Nuclear magnetic resonance (NMR)

Study of absorption of EMR in radio frequency region of spectrum f= 107 108 in the presence of
magnetic field is known as NMR spectroscopy.
If protons are studied it called as proton NMR.
If C-13 is studied technique is called C-13 NMR.
Spinning nucleus:
The nucleus spin on its axis generate a magnetic field such a nucleus behave as a tiny magnet, thus a
spinning nucleus behaves as a substance possessing nuclear magnetic movement. It also posses nuclear
angular momentum.

I =original spin.
I being the spin quantum number. The value of I depend upon particular nucleus or isotopes. It may be
0, , 1, 3/2, 5/2 etc.
Nucleus have I=0 NMR inactive while nucleus having I0 NMR active.
Effect of external applied field:
Spinning nucleus angular momentum are influenced by external magnetic field thus a spinning
nucleus When generate a magnetic field attempts to aline its magnetic movement along the external field
either parallel or antiparallel.
These are degenerate states i.e. at same energy level.
In the absence of external magnetic field thay are oriented in random direction however in the presence of
magnetic field it moves parallel or antiparallel.

Energy difference between two orientations (-) is directly proportional to the applied magnetic field.
So, by increasing the applied magnetic field is also increases which increase the sensitivity of the substance under
investigation.
How to get NMR signals:
To get NMR signals we need to get energy difference. The frequency corresponding to the E which is
absorbed by particular nucleus is called resonance frequency since r & 2 are constant. we keep the field
constant & change the frequency until the resonance frequency is obtained. The same process can be reverse
since E & H are equal.
CW-NMR (continuous wave-NMR):
In CW-NMR the frequency of EMR (electro magnetic radiation) is kept constant & strength of applied
field is gradually varied.
FT-NMR (Fourier transmittance NMR):
Strength of magnetic field is kept constant & the frequency of EMR (electro magnetic radiation) is
varied.
In CW- NMR the radio frequency region tp be studied is scanned from one end to the other while in FT-NMR
radio frequency is applied as a single powerful pulse which effectively covers the whole frequency region.
NMR photometers are widely available. Magnetic field corresponds to 90, 100, 300 MHz etc. the
instrumentation is named after its frequency.
Instrumentation:
Main component includes:
1. Sample tube
2. Permanent magnet/ magnet
3. Sweap coils
4. Radio frequency transmittance
5. Radio frequency receiver
6. Readout device

Sample tube:
It is usually 15cm long & 5mm in diameter. The tube should be chemically inert & durable transparent
to the frequency. Generally it is made up of boro-slicates.
Permanent magnet / magnet:
Magnet may be permanent or electro magnetic permanent magnet is cheapest & convenient to use
but it lacks flexibility. While in electromagnet the flux density can be varied by vary the current that passes
through the coil of magnet.
Sweap coils:
The applied magnetic field must be stable & homogeneous. If it is not homogeneous identical nuclei
will experience different magnetic field at different places & give different signals.
The applied magnetic field can be varied by field sweap coils.
Radio frequency transmittance:
It is often a highly stable crystal controlled oscillator the out put of which is multiplied to the desired
frequency. The coil of oscillator is wounded around the sample container perpendicular to the applied field so
that applied radio frequency should change the effective magnetic field.
Radio frequency receiver:
The receiver is also perpendicular to the applied field & is coiled around the sample tube.
Read out device:
Signal from receiver are weak & are amplified & calibrated with respect to carbon 13.
Working of NMR:
A radiation of controlled frequency from transmitter is applied to the sample perpendicular to the
magnetic field when it is absorbed by the sample it is detected by radio frequency receiver. The transmitter
coil & receiver coil are perpendicular to each other & also perpendicular to the magnetic field. If nuclei dont
resonate the detector will receive weak signals from the transmitter coil & enhance absorption will be
detected. If nuclei will resonate with applied frequency the signal from the receiver are use to make X- axis
while absorption is placed on Y-axis to make NMR spectrum.
Sample handling:
Two solvents
TMS (tetra methyl silane)
DSS(2,2,-dimethyl 2-it is easier to achieve complete homogenicity over a small area b/w the poles of magnet
therefore it is advantageous to use small sample about 100ml of approximately 5% solution of sample
in suitable solvent.
A few drops of reference substance(TMS,DSS) is added while liquid sample may be directly use.
TMS is taken as ideal reference compound b/c it needs following characters;
It is chemically inert
It is miscible with organic liquid therefore can be used as internal reference standard
It has low boiling point (27c)
Therefore can be easily removed and recover.
All protons in TMS are magnetically equivalent (12)
Silicon is electro +ive and tends to donate electron density to the methyl group. Therefore the shielding
effect of methyl group is increased.
TMS is not soluble in water in aqueous solution it is normally used as externally reference. Alternatively a
soluble sodium salt of dimethyl sila pentane sulfonic acid (DSS) is used as internal reference.

Application
Sturactural allucidation
Structure of unknown compounds is explained on the basis of following point
Number of main NMR signals should be equal to the number of proton.
Chemical shaft indicate what types of atoms are present.
Spin spin coupling reveals possible arrangement of grouip.
Determination of optical purty;

Diastriomers differ in there NMR character and is used for practical application of optical activity purity
determination

Keto enol toutomerism ;

NMR is best -------- for quantitative and qualitative assay of keto enol tautomerism

Drug macromolicular interaction ;

Micell formation by drug and drug macromolicule enzyme proiteinscarbohydrate can be studied for example
tetracyclin.

Chemical shift;
The differnce b/w absorption positiopn of proton and absorption of refferancer compound proton is known
as chemical shaft.
Such shaft in position of NMR absorptionarise due to shelding and desheilding of proton due to induce
magnetic field.
A proton in the molicule is surrounded by a cloud of electronic changes the applied magnetic field (Ho)
induces the circulation of electrons arround the protons in a plain perpendicular to the 2Ho2 according to the
left hand rule and right hand rule.