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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

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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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The function of proteins depends on their native three-dimensional structure, which is dictated by the amino acid sequence of the specific protein. Folding of the polypeptide chain takes place under specific conditions that energetically favor the folded conformation. In contrast, protein denaturation occurs spontaneously under unfavorable conditions that disrupt the integrity of the folded conformation. Thus, the chemical and physical environment of a protein, such as significant changes in pH...
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Protons in identical electronic environments within a molecule are chemically equivalent and have the same chemical shift. The replacement test is a useful tool to identify chemical equivalence and predict NMR spectra. A substituent replaces each of the protons being examined and the resulting molecules are compared. If the same molecule is obtained, the protons are equivalent or homotopic. Replacement of any hydrogens in ethane by chlorine yields chloroethane because all six protons are...
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The protons in unsubstituted alkanes are strongly shielded with chemical shifts below 1.8 ppm. Methine, methylene, and methyl protons appear at approximately 1.7, 1.2 and 0.7 ppm, while the proton signal from methane appears at 0.23 ppm. An electronegative substituent, such as chlorine, withdraws the electron density from the protons, increasing their chemical shift. Progressive substitution of the hydrogens in methane by chlorine shifts the proton signals increasingly downfield, to 3.05 ppm in...
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pH-induced conformational changes in histamine in the solid state.

Kanchanok Kodchakorn1,2, Piyarat Nimmanpipug1, Suttinun Phongtamrug3

  • 1Department of Chemistry, Faculty of Science and Center of Excellence for Innovation in Analytical Science and Technology, Chiang Mai University Chiang Mai 50200 Thailand piyarat.n@cmu.ac.th.

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Area of Science:

  • Biochemistry
  • Crystallography
  • Physical Chemistry

Background:

  • Histamine's structure and pH-dependent cation forms are not fully understood due to limited crystal structure data.
  • Conformational changes are sensitive to pH, impacting histamine's properties.

Purpose of the Study:

  • To analyze histamine's molecular packing structures at various pH levels.
  • To investigate the relationship between molecular conformation, hydrogen bonding, and proton conductivity.
  • To experimentally confirm predicted proton conductivity in histamine.

Main Methods:

  • X-ray diffraction analysis of histidine (histamine precursor) at different pH.
  • Vibrational spectroscopy and computational energy calculations.
  • Experimental measurement of proton conductivity during heating.

Main Results:

  • Identified diverse molecular conformations and tautomeric phenomena linked to hydrogen bonds.
  • Confirmed histamine's potential for proton conductivity, as predicted by simulations.
  • Observed a maximum conductivity of 10⁻⁴ S cm⁻¹ around 60 °C due to effective proton transfer.

Conclusions:

  • Hydrogen bonding plays a crucial role in histamine's structure and proton transfer capabilities.
  • Experimental evidence supports histamine's proton conductivity, particularly at elevated temperatures.
  • This research provides new insights into histamine's physical chemistry and potential applications.