PROTON NUCLEAR MAGNETIC

RESONANCE SPECTROSCOPY (1H

NMR)
 SIGNIFICANCE
 The application of NMR spectroscopy to the study of proteins and nucleic acids has provided
unique information on the dynamics and chemical kinetics of these systems
 NMR spectroscopy helps to identify the carbon- hydrogen framework of an organic compound
 The power of this technique compared to the others is that it not makes it possible to identify the
functionality at a specific carbon, but also lets us determine what the neighboring carbon look like
 In many cases NMR spectroscopy can be used to study or determine the entire structure of a
molecule
 NMR spectroscopy is non-invasive as the small quantities of the sample are recovered unchanged
after the experiment.
 Nuclear Magnetic Resonance Spectroscopy (NMR)
 Involve nucleus (proton + neutron) NOT electron
 Proton + neutrons = Nucleons
 Nucleons like electrons have spin and magnetic moment (acts like tiny magnet)
 Make use of radio waves of the electromagnetic spectrum
 Nuclei with even number of nucleon (12C and
16O)
 Even number of proton and neutron – NO net spin
 Nucleon spin cancel out each other –Nucleus have NO overall magnetic moment –
NOT absorb radio wave.
 Nuclei with odd number of nucleon (1H, 13C,
19F, 31P)
 Nucleon have net spin – Nucleus have NET magnetic moment – Absorb radio wave
 Knowledge
 Nuclei have a “spin” associated with them (i.e., they act as if they were spinning
about an axis) due to the spin associated with their protons and neutrons.
 Nuclei are positively charged; their spin induces a magnetic field
 Nuclei with net spin – magnetic moment will interact
with radio waves
 NMR spectroscopy does not work for nuclei with even number of protons and
neutrons - nuclei have no net spin.
 HOW IT WORKS
(BASIC PRINCIPLES OF 1H NMR)
 In the absence of the magnetic field the nuclear spins are randomly oriented
 However when the sample is placed in a magnetic field nuclei with spin +1/2 align
with the applied magnetic field( alpha spin state or in the lower energy state)
 And the nuclei with the -1/2 spin align against the applied field ( beta- spin state or
in the higher energy state)
 ∆E
The energy difference between the high
energy and low energy states depends
upon the strength of the magnetic
field(Bo).
Greater the strength of the magnetic field
greater is the difference in the energy.
 How does it work?
 The energy needed for the nuclei to reverse their spin and change their orientation in a
magnetic field can be provided by radio waves.
 When a sample is subjected to a brief intense pulse of radio waves of the electromagnetic
spectrum, the nuclei with the lower spin state can be promoted to the higher energy spin
state which is called flipping the spin.
 When this nuclei returns to their original state, they emit signals whose frequency
depends on the difference in energy (∆ E) between the two states.
 The spectrum detects these signals and displays them as a plot of signal frequency versus
intensity and NMR spectrum,
 Resonance
 The term nuclear magnetic resonance comes
form the fact that the nuclei are in resonance
with the radio frequency radiation. As they are
flipping back and forth between high energy
spin state and low energy spin state.
 In practice, a sample is placed in an
electromagnet. The field strength is varied
until the radio waves have the exact frequency
needed to make the nuclei flip over and spin in
the opposite direction. This is called resonance
and can be detected electronically and
recorded in the form of a spectrum
 Hydrogen nuclei in different chemical
environments have different chemical shifts
 As electrons shield the nucleus from the full effects of the external magnetic field,
differences in electron distribution produce different energy separations between
the two spin energy levels.
 The technique is a very useful analytical tool, as nuclei in different chemical
environments produce different signals in the spectrum.
 Proton or 1 H NMR is particularly useful. The hydrogen nuclei, present in all
organic molecules, effectively act as spies and give information about their position
in a molecule.
 TMS
 The signals are measured against the standard signal produced by the 12 hydrogen
nuclei in tetramethylsilane (TMS)
 CHEMICAL SHIFT
 The position of the NMR signal
relative to this standard is called the
chemical shift of the proton.
 Hydrogen nuclei in particular
environments have characteristic
chemical shifts.
 Some examples are given in the
table
Interpreting 1H NMR spectra