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Mass Spectrometry: Isotope Effect01:13

Mass Spectrometry: Isotope Effect

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Most elements exist in nature as a mixture of isotopes. The isotopes differ in weight due to their respective number of neutrons. The molecular weight of a molecule is different depending on the specific isotope of its elements involved. As a result, the mass spectrum of the molecule exhibits peaks from the same fragment at multiple positions. The positions of these mass signals depend on the mass differences between isotopes. Furthermore, the intensity of these signals is dependent on the...
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Nuclear Overhauser Enhancement (NOE)01:07

Nuclear Overhauser Enhancement (NOE)

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Irradiation of a spin-active nucleus causes an increase or decrease in the signal intensity of neighboring nuclei that are not necessarily chemically bonded or involved in J-coupling.  This phenomenon, called the Nuclear Overhauser Enhancement (NOE), results from through-space interactions between the nuclear spins. The NOE effect decreases with increasing internuclear distance and is generally not observed beyond 4 angstroms. In NOE, dipole-dipole interactions between neighboring...
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Isotopes01:12

Isotopes

62.9K
Elements have a set number of protons that determines their atomic number (Z). For example, all atoms with eight protons are oxygen; however, the number of neutrons can vary for atoms of the same element. The sum of the number of protons and the number of neutrons is the mass number (A). Atoms with the same atomic number but different mass numbers are called isotopes. Elements can have multiple isotopes, for example, carbon-12, carbon-13, and carbon-14.
An element's atomic mass, or weight,...
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Isotopes and Radioisotopes01:28

Isotopes and Radioisotopes

10.7K
In the early 1900s, English chemist Frederick Soddy realized that an element could have atoms with different masses that were chemically indistinguishable. These different types are called isotopes — atoms of the same element that differ in mass. Isotopes differ in mass because they have different numbers of neutrons but are chemically identical because they have the same number of protons. Soddy was awarded the Nobel Prize in Chemistry in 1921 for this discovery.
An isotope containing...
10.7K
Atomic Spectroscopy: Effects of Temperature01:27

Atomic Spectroscopy: Effects of Temperature

771
Atomization, converting samples into gas-phase atoms and ions, is essential for atomic spectroscopy. The flame temperature required for atomization affects the efficiency of the atomic spectroscopic methods by increasing the atomization efficiency and the relative population of the excited and ground states.
At thermal equilibrium, the relative populations of excited and ground state atoms can be estimated using the Maxwell–Boltzmann distribution. For example, an increase in temperature...
771
¹³C NMR: ¹H–¹³C Decoupling01:04

¹³C NMR: ¹H–¹³C Decoupling

1.5K
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...
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Related Experiment Video

Updated: Dec 15, 2025

Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method
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Isotopic Effect in Double Proton Transfer Process of Porphycene Investigated by Enhanced QM/MM Method

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Isotope Effects Induced by Molecular Compression.

Natalia N Breslavskaya1,2, Anatoly L Buchachenko2,3,4,5

  • 1Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow 117907, Russia.

The Journal of Physical Chemistry. A
|July 15, 2020
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Summary

Compression of molecules like water inside C60 cages significantly alters their zero-point energies (ZPEs), enhancing isotope effects. This compression effect could help explain large isotope effects in enzymatic reactions.

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Area of Science:

  • Computational Chemistry
  • Physical Chemistry
  • Molecular Physics

Background:

  • Zero-point energies (ZPEs) are fundamental quantum mechanical properties of molecules.
  • Isotope effects, particularly large ones in enzymatic reactions, are not fully understood.
  • Molecular compression can alter molecular properties, but its effect on ZPEs and isotope effects is less explored.

Purpose of the Study:

  • To compute the zero-point energies (ZPEs) of hydroxyl ion, hydrogen, and water molecules.
  • To investigate the impact of compression within C60 cages on molecular ZPEs and isotope effects.
  • To explore the potential of compression-induced isotope effects as a probe for enzymatic reactions.

Main Methods:

  • Quantum mechanical calculations were employed to determine ZPEs.
  • Molecules (hydroxyl ion, hydrogen, water) were studied both in free states and compressed within C60 cages.
  • Isotopic variations (including deuterium and tritium) were considered.

Main Results:

  • Compression within C60 cages results in excess molecular energy of 2-3 kcal/mol, dependent on isotopes.
  • Differences in ZPE for compressed isotopic molecules are significantly larger than for free molecules.
  • This leads to substantial deuterium and tritium isotope effects induced by compression.

Conclusions:

  • Compression of molecules, such as water in C60 cages, dramatically enhances isotope effects.
  • These compression-induced isotope effects can serve as a valuable probe for molecular compression in enzymatic sites.
  • The findings may offer insights into the large isotope effects observed in enzymatic reactions, potentially linked to tunneling.