directly measure the shear-induced nematic phase transition.

Main Methods:

  • Utilized a combination of rheology and nuclear magnetic resonance (NMR) spectroscopy/velocimetry.
  • Performed time-averaged and real-time measurements on CPyCl-NaSal solutions.
  • Employed H-NMR spectroscopy with a deuterated probe molecule (-decane).

Main Results:

  • Demonstrated the existence of shear banding fluctuations under Couette flow.
  • Correlated shear banding fluctuations with shear stress fluctuations (rheology).
  • Observed fluctuations in the constrained fraction of amphiphile chains (Δ) via H-NMR spectroscopy.
  • Reported direct measurement of the shear-induced nematic phase transition.

Conclusions:

  • Shear banding fluctuations in CPyCl-NaSal micellar systems are experimentally confirmed.
  • Fluctuations are consistent across rheological and NMR spectroscopic observations.
  • NMR velocimetry provides direct evidence of shear-induced phase transitions in micellar interiors.