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Nuclear Magnetic Resonance

NMR

Nuclear magnetic resonance spectroscopy (NMR) is one of the most important spectroscopic techniques for elucidating structures.Its application is relatively recent.In 1945 two groups of physicists working independently (Purcell, Torrey and Pound at Harvard University and Bloch, Hansen and Packard at Stanford University) first observed the NMR phenomenon in solids and liquids.This phenomenon was used to solve a chemical problem in the early 1950s.Since then, its importance has been growing, until in 1991 the Nobel Prize in Chemistry was awarded to R.R. Ernst for his contribution to the development of NMR experimental techniques.

Job request

It is recommended to put between 10 and 15 mg of sample in 0.66 mL of deuterated solvent to put the sample inside the NMR tubes.

In order to request the analysis of a sample by NMR, you must contact the staff responsible for the equipment.

You will need to give the toxicity and any storage precautions. Once the report has been delivered, if you do not collect the sample within one week, any remaining sample will be destroyed.

Characteristics of the devices

RMN 400MHz (9.4T)

Model:
Bruker Ultrashield ASCEND Nanobay
Year :
2014
Description:
  • BBFO probe (which allows you to observe 19F)
  • With ability to work at low temperature with N2L up to -90ºC

SampleXpress Lite:

16-position robot that allows the automatic entry of samples and the execution of the different NMR experiments

RMN 400MHz (9.4T)

Model :
Bruker Ultrashield AVANCE III400
Year :
2008
Description:
  • BBI probe (Broad Band Inverse)
  • Low temperature unit that allows you to work directly at -40ºC

How does it work?

The physical basis of NMR spectroscopy lies in the magnetic properties of the atomic nucleus.The interaction of the magnetic moment of a nucleus with an external magnetic field causes a splitting of the energy levels.Transitions between these different states can be generated and the energy absorption can be detected and recorded as a spectral line, called a resonance signal.In this way, spectra can be obtained for compounds containing atoms whose nuclei have non-zero magnetic moments.Among these are the 1H, 19F, 14N and 15N and others of interest in chemistry.The 12C nucleus, of great importance in organic chemistry, has an even atomic mass and atomic number, and therefore no magnetic moment.Thus, C NMR studies are limited to the 13C isotope, which has a natural abundance of only 1.1%.

From an NMR spectrum we can extract three basic pieces of information that we need to be able to determine the structure in solution of our molecule:

  1. The position of the signal (chemical shift, δ).Different resonance signals appear for the different protons in the molecule because these protons have different chemical environments.
  2. Not all lines are simple (singlets) but some are split into doublets, triples, quadruplets or other multiplicities.This splitting is due to spin-spin coupling.And it gives us an idea about the coupling system.
  3. The area under a signal is related to the number of 1Hs that give rise to the signal and can be measured by integration.It should also be taken into account that spectra can be made of other nuclei, such as 13C, 31P, 15N, etc.,and apply two-dimensional correlation techniques, special techniques that allow spectra to be recorded in two independent frequency dimensions.In many experiments one frequency axis contains chemical shifts and the other, coupling constants.
    COZY NMR spectrum

They can also contain frequencies of a single nucleus (homonuclear) or of different nuclei (heteronuclear).This type of experiment is important for the analysis of complex spectra with a large overlap of signals and allows the study of systems as complex as natural products, biopolymers, proteins or nucleic acids.

Applications / Practical cases

1.Determination of structures

Correlations between chemical shift or spin-spin coupling and the structure of compounds form the basis of the application of NMR to the determination of structures of unknown compounds.Thus, the chemical shift makes it possible to know the chemical environment in which a nucleus is located and the integration allows conclusions to be drawn regarding the number of nuclei present.Spin-spin coupling allows us to define the relative positions of the nuclei, since the magnitude of the spin-spin interaction (coupling constant, J) depends on the number and type of bonds separating the different nuclei.

2.Study of dynamic processes.Study of fast reversible reactions

Another application of NMR spectroscopy derives from the observation that the NMR spectrum of many compounds depends on temperature.That is, the shape of the NMR signal depends on dynamic processes and the rate at which these processes take place.Therefore, the spectroscopy of NMR can be used for the study of fast reversible reactions that cannot be followed with the classical kinetic methods.

3.Study of reaction mechanisms

In addition, NMR spectroscopy is also useful for the study of reaction mechanisms in all branches of chemistry.These experiments use isotopes of hydrogen, carbon or nitrogen (2H, 13C, 15N) to track a particular atom during the reaction of interest.

4.Interest in other scientific areas

In organic chemistry and biochemistry, 13C NMR spectroscopy plays a fundamental role, although 19F, 15N i 31P also provide valuable information.In inorganic chemistry, a large number of nuclei of interest can be used thanks to the rapid development of experimental techniques.Since almost every element in the periodic table contains a stable isotope with a magnetic moment, the area of application of NMR spectroscopy is very wide, even though the natural abundance of many of these isotopes is small.

More information

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